(19)
(11)EP 3 273 513 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 17181904.8

(22)Date of filing:  18.07.2017
(51)International Patent Classification (IPC): 
H01M 4/38(2006.01)
H01M 10/052(2010.01)
C08G 73/10(2006.01)
H01M 4/62(2006.01)
C08G 69/36(2006.01)
H01M 4/02(2006.01)

(54)

BINDER, METHOD OF PREPARING THE BINDER, AND ANODE AND LITHIUM BATTERY INCLUDING THE BINDER

BINDER, METHODE ZUR HERSTELLUNG DES BINDERS, ANODE UND LITHIUM BATTERIE DIE DEN BINDER ENTHÄLT

LIANT, MÉTHODE POUR LA PRODUCTION DU LIANT, ANODE ET BATTERIE AU LITHIUM COMPRENANT LE LIANT


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 22.07.2016 KR 20160093461
05.07.2017 EP 17179854

(43)Date of publication of application:
24.01.2018 Bulletin 2018/04

(73)Proprietors:
  • Samsung Electronics Co., Ltd.
    Gyeonggi-do 16677 (KR)
  • Samsung SDI Co., Ltd.
    Gyeonggi-do (KR)

(72)Inventors:
  • BAE, Woojin
    16678, Gyeonggi-do, (KR)
  • KWON, Seunguk
    16678, Gyeonggi-do, (KR)
  • MAH, Sangkook
    16678, Gyeonggi-do, (KR)
  • YANG, Jeeeun
    16678, Gyeonggi-do, (KR)
  • YOON, Dukhyoung
    Gyeonggi-do, (KR)
  • HAN, Sungsoo
    16678, Gyeonggi-do, (KR)

(74)Representative: Elkington and Fife LLP 
Prospect House 8 Pembroke Road
Sevenoaks, Kent TN13 1XR
Sevenoaks, Kent TN13 1XR (GB)


(56)References cited: : 
WO-A1-2015/186814
US-A1- 2007 048 609
  
  • PADAVAN D T ET AL: "Synthesis, characterization and in vitro cell compatibility study of a poly(amic acid) graft/cross-linked poly(vinyl alcohol) hydrogel", ACTA BIOMATERIALIA, ELSEVIER, AMSTERDAM, NL, vol. 7, no. 1, 1 January 2011 (2011-01-01) , pages 258-267, XP027448767, ISSN: 1742-7061, DOI: 10.1016/J.ACTBIO.2010.07.038 [retrieved on 2010-08-03]
  • LIU YONG ET AL: "The effects of polyamic acid on curing behavior, thermal stability, and mechanical properties of epoxy/DDS system", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 127, no. 4, 15 February 2013 (2013-02-15), pages 3213-3220, XP055402366, US ISSN: 0021-8995, DOI: 10.1002/app.37759
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

FIELD OF THE INVENTIVON



[0001] The present disclosure relates to a binder, a method of preparing the binder, and an electrode and a lithium battery including the binder.

BACKGROUND OF THE INVENTION



[0002] In a lithium battery with an electrode including a carbonaceous active material, a water-soluble binder such as styrene-butadiene rubber/carboxymethylcellulose (SBR-CMC) binder provides the mechanical properties and binding strength that is suitable for a battery.

[0003] In a lithium battery with an electrode including a metallic active material such as silicon having a large volume change during charging/discharging, a water-soluble binder may not provide suitable mechanical properties or binding strength for a battery.

[0004] A polyimide (PI) binder has desirable mechanical properties, chemical resistance, and heat resistance, but is not soluble in water and has a low initial charging/discharging efficiency.

[0005] A polyvinyl alcohol (PVA) binder is water-soluble and has desirable initial charging/discharging efficiency and lifespan characteristics but has poor workability in relation to slurry stability and electrode plate uniformity. Also, when the PVA binder is used, cracks may develop in an active material layer and the active material layer may be separated from a current collector, and thus stability of the electrode decreases.

[0006] Therefore, there is a need for a binder that reduces and/or suppresses volume change of an electrode in a lithium battery including a metallic active material while also having a desirable initial efficiency, improved lifespan characteristics, and improved electrode stability.

[0007] In D.T. Padavan et al., "Synthesis, characterization and in vitro cell compatibility study of a poly(amic acid) graft/cross-linked poly(vinyl alcohol) hydrogel", Acta Biomaterialia, 7(1):258-267, poly(amic acid) (PAA), derived from ethylene diamine tetraacetic dianhydride was grafted/cross-linked onto physically cross-linked PVA to provide cell compatibility. Functionalization was achieved via a one-step esterification reaction using 1,3-dicyclohexylcarbodiimide as the coupling agent and 4-dimethylaminopyridine as the catalyst.

[0008] In L. Yong et al., "The effects of polyamic acid on curing behavior, thermal stability, and mechanical properties of epoxy/DDS system", Journal of Applied Polymer Science, volume127, issue 4, 15 February 2013, pages 3213-3220, a thermoplastic modification method was studied for the purpose of improving the toughness and heat resistance and decreasing the curing temperature of the cured epoxy/4, 4'-diaminodiphenyl sulfone resin system.

[0009] WO 2015/186814 discloses an electrode manufacturing method, wherein an electrode mixture layer is formed, on the surface of a current collector, by an electrode mixture composition that contains a specific cross-linking agent, and a polyimide precursor aqueous composition obtained by dissolving a specific polyamide acid with a specific imidazole in an aqueous solvent, after which the solvent is removed and the polyamide acid subjected to an imidization reaction by heating.

SUMMARY OF THE INVENTION



[0010] Provided is a binder that has improved initial capacity, lifespan characteristics, and electrode stability and is capable of suppressing the volume change of an electrode.

[0011] Provided is an electrode including the binder.

[0012] Provided is a lithium battery including the electrode.

[0013] Provided is a method of preparing the binder.

[0014] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.

[0015] According to an aspect of an embodiment, a binder is provided in accordance with claim 1.

[0016] According to an aspect of another embodiment, an electrode includes: the binder; and a cathode active material or an anode active material.

[0017] According to an aspect of still another embodiment, a lithium battery includes: a first electrode including the electrode; a second electrode; and an electrolyte disposed between the first electrode and the second electrode.

[0018] According to an aspect of still another embodiment, a method of preparing a binder is provided in accordance with claim 14.

BRIEF DESCRIPTION OF THE DRAWINGS



[0019] These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:

FIG. 1 shows methods and equations that can be used to measure the modulus of the third polymer.

FIG. 2 is a graph of intensity (arbitrary units, a.u.) versus wavenumber (inverse centimeters, cm-1) and shows IR spectra of polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2;

FIG. 3 is a graph of intensity (a.u.) versus diffraction angle (degrees 2-theta, 2θ) and shows X-ray diffraction (XRD) spectra of polymers prepared in Examples 1 to 4 and Comparative Examples 1 and 2;

FIG. 4 is a graph of weight percent (%) versus temperature (°C) and shows the DSC measurement results of polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2;

FIG. 5 shows an image of an anode that is dissociated after charging coin cell lithium batteries, prepared in Examples 7 and 9 and Comparative Examples 5 to 7, twice; and

FIG. 6 shows a schematic view of a lithium battery according to an embodiment.


DETAILED DESCRIPTION OF THE EMBODIMENTS



[0020] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

[0021] It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

[0022] It will be understood that, although the terms "first," "second," "third," etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, "a first element," "component," "region," "layer," or "section" discussed below could be termed a second element, component, region, layer, or section without departing from the teachings herein.

[0023] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms, including "at least one," unless the content clearly indicates otherwise. "At least one" is not to be construed as limiting "a" or "an." It will be further understood that the terms "comprises" and/or "comprising," or "includes" and/or "including" when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

[0024] Furthermore, relative terms, such as "lower" or "bottom" and "upper" or "top," may be used herein to describe one element's relationship to another element as illustrated in the Figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures. For example, if the device in one of the figures is turned over, elements described as being on the "lower" side of other elements would then be oriented on "upper" sides of the other elements. The exemplary term "lower," can therefore, encompasses both an orientation of "lower" and "upper," depending on the particular orientation of the figure. Similarly, if the device in one of the figures is turned over, elements described as "below" or "beneath" other elements would then be oriented "above" the other elements. The exemplary terms "below" or "beneath" can, therefore, encompass both an orientation of above and below.

[0025] "About" or "approximately" as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ± 30%, 20%, 10%, or 5% of the stated value.

[0026] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0027] Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.

[0028] Hereinafter, according to one or more exemplary embodiments, a binder, an electrode and a lithium battery including the binder, and a method of preparing the binder will be described in detail.

[0029] As used herein, the term "cross-link" and/or "cross-linked" denotes a bond that links one polymer chain to another polymer chain. As used herein, a cross-linking group is a covalent bond. As used herein, the term "linker or cross-linker" denotes a functional group that links one polymer chain with another polymer chain. As used herein, the term "cross-linked polymer" denotes a polymer having one polymer chain and another polymer chain that are connected by one or more linking groups. Also, the cross-linked polymer is a product of cross-linking one or more polymers.

[0030] According to an embodiment, a binder includes a third polymer, which is a cross-linking, i.e. a cross-linked, product of a first polymer and a second polymer, wherein the first polymer is at least one selected from a polyamic acid and a polyimide cured from the polyamic acid, wherein the polyamic acid is represented by Formula 1 or Formula 2:



wherein, in Formulae 1 and 2,

M is an alkali metal;

Ar1 and Ar3 are each independently an aromatic group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring comprising at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-,-C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

Ar2 and Ar4 are each independently an aromatic group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring having at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

X1 is -C(=O)OH, -OH, -C(=O)-NH2, or -C(=O)H; and

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1; wherein the second polymer is a polyvinyl alcohol, and wherein the first polymer and the second polymer are cross-linked by an ester bond.



[0031] The third polymer is a cross-linked polymer of the first polymer and the second polymer. Since the binder includes a third polymer, which is a cross-linked polymer produced by cross-linking the first polymer and the second polymer via an ester bond, excellent electrode stability and suppression of volume expansion derived from a polyimide as well as improved initial charging/discharging efficiency and lifespan characteristics derived from a water-soluble polymer may be simultaneously provided to a lithium battery having an electrode including the binder.

[0032] In the binder, the first polymer may further include an alkali metal (i.e., an alkali metal ion). The alkali metal may be sodium or lithium. The first polymer may be substituted or doped with an alkali metal. For example, in a polyamic acid, the hydrogen of the carboxyl group connected to the tetravalent aromatic group in the polyamic acid may be substituted with an alkali metal (i.e., an alkali metal cation). For example, a polyimide may be doped with an alkali metal ion and thus may be coordinated to an amide group. When the first polymer includes an alkali metal (prelithiation), initial charging/discharging efficiency may improve.

[0033] An amount of the alkali metal included in the first polymer may be in a range of 0.2 equivalents to 1.0 equivalents at an equivalent ratio with respect to a carboxyl group or an amide group. For example, an amount of the alkali metal included in the first polymer may be in a range of 0.2 equivalents to about 0.8 equivalents at an equivalent ratio with respect to a carboxyl group or an amide group. For example, an amount of the alkali metal included in the first polymer may be in a range of about 0.3 equivalents to about 0.7 equivalents at an equivalent ratio with respect to a carboxyl group or an amide group. For example, an amount of the alkali metal included in the first polymer may be in a range of about 0.4 equivalents to about 0.6 equivalents at an equivalent ratio with respect to a carboxyl group or an amide group. For example, an amount of the alkali metal included in the first polymer may be in a range of about 0.45 equivalents to about 0.55 equivalents at an equivalent ratio with respect to a carboxyl group or an amide group. When an amount of the alkali metal is within these ranges, the physical properties of a binder may further improve.

[0034] When an amount of lithium of in polyamic acid, that is, a substitution degree of lithium ions, is lower than 0.2 equivalents at an equivalent ratio with respect to a carboxyl group, a ratio of prelithiation is low, and thus an effect on suppressing an irreversible lithiation reaction at the first cycle may be minimal. Also, when an amount of lithium in the polyamic acid, or a substitution degree of lithium ions, is greater than 1.0 equivalents at an equivalent ratio with respect to a carboxyl group, an imidification ratio may significantly decrease, which may decrease lifespan characteristics. To obtain the amount of lithium in the polyamic acid, or a substitution degree of lithium ions, within these ranges, an amount of LiOH that is used to lithiate the polyamic acid may be in a range of 0.2 equivalents to 1.0 equivalents at an equivalent ratio with respect to a carboxyl group of the polyamic acid.

[0035] The polyamic acid is represented by Formula 1 or Formula 2:





[0036] In Formulae 1 and 2, M is an alkali metal; Ar1 and Ar3 are each independently an aromatic group that is selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring including at least two aromatic rings fused to each other, or a ring including at least two aromatic rings that are linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, - Si(Ra)(Rb)- (where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-; Ar2 and Ar4 are each independently an aromatic group that is selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heteroarylene group, wherein the aromatic ring is one aromatic ring, a ring including at least two aromatic rings fused to each other, or a ring including at least two aromatic rings that are linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)- (where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-; X1 is -C(=O)OH,-OH, -C(=)-NH2, or -C(=O)H; and n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.

[0037] For example, the polyamic acid may be represented by Formula 3 or Formula 4:





[0038] In Formulae 3 and 4, M is lithium or sodium; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a hydrogen, a halogen,-C(=O)OH, -OH, -C(=O)-NH2, -C(=O)H, a C1-C10 alkyl group substituted or unsubstituted with a halogen, a C6-C20 aryl group substituted or unsubstituted with a halogen, or a C2-C20 heteroaryl group substituted or unsubstituted with a halogen; Y1 is a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)- (where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein R is a C1-C10 alkyl group; at least one selected from R3, R4, R5, and R6 is-C(=OO)OH, -OH, -C(=O)-NH2, or -C(=O)H; and n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.

[0039] For example, the polyimide may be represented by Formula 5 or Formula 6:





[0040] In Formulae 5 and 6, M is an alkali metal; Ar1 and Ar3 are each independently an aromatic group that is selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring including at least two aromatic rings fused to each other, or a ring including at least two aromatic rings that are linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, - Si(Ra)(Rb)- (where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-O; Ar2 and Ar4 are each independently an aromatic group that is selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring including at least two aromatic rings fused to each other, or a ring including at least two aromatic rings that are linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)- (where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-; X1 is -C(=O)OH,-OH, -CO-NH2, or -C(=O)H; and n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.

[0041] For example, the polyimide may be represented by Formula 7 or Formula 8:





[0042] In Formulae 7 and 8, M is lithium or sodium; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a hydrogen, a halogen,-C(=O)OH, -OH, -C(=O)-NH2, -C(=O)H, a C1-C10 alkyl group substituted or unsubstituted with a halogen, a C6-C20 aryl group substituted or unsubstituted with a halogen, or a C2-C20 heteroaryl group substituted or unsubstituted with a halogen; Y1 is a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)- (where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-; at least one selected from R3, R4, R5, and R6 is -C(=O)OH, -OH, -C=(O)-NH2, or -C(=O)H; and n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.

[0043] For example, in the binder, the polyamic acid may be represented by Formula 9 or Formula 10, and the polyimide may be represented by Formula 11 or Formula 12:









[0044] In Formulae 9 to 11, n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.

[0045] For example, in the first polymer represented by one of Formulae 1 to 12, the molar ratios, n and m, of a repeating unit including a cross-linking group and a repeating unit not including a cross-linking group may satisfy 0<n<0.5, 0.5<m<1, and n+m=1. For example, in the first polymer represented by one of Formulae 1 to 12, the molar ratios, m and n, of a repeating unit including a cross-linking group and a repeating unit not including a cross-linking group may satisfy 0.1<n<0.4, 0.6<m<0.9, and n+m=1. For example, in the first polymer represented by one of Formulae 1 to 12, the molar ratios, m and n, of a repeating unit including a cross-linking group and a repeating unit not including a cross-linking group may satisfy 0.15<n<0.35, 0.65<m<0.85, and n+m=1. For example, in the first polymer represented by one of Formulae 1 to 12, the molar ratios, m and n, of a repeating unit including a cross-linking group and a repeating unit not including a cross-linking group may satisfy 0.2<n<0.3, 0.7<m<0.8, and n+m=1. When the molar ratios are within these ranges, a binder may provide improved physical properties.

[0046] For example, the first polymer represented by one of Formulae 1 to 12 may be a random copolymer, for example a random block copolymer. For example, the first polymer represented by one of Formulae 1 to 12 may be a block copolymer.

[0047] A weight average molecular weight of the first polymer may be in a range of about 10,000 to about 1,200,000 Daltons (Da). For example, a weight average molecular weight of the first polymer may be in a range of about 10,000 to about 1,100,000 Da. For example, a weight average molecular weight of the first polymer may be in a range of about 10,000 to about 1,000,000 Da. For example, a weight average molecular weight of the first polymer may be in a range of about 10,000 to about 500,000 Da. For example, a weight average molecular weight of the first polymer may be in a range of about 100,000 to about 500,000 Da. For example, a weight average molecular weight of the first polymer may be in a range of about 100,000 to about 400,000 Da. For example, a weight average molecular weight of the first polymer may be in a range of about 100,000 to about 300,000 Da. When the weight average molecular weight of the first polymer is within these ranges, physical properties of the binder may improve.

[0048] In the binder, the second polymer is a polyvinyl alcohol (PVA). For example, polyvinyl alcohol may be a hydrolysate obtained by hydrolyzing polyvinyl acetate with a base such as potassium hydroxide.

[0049] A saponification degree of the polyvinyl alcohol may be in a range of 60% to 99%. For example, a saponification degree of the polyvinyl alcohol may be in a range of about 70% to about 95%. For example, a saponification degree of the polyvinyl alcohol may be in a range of about 75% to about 90%. For example, a saponification degree of the polyvinyl alcohol may be in a range of about 80% to about 90%. For example, a saponification degree of the polyvinyl alcohol may be in a range of about 85% to about 90%. When the saponification degree of the polyvinyl alcohol is within these ranges, the binder may provide improved physical properties.

[0050] A weight average molecular weight of the polyvinyl alcohol may be in a range of 10,000 to 500,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 10,000 to about 450,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 10,000 to about 400,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 10,000 to about 300,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 10,000 to about 200,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 50,000 to about 150,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 70,000 to about 100,000 Da. For example, a weight average molecular weight of the polyvinyl alcohol may be in a range of about 80,000 to about 100,000 Da. When the weight average molecular weight of the polyvinyl alcohol is within these ranges, the physical properties of the binder may improve.

[0051] In the binder, a weight ratio of the first polymer and the second polymer included in the third polymer may be in a range of 1:99 to 50:50. For example, in the binder, a weight ratio of the first polymer and the second polymer included in the third polymer may be in a range of about 5:95 to about 45:55. For example, in the binder, a weight ratio of the first polymer and the second polymer included in the third polymer may be in a range of about 5:95 to about 40:60. For example, in the binder, a weight ratio of the first polymer and the second polymer included in the third polymer may be in a range of about 5:95 to about 35:65. For example, in the binder, a weight ratio of the first polymer and the second polymer included in the third polymer may be in a range of about 10:90 to about 30:70. When the weight ratio of the first polymer to the second polymer is within these ranges, the physical properties of the binder may improve.

[0052] In the binder, the cross-linking reaction may be at a temperature of 160°C or greater. For example, the cross-linking reaction may be performed by heat-treating a composition including the first polymer and the second polymer at a temperature of 160°C or greater. For example, the cross-linking reaction may be performed by heat-treating a composition including the first polymer and the second polymer at a temperature of 165°C or greater. For example, the cross-linking reaction may be performed by heat-treating a composition including the first polymer and the second polymer at a temperature of about 170°C or greater. For example, the cross-linking reaction may be performed by heat-treating a composition including the first polymer and the second polymer at a temperature of about 175°C or greater. When the cross-linking reaction is performed within these temperature ranges, a cross-linked polymer may be produced. When the cross-linking reaction is performed at a temperature lower than 160°C, a cross-linked polymer may not be obtained. When the cross-linking reaction of the binder is performed at a temperature of about 160°C or greater, the cross-linking reaction may be a catalyst-free reaction. When a catalyst such as an acid is additionally included in the cross-linking reaction, a suitable temperature for the cross-linking reaction to occur may be lowered from about 160°C to about 120°C. Also, when a separate cross-linking agent is used, a suitable temperature for the cross-linking reaction to occur may be about 120°C or lower.

[0053] Also, when the cross-linking reaction of the binder is performed at a temperature of 160°C or greater, the polyamic acid may be cured to obtain a polyimide. For example, the polyamic acid may provide an imidification ratio of about 60% or greater at a cross-linking reaction temperature of 160°C or greater. For example, the polyamic acid may provide an imidification ratio of about 70% or greater at a cross-linking reaction temperature of about 160°C or greater. For example, the polyamic acid may provide an imidification ratio of about 80% or greater at a cross-linking reaction temperature of about 160°C or greater. For example, the polyamic acid may provide an imidification ratio of about 90% or greater at a cross-linking reaction temperature of about 160°C or greater. An imidification ratio of the polyamic acid may be calculated by using proton nuclear magnetic resonance (1H-NMR). In the binder, when the polyamic acid is cured into polyimide, the mechanical properties of the binder may be improved.

[0054] In one embodiment, an acid equivalent of the polyamic acid may be less than about 300 grams per equivalent (g/eq). For example, an acid equivalent of the polyamic acid may be in a range of about 50 g/eq to about 250 g/eq. When an acid equivalent of the polyamic acid is less than about 300 g/eq, an amount of carboxyl group (-C(=O)OH) and/or carboxylate group (-C(=O)O-) per unit weight may increase. In a case where an amount of carboxyl group and/or carboxylate per unit weight increases, for example, when a silicon-based anode active material is used as an anode material, an interaction between the binder and the silicon-based anode active material having a hydroxyl group on a surface thereof may increase, and thus a binding strength of the binder with the anode active material may improve. When an acid equivalent is about 300 g/ep or greater, an initial efficiency and lifespan characteristics of a lithium battery may deteriorate.

[0055] In the binder, a modulus of the third polymer may be greater than each of a modulus of the first polymer and a modulus of the second polymer. Since the third polymer is a cross-linked polymer formed by cross-linking the first polymer and the second polymer, the modulus of the third polymer may be increased, and thus stiffness of the third polymer may increase. For example, a modulus of the third polymer may be about 30 GPa or greater. For example, a modulus of the third polymer may be about 35 GPa or greater. For example, a modulus of the third polymer may be about 38 GPa or greater. A modulus of the third polymer may be an indentation modulus. A modulus of the third polymer can be measured with a microindenter by applying 1mN on the third polymer, measuring displacement, and using equations as shown in FIG. 1.

[0056] In the binder, an indentation hardness of the third polymer may be greater than each of an indentation hardness of the first polymer and an indentation hardness of the second polymer. For example, since the third polymer is a cross-linked polymer that is formed by cross-linking the first polymer and the second polymer, indentation hardness of the third polymer may be increased. For example, an indentation hardness of the third polymer may be about 1630 Newtons per square millimeter (N/mm2) or greater. For example, an indentation hardness of the third polymer may be about 1700 N/mm2 or greater. For example, an indentation hardness of the third polymer may be about 1800 N/mm2 or greater. For example, an indentation hardness of the third polymer may be about 1900 N/mm2 or greater. For example, an indentation hardness of the third polymer may be about 2000 N/mm2 or greater. For example, an indentation hardness of the third polymer may be about 2100 N/mm2 or greater. For example, an indentation hardness of the third polymer may be about 2200 N/mm2 or greater. A modulus of the third polymer can be measured with a microindenter by applying 1mN on the third polymer, measuring displacement, and using equations as shown in FIG. 1.

[0057] In the binder, the third polymer, which is a cross-linked polymer, may have a 3-dimensional network structure including a plurality of first polymer chains and a plurality of second polymer chains that are cross-linked by a linker or a cross-linker. When the third polymer has this network structure, the volume change during charging/discharging of an electrode including the binder may be reduced, for example suppressed.

[0058] In the binder, a weight average molecular weight of the third polymer may be in a range of 10,000 to about 1,500,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of 10,000 to about 1,200,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of 10,000 to about 1,100,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of 10,000 to 1,000,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of 10,000 to about 500,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of about 100,000 to about 500,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of about 100,000 to about 400,000 Da. For example, in the binder, a weight average molecular weight of the third polymer may be in a range of about 100,000 to about 300,000 Da. When the weight average molecular weight of the third polymer is within these ranges, the physical properties of the binder may improve.

[0059] For example, in the binder, the third polymer may be represented by at least one selected from Formulae 13 to 16:









[0060] In Formulae 13 to 16, n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1; and p is a polymerization degree which is in a range of 250 to 12,500.

[0061] The binder may further include a fourth polymer that is water-soluble and selected from hydroxyethyl cellulose ether, dextran, carboxymethylcellulose (CMC), alginate, cellulose nanofiber, xanthan gum, and guar gum. When the binder further includes the fourth polymer, the physical properties of the binder may be further controlled.

[0062] Although a use of the binder is not limited, the binder, for example, may be used in an electrochemical battery. A type of the electrochemical battery is not limited to a device that may store energy through an electrochemical reaction, and examples of the device may include a primary battery and a secondary battery. Examples of the electrochemical battery may include an alkali metal battery such as a lithium battery or a sodium battery, an alkaline-earth metal battery such as a magnesium battery, a metal air battery, a super capacitor, or a fuel battery.

[0063] According to another embodiment, an electrode includes the binder; and a cathode active material or an anode active material. For example, the electrode may be a cathode that includes a binder and a cathode active material. For example, the electrode may be an anode that includes a binder and an anode active material.

[0064] For example, the electrode may be an anode that includes a metallic anode active material.

[0065] For example, the metallic anode active material may be at least one selected from a lithium metal; a lithium-alloyable metal; a composite of a lithium-alloyable metal and carbon; a composite of a lithium-alloyable metal and nitrogen; a composite of a lithium-alloyable metal, nitrogen, and carbon; a composite of a lithium-alloyable metal and a metal that is inert to lithium; a composite of a lithium-alloyable metal and a metal oxide that is inert to lithium; a composite of a lithium-alloyable metal and a metal nitride that is inert to lithium; and a composite of a lithium-alloyable metal and a metal nitrate that is inert to lithium. For example, the metallic anode active material may include at least one selected from a silicon-based active material, a tin-based active material, a silicon-tin alloy-based active material, and a silicon-carbonaceous (silicon-carbon) active material.

[0066] Examples of the lithium-alloyable metal are Si, Sn, Al, Ge, Pb, Bi, Sb, a Si-X alloy (where X is an alkali metal, an alkali earth metal, a Group XIII element, a Group XIV element, a transition metal, a rare earth element, or a combination thereof, and X is not Si), and a Sn-X' alloy (where X' is an alkali metal, an alkali earth metal, a Group XIII element, a Group XIV element, a transition metal, a rare earth element, or a combination thereof, and X' is not Sn). In some embodiments, X and/or X' may be magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), rutherfordium (Rf), vanadium (V), niobium (Nb), tantalum (Ta), dubnium (Db), chromium (Cr), molybdenum (Mo), tungsten (W), seaborgium (Sg), technetium (Tc), rhenium (Re), bohrium (Bh), iron (Fe), lead (Pb), ruthenium (Ru), osmium (Os), hassium (Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), tin (Sn), indium (In), titanium (Ti), germanium (Ge), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulfur (S), selenium (Se), tellurium (Te), polonium (Po), or combinations thereof.

[0067] For example, the composite of a lithium-alloyable metal and carbon may be an alloy or a composite that is represented by Formula SixSnqMyCz (where q, x, y, and z denote atom percent values, (a) (q + x) > 2y + z; (b) x, y and z are each independently greater than 0; (c) q is 0 or greater; (d) M is at least one metal selected from manganese, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chrome, nickel, cobalt, zirconium, yttrium, or a combination thereof).

[0068] For example, the composite of a lithium-alloyable metal and a metal that is inert to lithium may be an alloy or a composite that is represented by Formula SixMyAlz (where x, y, and z denote atom percent values, (a) x + y + z = 100, (b) x ≥ 55, (c) y < 22, (d) z > 0, (e) M is at least one metal selected from manganese, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chrome, nickel, cobalt, zirconium, yttrium, or a combination thereof). The oxidation state of a metal that is inert to lithium includes any suitable oxidation state of the metal that is inert, i.e. non-reactive, towards lithium metal.

[0069] The anode may further include as an anode active material at least one selected from a transition metal oxide, a non-transition metal oxide, and a carbonaceous material.

[0070] Examples of the transition metal oxide include a lithium titanium oxide, a vanadium oxide, and a lithium vanadium oxide. Examples of the non-transition metal oxide include SnO2 and SiOx (where 0<x<2). Examples of the carbonaceous material are crystalline carbon, amorphous carbon, and combinations thereof. An example of the crystalline carbon is graphite, such as natural graphite or artificial graphite, in shapeless, plate, flake, spherical, or fibrous form. Examples of the amorphous carbon are soft carbon (carbon sintered at low temperatures), hard carbon, meso-phase pitch carbides, and sintered cokes.

[0071] In the electrode, a thickness expansion ratio of the electrode defined according to Equation 1 may be less than about 54%. For example, the electrode may be an anode.



[0072] For example, a thickness expansion ratio of the anode may be about 52% or less. For example, a thickness expansion ratio of the anode may be about 50% or less. For example, a thickness expansion ratio of the anode may be about 48% or less. For example, a thickness expansion ratio of the anode may be about 46% or less. For example, a thickness expansion ratio of the anode may be about 44% or less. For example, a thickness expansion ratio of the anode may be about 42% or less. When the binder includes the cross-linked polymer having an increased modulus, binding strength of the binder increases, which may suppress volume change of the anode including the binder during charging/discharging. The charging/discharging conditions may refer to Evaluation Example 7.

[0073] For example, the anode is prepared as follows. For example, an anode active material, a conducting agent, the cross-linked polymer binder, and a solvent are combined to prepare an anode active material composition. In some embodiments, the anode active material composition may be directly coated on a current collector such as copper foil to prepare an anode plate. In some embodiments, the anode active material composition may be cast on a separate support to form an anode active material film, which may then be separated from the support and laminated on a copper current collector to prepare an anode plate.

[0074] Alternatively, an anode may be prepared as follows. For example, an anode active material composition including an anode active material, a conducting agent, a solvent, the first polymer, and the second polymer may be prepared, and the anode active material composition may then be coated on a current collector and cross-linking polymerization performed thereon by heat-treating the current collector at a temperature of about 160°C or greater to prepare an anode including a binder that includes a cross-linked polymer (the third polymer). Alternatively, the anode active material composition may be cast on a separate support and cross-linking polymerization performed thereon by heat-treating the current collector at a temperature of about 160°C or greater to prepare an anode active material film including a binder that includes a cross-linked polymer, and the anode active material film separated from the support may be laminated on a copper current collector to prepare an anode plate. The anode is not limited to the examples described above, and may be one of a variety of types.

[0075] Examples of the conducting agent may include natural graphite, artificial graphite, carbon black, acetylene black, or Ketjen black; carbon fibers; or a metal powder or metal fibers of copper, nickel, aluminum, or silver. Also, a conducting material such as a polyphenylene derivative or a combination including a conducting material may be used, but examples of the conducting material are not limited thereto, and any material available as a conducting material in the art may be used. Also, a crystalline material may be added as a conducting material.

[0076] The binder may further include a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), a styrene-butadiene rubber polymer, or combinations thereof, in addition to the cross-linked polymer, but embodiments are not limited thereto, and any suitable material available as a binder, in the art, may be additionally used.

[0077] Examples of the solvent may include N-methylpyrrolidone, acetone, or water, but embodiments are not limited thereto, and any suitable material available as a solvent, including those in the art, may be used.

[0078] The amounts of the anode active material, the conducting agent, the binder, and the solvent may be in ranges that are suitable for use in lithium batteries. At least one of the conducting agent, the binder, and the solvent may be omitted according to a use and a structure of the lithium battery.

[0079] The cathode may be prepared in the same manner as the anode, except that a cathode active material is used instead of an anode active material. Also, the same conducting agent, binder, and solvent used in the preparation of the anode may be used in the preparation of a cathode active material composition.

[0080] For example, a cathode active material, a conducting agent, a binder, and a solvent may be combined, for instance mixed together, to prepare a cathode active material composition. The cathode active material composition may be directly coated on an aluminum current collector to prepare a cathode plate. In some embodiments, the cathode active material composition may be cast on a separate support to form a cathode active material film, which may then be separated from the support and laminated on an aluminum current collector to prepare a cathode plate.

[0081] Alternatively, a cathode may be prepared as follows. A cathode active material composition including a cathode active material, a conducting agent, a binder, a solvent, the first polymer and the second polymer may be prepared, and the cathode active material composition may then be coated on a current collector and cross-linking polymerization performed thereon by heat-treating the current collector at a temperature of about 160°C or greater to prepare an anode including a binder that includes a cross-linked polymer (the third polymer). Alternatively, the cathode active material composition may be cast on a separate support and cross-linking polymerization performed thereon by heat-treating the current collector at a temperature of about 160°C or greater to prepare a cathode active material film including a binder that includes a cross-linked polymer, and the cathode active material film separated from the support may be laminated on a copper current collector to prepare a cathode plate. The cathode is not limited to the examples described above, and may be one of a variety of suitable types.

[0082] The cathode active material may include at least one selected from a lithium cobalt oxide, a lithium nickel cobalt manganese oxide, a lithium nickel cobalt aluminum oxide, a lithium iron phosphate, and a lithium manganese oxide, but embodiments are not limited thereto, and any suitable material available as a cathode active material, including those in the art, may be used.

[0083] For example, the cathode active material may be a compound represented by one of the following formulae: LiaA1-bB'bD2 (where 0.90 ≤ a ≤ 1.8 and 0 ≤ b ≤ 0.5); LiaE1-bB'bO2-cDc (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, and 0 ≤ c ≤ 0.05); LiE2-bB'bO4-cDc (where 0 ≤ b ≤ 0.5 and 0 ≤ c ≤ 0.05); LiaNi1-b-cCobB'cDα (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α ≤ 2); LiaNi1-b-cCobB'cO2-αF'α (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2); LiaNi1-b-cCobB'cO2-αF'2 (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2); LiaNi1-b-cMnbB'cDα (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α ≤ 2); LiaNi1-b-cMnbB'cO2-αF'α (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2); LiaNi1-b-cMnbB'cO2-αF'2 (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, and 0 < α < 2); LiaNibEcGdO2 (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, and 0.001 ≤ d ≤ 0.1); LiaNibCocMndGeO2 (where 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.5, and 0.001 ≤ e ≤ 0.1); LiaNiGbO2 (where 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); LiaCoGbO2 (where 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); LiaMnGbO2 (where 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); LiaMn2GbO4 (where 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiI'O2; LiNiVO4; Li(3-f)J2(PO4)3 (where 0 ≤ f ≤ 2); Li(3-f)Fe2(PO4)3 (where 0 ≤ f ≤ 2); and LiFePO4.

[0084] In the formulae above, A may be selected from nickel (Ni), cobalt (Co), manganese (Mn), and combinations thereof; B' may be selected from aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), a rare earth element, and combinations thereof; D may be selected from oxygen (O), fluorine (F), sulfur (S), phosphorus (P), and combinations thereof; E may be selected from cobalt (Co), manganese (Mn), and combinations thereof; F' may be selected from fluorine (F), sulfur (S), phosphorus (P), and combinations thereof; G may be selected from aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr), vanadium (V), and combinations thereof; Q is selected from titanium (Ti), molybdenum (Mo), manganese (Mn), and combinations thereof; I' is selected from chromium (Cr), vanadium (V), iron (Fe), scandium (Sc), yttrium (Y), and combinations thereof; and J may be selected from vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), and combinations thereof

[0085] The compounds listed above as cathode active materials may have a surface coating layer (hereinafter, also referred to as "coating layer"). Alternatively, a combination of a compound without a coating layer and a compound having a coating layer, the compounds being selected from the compounds listed above, may be used. In some embodiments, the coating layer may include at least one compound of a coating element selected from an oxide, a hydroxide, an oxyhydroxide, an oxycarbonate, and a hydroxycarbonate of the coating element. In some embodiments, the compounds for the coating layer may be amorphous or crystalline. In some embodiments, the coating element for the coating layer may be magnesium (Mg), aluminum (Al), cobalt (Co), potassium (K), sodium (Na), calcium (Ca), silicon (Si), titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr), or a combination thereof. In some embodiments, the coating layer may be formed using any suitable method that does not adversely affect the physical properties of the cathode active material when a compound of the coating element is used. For example, the coating layer may be formed using a spray coating method or a dipping method. The suitable coating methods may be well understood, including by by one of ordinary skill in the art, and thus a detailed description thereof will be omitted.

[0086] In some embodiments, the cathode active material may be LiCoO2, LiMnxO2x (where x=1 or 2), LiNi1-xMnxO2x (where 0<x<1), LiNi1-x-yCoxMnyO2 (where 0≤x≤0.5 and 0≤y≤0.5), or LiFePO4.

[0087] According to another embodiment, a lithium battery includes the first electrode; a second electrode; and an electrolyte between the first electrode and the second electrode. For example, a first electrode may be a cathode, and a second electrode may be an anode; or a first electrode may be an anode, and a second electrode may be a cathode.

[0088] The lithium battery may be prepared as follows.

[0089] An anode may be prepared by using the anode preparation method, and a cathode may be prepared by using the cathode preparation method.

[0090] A separator to be disposed between the cathode and the anode is prepared. The separator for the lithium battery may be any suitable separator used in lithium batteries. In some embodiments, the separator may have a low resistance to the migration of ions in an electrolyte and have an excellent electrolyte-retaining ability. Examples of the separator are glass fiber, polyester, polyethylene, polypropylene, PTFE (also known as TEFLON), and a combination thereof, each of which may be a non-woven or woven fabric. For example, a rollable separator including polyethylene or polypropylene may be used for a lithium ion battery. A separator with a desirable organic electrolytic solution-retaining ability may be used for a lithium ion polymer battery. For example, the separator may be manufactured in the following manner.

[0091] In some embodiments, a polymer resin, a filler, and a solvent may be combined, for instance mixed together, to prepare a separator composition. Then, the separator composition may be coated, for instance directly coated, on an electrode, and then dried to form the separator. In some embodiments, the separator composition may be cast on a support and then dried to form a separator film, which may then be separated from the support and laminated on an electrode to form the separator.

[0092] The polymer resin used to manufacture the separator may be any suitable material used as a binder for electrode plates. Examples of the polymer resin are a vinylidene fluoride/hexafluoropropylene copolymer, a polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, and a combination thereof.

[0093] An electrolyte may be prepared as follows.

[0094] In some embodiments, the electrolyte may be an organic electrolyte solution. In some embodiments, the electrolyte may be in a solid phase. Examples of the electrolyte are boron oxide and lithium oxynitride. Any suitable material available as a solid electrolyte, including those in the art, may be used. In some embodiments, the solid electrolyte may be formed on the anode by, for example, sputtering.

[0095] In some embodiments, the organic electrolyte solution may be prepared by dissolving a lithium salt in an organic solvent.

[0096] The organic solvent may be any suitable solvent available as an organic solvent, including those in the art. In some embodiments, the organic solvent may be propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylisopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N,N-dimethyl formamide, dimethyl acetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulforane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, dimethyl ether, or a combination thereof.

[0097] In some embodiments, the lithium salt may be any suitable material available as a lithium salt, including those in the art. In some embodiments, the lithium salt may be LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) (wherein x and y are each independently a natural number), LiCI, Lil, or a combination thereof.

[0098] Referring to FIG. 5, a lithium battery 31 includes a cathode 33, an anode 32, and a separator 34. In some embodiments, the cathode 33, the anode 32, and the separator 34 may be wound or folded, and then sealed in a battery case 35. In some embodiments, the battery case 35 may be filled with an organic electrolytic solution and sealed with a cap assembly 36, thereby completing the manufacture of the lithium battery 31. In some embodiments, the battery case 35 may be a cylindrical type, a rectangular type, or a thin-film type. For example, the lithium battery 31 may be a thin-film type battery. In some embodiments, the lithium battery 31 may be a lithium ion battery.

[0099] In some embodiments, the separator may be disposed between the cathode and the anode to form a battery assembly. In some embodiments, the battery assembly may be stacked in a bi-cell structure and impregnated with the electrolytic solution. In some embodiments, the resultant assembly may be inserted into a pouch and hermetically sealed, thereby completing the manufacture of a lithium ion polymer battery.

[0100] In some embodiments, a plurality of battery assemblies may be stacked to form a battery pack, which may be used in any device that requires high capacity and high output, for example, in a laptop computer, a smart phone, or an electric vehicle.

[0101] The lithium battery may have improved lifetime characteristics and high-rate characteristics, and thus may be used in an electric vehicle (EV), for example, in a hybrid vehicle such as a plug-in hybrid electric vehicle (PHEV).

[0102] According to another embodiment, a method of preparing a binder includes preparing a third composition by mixing together a first composition including a non-aqueous solvent and a first polymer and a second composition including a second polymer and water; and then heat-treating (heating) the third composition at a temperature of 160°C or greater to prepare a third polymer.

[0103] The first polymer, the second polymer, and the third polymer are the same as those defined in relation to the binder described above. A non-aqueous solvent included in the first composition may be a polar solvent such as N-methylpyrrolidone (NMP) or an alcohol. The first composition may further include water. The second composition may further include a polar organic solvent such as an alcohol mixed with water in addition to an aqueous solution including water. Therefore, the first composition and the second composition may be suitably mixed. Although a period of time for heat-treating the third composition at a temperature of 160°C or greater is not limited, the third composition, for example, may be heat-treated at a temperature of 160°C or greater for about 1 hour to about 10 hours. For example, the third composition may be heat-treated at a temperature of 160°C or greater for about 1 hour to about 5 hours. For example, the third composition may be heat-treated at a temperature of 160°C or greater for about 1 hour to about 3 hours. When the period of time for heat-treating the third composition is too short, cross-linking may not be sufficient, and when the period of time for heat-treating the third composition is too long, a degree of cross-linking compared to the heat-treating time may be insignificant. The heat-treating temperature may be lowered to about 120°C when a cross-linking catalyst such as an acid is added, and when a separate cross-linking agent is added, the heat-treating temperature may be further lowered to about 120°C or less. However, when the heat-treating temperature is too low, the polyamic acid may not be hardened to produce the polyimide.

[0104] In the method of preparing the binder, the third composition may be an electrode active material composition that further includes an electrode active material including a cathode active material or an anode active material. Thus, when the electrode active material composition is heat-treated at a temperature of 160°C or greater for 1 hour to 10 hours, the electrode may be prepared at the same time. In this case, the cross-linked binder may be homogenously bound to the electrode active material. For example, the cross-linked polymer binder may be homogeneously distributed in the anode and may be strongly attached to a metallic anode active material, and thus a volume change of the anode may be effectively reduced, for example suppressed.

[0105] In the method of preparing a binder, the first polymer may include an alkali metal. The first polymer may be substituted or doped with an alkali metal. The first polymer that is substituted or doped with an alkali metal may be referred to in the description of the binder above.

[0106] As used herein, a substituent may be derived by substitution of at least one hydrogen atom in a group with another atom or a functional group. Unless stated otherwise, a substituted functional group refers to a functional group substituted with at least one substituent selected from a C1-C40 alkyl group, a C2-C40 alkenyl group, a C3-C40 cycloalkyl group, a C3-C40 cycloalkenyl group, a C6-C40 aryl group, a C7-C40 alkylaryl group, and a C7-C40 arylalkyl group. When a functional group is "optionally" substituted, the functional group may be substituted with such a substituent listed above.

[0107] As used herein, in the expressions regarding the number of carbon atoms, i.e., a capital "C" followed by a number, for example, "C1-C20", "C3-C20", or the like, a number such as "1", "3", or "20" following "C" indicates the number of carbon atoms in a particular functional group. That is, a functional group may include 1 to 20 carbon atoms, exclusive of any substitutions. For example, a "C1-C4 alkyl group" refers to an alkyl group having 1 to 4 carbon atoms, such as CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, CH3CH2CH(CH3)-, and (CH3)3C-, where the alkyl group may be substituted or not.

[0108] As used herein, a particular radical may refer to a monovalent radical or a divalent radical depending on the context. For example, when a substituent needs two binding sites for binding with the rest of the molecule, the substituent may be understood as a divalent radical. For example, a substituent specified as an alkyl group that needs two binding sites may be a divalent radical, such as -CH2-,-CH2CH2-, or -CH2CH(CH3)CH2-. The term "alkylene" clearly indicates that the radical means a di-radical.

[0109] As used herein, the term "alkyl group" or "alkylene group" refers to a branched or unbranched aliphatic hydrocarbon group. For example, the alkyl group may or may not be substituted. Non-limiting examples of the alkyl group are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, each of which may be optionally substituted, i.e., substituted or not. In some embodiments, the alkyl group may have 1 to 6 carbon atoms. For example, a C1-C6 alkyl group may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, a 3-pentyl group, or a hexyl group, but is not limited thereto.

[0110] As used herein, the term "alkenyl group" refers to a branched or unbranched hydrocarbon group including 2 to 20 carbon atoms with at least one carbon-carbon double bond. Non-limiting examples of the alkenyl group are an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. These alkenyl groups may be substituted or not. For example, an alkenyl group may have 2 to 40 carbon atoms.

[0111] As used herein, the term "alkynyl group" refers to a branched or unbranched hydrocarbon group including 2 to 20 carbon atoms with at least one carbon-carbon triple bond. Non-limiting examples of the alkynyl group are an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a 2-butynyl group. These alkynyl groups may be substituted or not. For example, an alkynyl group may have 2 to 40 carbon atoms.

[0112] As used herein, the term "cycloalkyl group" refers to a carbocyclic ring or ring system that is fully saturated. For example, the "cycloalkyl group" may refer to a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

[0113] As used herein, the term "aromatic" refers to a ring or ring system with a conjugated π electron system, and may refer to a carbocyclic aromatic group (for example, a phenyl group) and a heterocyclic aromatic group (for example, a pyridine group). For example, an aromatic ring system as a whole may include a single ring or a fused polycyclic ring (i.e., a ring that shares adjacent atom pairs).

[0114] As used herein, the term "aryl group" refers to an aromatic group of at least one ring including only carbon atoms in its backbone, a ring system (i.e., a ring fused from at least two rings, which shares two or more adjacent carbon atoms), or a plurality of aromatic rings that are linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)- (where Ra and Rb are each independently a C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-. When the aryl group is a ring system, each ring in the ring system may be aromatic. Non-limiting examples of the aryl group are a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, and a naphthacenyl group. These aryl groups may be substituted or not.

[0115] As used herein, the term "arylene group" refers to an aryl group that requires at least two linking sites, i.e., is at least divalent. A tetravalent arylene group is an aryl group that requires four linking sites, and a divalent arylene group is an aryl group that requires two linking sites. For example, the divalent arylene group may be -C6H5-O-C6H5- .

[0116] As used herein, the term "heteroaryl group" refers to an aromatic ring system with one ring, a plurality of rings that are fused to each other, or an aromatic ring system having a plurality of rings that are linked by a single bond, -O-, -S-, -C(=O)-,-S(=O)2-, -Si(Ra)(Rb)- (where Ra and Rb are each independently a C1-C10 alkyl group), a C1-C10 alkylene group substituted or unsubstituted with a halogen, or-C(=O)-NH-, in which at least one member of the aromatic ring system is a heteroatom, i.e., not carbon. In the fused ring system, at least one heteroatom may be in one ring. For example, the heteroatom may be oxygen, sulfur, phosphorus, or nitrogen, but is not limited thereto. Non-limiting examples of the heteroaryl group are a furanyl group, a thienyl group, an imidazolyl group, a quinazolinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a pyridinyl group, a pyrrolyl group, an oxazolyl group, and an indolyl group.

[0117] As used herein, the term "heteroarylene group" refers to a heteroaryl group that requires at least two linking sites. A tetravalent heteroarylene group is a heteroaryl group that requires four linking sites, and a divalent heteroarylene group is a heteroaryl group that requires two linking sites.

[0118] As used herein, the term "aralkyl group" or "arylalkyl group" refers to an aryl group linked to a substituent via an alkylene group, such as a C7-C14 aralkyl group. Non-limiting examples of the aralkyl group or arylalkyl group are a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a naphthylalkylene group. For example, the alkylene group may be a lower alkylene group (i.e., a C1-C4 alkylene group). As used herein, the term "alkaryl group" or "alkylaryl group" refers to an alkyl group linked to a substituent via an arylene group, such as a C7-C14 alkylaryl group. Non-limiting examples of the alkaryl group or "alkylaryl group group are 4-methylphenylene.

[0119] As used herein, the terms "cycloalkenyl group" refers to a non-aromatic carbocyclic ring or ring system with at least one double bond without an aromatic ring. For example, the cycloalkenyl group may be a cyclohexenyl group.

[0120] As used herein, the terms "heterocyclic group" refers to a non-aromatic ring or ring system including at least one heteroatom in its cyclic backbone.

[0121] As used herein, the term "halogen" refers to a stable atom belonging to Group 17 of the periodic table of elements, for example, fluorine, chlorine, bromine, or iodine. For example, the halogen atom may be fluorine and/or chlorine.

[0122] Weight average molecular weights (Mw) of the first polymer, the second polymer, and the third polymer are measured by gel permeation chromatography (GPC) with respect to a standard sample.

[0123] Hereinafter, one or more embodiments will be described in detail with reference to the following examples. However, these examples are not intended to limit the scope of the one or more embodiments of the present specification.

Preparation of cross-linked polymer


Example 1: LiPI:PVA=10:90



[0124] After filling a three-neck round-bottom flask with nitrogen, 9.9790 g (0.0498 mol) of 4,4'-oxydianiline (ODA) and 2.5275 g (0.0166 mol) of 1,3-diaminobenzoic acid (DABA) were added to the flask, 153 g of N-methylpyrrolidone (NMP) was added thereto, and the resulting mixture was stirred using a mechanical stirrer until the components had completely dissolved. Then, 14.4935 g (0.0664 mol) of pyromellitic dianhydride (PMDA) was added thereto, and the mixture was stirred at room temperature for 24 hours to prepare a polyamic acid (PMDA/ODA/DABA, having an acid equivalent of 210 g/eq and an Mw of about 1,000,000 Da) represented by Formula 9. The polyamic acid was a random copolymer. A molar ratio of PMDA:ODA:DABA was 4:3:1. A molar ratio, n:m, in Formulae 9 and 10 was 3:1.

[0125] 10 g of an aqueous LiOH solution at a 0.5 equivalent ratio with respect to carboxylic acid was added to the polyamic acid (PMDA/ODA/DABA, having an acid equivalent of 210 g/eq and an Mw of about 1,000,000 Da) represented by Formula 9 to prepare an aqueous polyamic acid represented by Formula 10 which had a 0.5 equivalent ratio of -C(=O)OH among the -C(=O)OH of the polyamic acid substituted with -C(=O)O-Li+. The aqueous polyamic acid represented by Formula 10 and a polyvinyl alcohol (having an Mw of 78,000 Da and a saponification degree of 88%, available from Polysciences, 15132) were mixed at a weight ratio of 10:90, and the mixture was heat-treated at 180°C for 2 hours in a vacuum oven to perform a cross-linking reaction, and thus a cross-linked polymer was prepared. When an ester linker was formed by the reaction between a carboxyl group in the polyamic acid and a hydroxyl group of the polyvinyl alcohol, a cross-linked polymer of the polyamic acid and the polyvinyl alcohol was prepared. The cross-linked polymer had a 3-dimensional network structure as the polyamic acid and the polyvinyl alcohol cross-linked at a plurality of sites.




Example 2: LiPI:PVA=20:80



[0126] A cross-linked polymer was prepared in the same manner as in Example 1, except that the aqueous polyamic acid represented by Formula 10 and the polyvinyl alcohol were mixed at a weight ratio of 20:80.

Example 3: LiPI:PVA=30:70



[0127] A cross-linked polymer was prepared in the same manner as in Example 1, except that the aqueous polyamic acid represented by Formula 10 and the polyvinyl alcohol were mixed at a weight ratio of 30:70.

Example 4: LiPI:PVA=50:50



[0128] A cross-linked polymer was prepared in the same manner as in Example 1, except that the aqueous polyamic acid represented by Formula 10 and the polyvinyl alcohol were mixed at a weight ratio of 50:50.

Example 5: PI:PVA=10:90, Li-unsubstituted



[0129] After filling a three-neck round-bottom flask with nitrogen, 9.9790 g (0.0498 mol) of 4,4'-oxydianiline (ODA) and 2.5275 g (0.0166 mol) of 1,3-diaminobenzoic acid (DABA) were added to the flask, 153 g of N-methylpyrrolidone (NMP) was added thereto, and the resulting mixture was stirred using a mechanical stirrer until the components had completely dissolved. Then, 14.4935 g (0.0664 mol) of PMDA was added thereto, and the mixture was stirred at room temperature for 24 hours to prepare a polyamic acid (PMDA/ODA/DABA, having an acid equivalent of 210 g/eq and an Mw of about 1,000,000 Da) represented by Formula 9. The polyamic acid was a random copolymer. A molar ratio of PMDA:ODA:DABA was 4:3:1. A molar ratio, n:m, in Formulae 9 and 10 was 3:1.

[0130] The aqueous polyamic acid represented by Formula 9 and the polyvinyl alcohol (having an Mw of 78,000 Da and a saponification degree of 88%, available from Polysciences, 15132) were mixed at a weight ratio of 10:90, and the mixture was heat-treated at 180°C for 2 hours in a vacuum oven to perform a cross-linking reaction, and thus a cross-linked polymer was prepared. When an ester linker was formed due to the reaction between a carboxyl group in the polyamic acid and a hydroxyl group of the polyvinyl alcohol, a cross-linked polymer of the polyamic acid and the polyvinyl alcohol was prepared.


Comparative Example 1: LiPI:PVA=100:0



[0131] A lithium-substituted polyamic acid represented by Formula 10 and prepared in Example 1 was used as it was.

Comparative Example 2: LiPI:PVA=0:100



[0132] A polyvinyl alcohol used in Example 1 was used as it was.

Comparative Example 3: SBR/CMC



[0133] A mixture of styrene-butadiene (SBR) and carboxymethylcellulose (CMC) at a weight ratio of 1:1 was prepared.

Comparative Example 4: PI:PVA=20:80, Li-unsubstituted, no cross-linker



[0134] After filling a three-neck round-bottom flask with nitrogen, 12.9230 g (0.0645 mol) of 4,4'-oxydianiline (ODA) was added to the flask, 153 g of N-methylpyrrolidone (NMP) was added thereto, and the resulting mixture was stirred using a mechanical stirrer until the components had completely dissolved. Then, 14.0770 g (0.0645 mol) of PMDA was added thereto, and the mixture was stirred at room temperature for 24 hours to prepare a polyamic acid (PMDA/ODA, having an acid equivalent of 210 g/eq and an Mw of about 1,000,000 Da) represented by Formula 9a. A molar ratio of PMDA:ODA was 1:1. In Formula 9a, p is a polymerization degree which ranges from about 2,000 to about 10,000.

[0135] The polyamic acid represented by Formula 9a and the polyvinyl alcohol (having an Mw of 78,000 Da and a saponification degree of 88%, available from Polysciences, 15132) were mixed at a weight ratio of 20:80, and the mixture was heat-treated at 180°C for 2 hours in a vacuum oven to prepare a polymer.


Preparation of anode and lithium battery


Example 6



[0136] A Si-C composite (having an average particle diameter of 15 µm, available from Shin-Etsu) as an anode active material, artificial graphite as a conducting agent, and a mixture composition of lithium-substituted polyamic acid represented by Formula 10 and a polyvinyl alcohol at a weight ratio of 10:90 were mixed at a weight ratio of 25:67:8, and the mixture was mixed with NMP by using an agate mortar to prepare an anode active material slurry.

[0137] The anode active material slurry was coated on a copper foil current collector having a thickness of 10 micrometers (µm) to prepare an anode plate, and the completed anode plate with the coating was primarily dried in an oven at a temperature of 80°C for 1 hour, secondarily dried in an oven at a temperature of 180°C for 2 hours, and pressed by using a press to prepare an anode having a mixture density of 1.57 grams per cubic centimeter (g/cc) and a thickness of 660 µm.

[0138] The anode, a Li metal as a counter electrode, a polypropylene separator (Cellgard 3510) as a separator, and a solution including 1.3 M of LiPF6 dissolved in a solvent mixture having ethylene carbonate (EC), fluoroethyl carbonate (FEC), and diethyl carbonate (DEC) (at a volume ratio of 2:2:6) as an electrolyte were used to prepare a CR-2032 coin half-cell.

Example 7



[0139] An anode and a lithium battery were prepared in the same manner as in Example 6, except that a composition mixture of the lithium-substituted polyamic acid and the polyvinyl alcohol mixed at a weight ratio of 20:80 as used in Example 2 was used.

Example 8



[0140] An anode and a lithium battery were prepared in the same manner as in Example 6, except that a composition mixture of the lithium-substituted polyamic acid and the polyvinyl alcohol mixed at a weight ratio of 30:70 as used in Example 3 was used.

Example 9



[0141] An anode and a lithium battery were prepared in the same manner as in Example 6, except that a composition mixture of the lithium-substituted polyamic acid and the polyvinyl alcohol mixed at a weight ratio of 50:50 as used in Example 4 was used.

Example 10



[0142] An anode and a lithium battery were prepared in the same manner as in Example 6, except that a composition mixture of the polyamic acid and the polyvinyl alcohol mixed at a weight ratio of 10:90 as used in Example 5 was used.

Comparative Example 5



[0143] An anode and a lithium battery were prepared in the same manner as in Example 6, except that the lithium-substituted polyamic acid prepared in Comparative Example 1 was used as a binder.

Comparative Example 6



[0144] An anode and a lithium battery were prepared in the same manner as in Example 6, except that the polyvinyl alcohol prepared in Comparative Example 2 was used as a binder.

Comparative Example 7



[0145] An anode and a lithium battery were prepared in the same manner as in Example 6, except that the SBR/CMC prepared in Comparative Example 3 was used as a binder.

Comparative Example 8



[0146] An anode and a lithium battery were prepared in the same manner as in Example 6, except that the polyimide represented by Formula 9a and the polyvinyl alcohol prepared in Comparative Example 4 were used as a binder.

Comparative Example 9



[0147] An anode and a lithium battery were prepared in the same manner as in Example 6, except that the lithium-substituted polyacrylamide (LiPAA) represented by the following formula was used as a binder.


Evaluation Example 1: IR spectrum analysis



[0148] Fourier Transform Infrared (IR) spectra of the polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were obtained to confirm whether or not cross-linking occurred in the polymers.

[0149] As shown in FIG. 1, a peak within 3700 to 2700 cm-1 corresponding to a hydroxyl group was observed at a high intensity from the polymers prepared in Comparative Examples 1 and 2.

[0150] The cross-linked polymers of Examples 1 to 3 had a peak with a decreased intensity within 3700 to 2700 cm-1 corresponding to a hydroxyl group due to formation of an ester bond by a cross-linking reaction, and thus it confirmed that cross-linking occurred during preparation of the polymers.

Evaluation Example 2: X-ray diffraction (XRD) spectrum analysis



[0151] XRD spectra of the polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were obtained to confirm whether or not cross-linking occurred in the polymers.

[0152] As shown in FIG. 2, the polyvinyl alcohol of Comparative Example 2 exhibited high crystallinity, but when cross-linking of the polyimide and the polyvinyl alcohol increased in Examples 1 to 3, the crystallinity decreased.

Evaluation Example 3: Thermogravimetric analysis (TGA)



[0153] The thermal stability of the polymers prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated by TGA.

[0154] As shown in FIG. 3, the cross-linked polymers of Examples 1 to 3 and polyvinyl alcohol (PVA) of Comparative Example 2 had almost no change in their weights at a temperature of 200°C or lower, and thus thermal stability of the cross-linked polymers improved compared to that of the polyimide (PI) of Comparative Example 1. Also, at a temperature of 300°C or greater, a decrease in weight was suppressed in the cross-linked polymers of Examples 1 to 3 as compared with that which occurred in polyvinyl alcohol, and thus thermal stability of the cross-linked polymers of Examples 1 to 3 improved compared to that of polyvinyl alcohol.

Evaluation Example 4: Mechanical physical property evaluation of cross-linked polymer



[0155] A polymer film having a size of 5×5 square centimeters (cm2) and a thickness of 50 µm was prepared on a glass substrate by using one of the polymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4 to evaluate mechanical physical properties of the polymers as follows.

[0156] Extension, recovery, modulus, and hardness of the polymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured by using a microindenter (DUH-211, available from Shimadzu). A force applied on the polymer film sample was 10 milliNewtons (mN).

[0157] The results of the measurement are shown in Table 1. An extension is a distance of a tip of the microindenter moved in a sample until a constant force was applied to the tip, and a recovery is a ratio of a distance of the tip moved from the deepest point in the sample to a point where the force applied to the tip was zero in a direction toward a surface of the sample with respect to the distance of the tip initially moved in the sample. The modulus is an indentation modulus and the hardness is an indentation hardness, and are calculated using a force applied to the tip from the sample according to a moving distance of the tip of the microindenter.
Table 1
 Extension [mm]Recovery [%]Modulus [GPa]Hardness [N/mm2]
Example 1 0.35 60.8 39.0 2399
Example 2 0.32 70.7 45.0 2156
Example 3 0.39 68.6 38.1 1578
Example 4 0.35 72.5 31.0 1630
Comparative Example 1 0.35 66.5 29.5 1624
Comparative Example 2 0.33 66.5 29.5 1695
Comparative Example 3 1.23 53.9 4.2 169
Comparative Example 4 0.49 80.0 17.3 920
GPa: gigapascals


[0158] As shown in Table 1, since strengths of the binders increased as moduli, or elasticity moduli, of the cross-linked polymers of Examples 1 to 4 increased compared to those of the polymers of Comparative Examples 1 to 4, expansion of the electrodes was suppressed.

[0159] Moduli of the cross-linked polymers of Examples 1 to 4 improved compared to a binder prepared by using polyamic acid or polyvinyl alcohol alone. Such an improvement in physical properties was deemed as caused by the formation of a cross-linked polymer.

[0160] The rubber-based binder of Comparative Example 3 had a significantly low hardness and strength.

[0161] The polymer of Comparative Example 4 is a mixture of polyimide and polyvinyl alcohol, which was prepared without a cross-linking process, and thus the modulus and hardness of the polymer were significantly lower than those of the cross-linked polymers of Examples 1 to 4.

Evaluation Example 5: Mechanical physical property evaluation of non-cross-linked polymer



[0162] Polymers of Reference Example 1, Reference Example 2, Reference Example 3, and Reference Example 4 were prepared in the same manner as in Example 2 (LiPPA:PVA=20:80), Example 4 (LiPPA:PVA=50:50), Comparative Example 1 (LiPPA:PVA=100:0), and Comparative Example 2 (LiPPA:PVA=0:100), respectively, except that the heat-treating temperature was changed to 150°C, each polymer was used to prepare a polymer film having a size of 5×5 cm2 and a thickness of 50 µm on a glass substrate, and the mechanical physical properties of each of the polymers were evaluated in the same manner as in Evaluation Example 4. The results are shown in Table 2.
Table 2
 Extension [mm]Modulus [GPa]
Reference Example 1 0.38 16.8
Reference Example 2 0.37 16.4
Reference Example 3 0.39 21.1
Reference Example 4 0.38 18.5


[0163] As shown in Table 2, when polyamic acid and polyvinyl alcohol were mixed in the manner as the polymers mixed in Reference Examples 1 to 4, moduli of the polymers decreased, and thus it was confirmed that no cross-linking reaction occurred between the polyamic acid and the polyvinyl alcohol.

Evaluation Example 6: Electrode plate stability evaluation



[0164] The lithium batteries (coin cells) prepared in Examples 7 and 9 and Comparative Examples 5, 6, and 7 were charged with a constant current at a rate of 0.1 C until a voltage of 0.01 V (vs. Li) was reached, and charged with a constant voltage until a constant current of 0.01 C was reached while maintaining the voltage at 0.01 V. Once the charging was completed, the lithium batteries were rested for about 10 minutes, and then the batteries were each discharged with a constant current of 0.1 C until a voltage of 1.5 V (vs. Li) was reached during a discharging process (1st cycle).

[0165] Subsequently, the batteries were each charged with a constant current at a rate of 0.2 C until a voltage of 0.01 V (vs. Li) was reached, and charged with a constant voltage until a constant current of 0.01 C was reached while maintaining the voltage at 0.01 V.

[0166] The charged coin cells were disassembled to evaluate stability of the electrode plate. The stability of the electrode plate was evaluated by confirming whether an initial shape of an electrode was maintained after the charging/discharging process as binding within the active material layer and between the active material layer and the current collector was maintained.

[0167] As shown in FIG. 4, cracks occurred in the anode of Comparative Example 6 prepared by using polyvinyl alcohol, and thus the active material layer was separated from the current collector. Also, the anode of Comparative Example 7 prepared using a binder of SBR-CMC had cracks which occurred therein.

[0168] The anode of Comparative Example 5 prepared using the polyimide and the anodes of Examples 7 and 9 prepared using the cross-linked polymers maintained the initial shapes of the anode plates without cracks.

[0169] Therefore, stability of the anode plates improved by using the binder of Examples 7 and 9. That is, the cross-linked polymer maintained both cohesion between the materials of the active material layer and cohesion between the active material layer and the current collector, thus preventing cracking of the electrode.

[0170] Also, polyvinyl alcohol was observed to generate cracks and thus may not be used alone as a binder in an electrode.

Evaluation Example 7: Charging/discharging characteristics evaluation



[0171] At 25°C, the lithium batteries (coin cells) prepared in Examples 6 to 10 and Comparative Examples 5 to 9 were charged with a constant current at a rate of 0.1 C until a voltage of 0.01 V (vs. Li) was reached, and charged with a constant voltage until a constant current of 0.01 C was reached while maintaining the voltage at 0.01 V. Once the charging was completed, the lithium batteries were rested for about 10 minutes, and then the batteries were each discharged with a constant current of 0.1 C until a voltage of 1.5 V (vs. Li) was reached during a discharging process (1st cycle).

[0172] Subsequently, the batteries were each charged with a constant current at a rate of 0.2 C until a voltage of 0.01 V (vs. Li) was reached, and charged with a constant voltage until a constant current of 0.01 C was reached while maintaining the voltage at 0.01 V. Once the charging was completed, the lithium batteries were rested for about 10 minutes, and then the batteries were each discharged with a constant current of 0.2 C until a voltage of 1.5 V (vs. Li) was reached during a discharging process (2nd cycle) (a formation process includes the 1st and 2nd cycles).

[0173] At 25°C, the coin cells after the formation process were each charged with a constant current at a rate of 0.1 C until a voltage of 0.01 V (vs. Li) was reached, and charged with a constant voltage until a constant current of 0.01 C was reached while maintaining the voltage at 0.01 V. Once the charging was completed, the lithium batteries were rested for about 10 minutes, and then the batteries were each discharged with a constant current of 1.0 C until a voltage of 1.5 V (vs. Li) was reached during a discharging process. This cycle was repeated 50 times. The results of the charging/discharging test are shown in Table 3.

[0174] The electrode thickness expansion ratios, initial efficiencies, and capacity retention rates of the electrode were each calculated according to Equations 1 to 3, respectively. The electrode thickness expansion ratio relates to an anode electrode.





Table 3
 Initial efficiency [%]1st cycle discharge capacity [mAh/g]Capacity retention ratio [%]Electrode thickness expansion ratio [%]
Example 6 84,4 646 97.5 48
Example 7 84.0 654 97.4 42
Example 8 83.0 644 97.3 50
Example 9 81.1 635 95.7 52
Example 10 82.2 655 96.7 60
Comparative Example 5 79.3 643 95.6 55
Comparative Example 6 83.7 637 95.2 60
Comparative Example 7 84.5 630 79.2 108
Comparative Example 8 82.4 647 93.3 66
Comparative Example 9 83.4 636 94.2 56
mAh/g: milliampere hours per gram


[0175] As shown in Table 3, the lithium batteries of Examples 6 to 10 had improved lifespan characteristics compared to those of the lithium batteries of Comparative Examples 5 to 9. The lithium batteries of Examples 6 to 10 had improved initial efficiencies compared to those of the lithium battery of Comparative Example 5 including polyimide. The lithium batteries of Examples 6 to 10 had significantly decreased electrode thickness expansion ratios compared to those of the lithium batteries of Comparative Examples 7 to 8 including a binder.

[0176] As described above, according to one or more embodiments, the initial efficiency, lifespan characteristics, and electrode stability of a lithium battery may improve by using a binder including a cross-linked polymer, in which polyimide and an aqueous binder are cross-linked. Also, the volume change of the lithium battery may be suppressed.

[0177] It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.

[0178] While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope as defined by the following claims.


Claims

1. A binder comprising:

a third polymer comprising a cross-linked product of a first polymer and a second polymer;

wherein the first polymer is at least one selected from a polyamic acid and a polyimide cured from the polyamic acid,

wherein the polyamic acid is represented by Formula 1 or Formula 2:



wherein, in Formulae 1 and 2,

M is an alkali metal;

Ar1 and Ar3 are each independently an aromatic group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring comprising at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-,-C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

Ar2 and Ar4 are each independently an aromatic group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring having at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

X1 is -C(=O)OH, -OH, -C(=O)-NH2, or -C(=O)H; and

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1;

wherein the second polymer is a polyvinyl alcohol, and

wherein the first polymer and the second polymer are cross-linked by an ester bond.


 
2. The binder of claim 1, wherein the first polymer further comprises an alkali metal, preferably wherein an amount of the alkali metal in the first polymer is in a range of 0.2 equivalents to 1.0 equivalents at an equivalent ratio with respect to a carboxyl group or an amide group.
 
3. The binder of claims 1 or 2, wherein the polyamic acid is represented by Formula 3 or Formula 4:



wherein, in Formulae 3 and 4,

M is lithium or sodium;

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a hydrogen, a halogen, -C(=O)OH, -OH, -C(=O)-NH2,-C(=O)H, a C1-C10 alkyl group substituted or unsubstituted with a halogen, a C6-C20 aryl group substituted or unsubstituted with a halogen, or a C2-C20 heteroaryl group substituted or unsubstituted with a halogen;

Y1 is a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group, and R is a C1-C10 alkyl group;

at least one selected from R3, R4, R5, and R6 is -C(=O)OH, -OH,-C(=O)-NH2, or -C(=O)H; and

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.


 
4. The binder of any of claims 1 to 3, wherein the polyimide is represented by Formula 5 or Formula 6:



wherein, in Formulae 5 and 6,

M is an alkali metal;

Ar1 and Ar3 are each independently an aromatic group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a group comprising at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-,-S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

Ar2 and Ar4 are each independently an aromatic group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring comprising at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-, - C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

X1 is -C(=O)OH, -OH, -C(=O)-NH2, or -C(=O)H; and

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1, or

wherein the polyimide is represented by Formula 7 or Formula 8:



wherein, in Formulae 7 and 8,

M is lithium or sodium;

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 are each independently a hydrogen, a halogen, -C(=O)OH, -OH, -C(=O)-NH2,-C(=O)H, a C1-C10 alkyl group substituted or unsubstituted with a halogen, a C6-C20 aryl group substituted or unsubstituted with a halogen, or a C2-C20 heteroaryl group substituted or unsubstituted with a halogen;

Y1 is a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, where Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

at least one selected from R3, R4, R5, and R6 is -C(=O)OH, -OH,-C(=O)-NH2, or -C(=O)H; and

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1.


 
5. The binder of any of claims 1 to 4, wherein the polyamic acid is represented by Formula 9 or Formula 10, and the polyimide is represented by Formula 11 or Formula 12:







wherein, in Formulae 9 to 12,
n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1, preferably wherein 0<n<0.5, 0.5<m<1, and n+m=1.
 
6. The binder of any of claims 1 to 5, wherein a saponification degree of the polyvinyl alcohol is in a range of 60% to 99%, and/or wherein a weight average molecular weight of the polyvinyl alcohol is in a range of 10,000 Daltons to 500,000 Daltons.
 
7. The binder of any of claims 1 to 6, wherein a weight ratio of the first polymer and the second polymer is in a range of 1:99 to 50:50.
 
8. The binder of any of claims 1 to 7, wherein the cross-linking is at a temperature of 160°C or greater.
 
9. The binder of any of claims 1 to 8, wherein an indentation modulus of the third polymer is greater than each of a modulus of the first polymer and a modulus of the second polymer, and/or wherein an indentation hardness of the third polymer is greater than each of an indentation hardness of the first polymer and an indentation hardness of the second polymer.
 
10. The binder of any of claims 1 to 9, wherein the third polymer has a network structure comprising the cross-linked product of the first polymer and the second polymer, and/or wherein a weight average molecular weight of the third polymer is in a range of 10,000 Daltons to 1,000,000 Daltons.
 
11. The binder of any of claims 1 to 10, wherein the third polymer is represented by one of Formulae 13 to 16:









wherein, in Formulae 13 to 16,

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1; and

p is a polymerization degree which is in a range of 250 to 12,500.


 
12. An electrode comprising
the binder of any of claims 1 to 11; and
a cathode active material or an anode active material, preferably wherein the anode active material comprises at least one selected from a lithium metal; a lithium-alloyable metal; a composite of a lithium-alloyable metal and carbon; a composite of a lithium-alloyable metal and nitrogen; a composite of a lithium-alloyable metal, nitrogen, and carbon; a composite of a lithium-alloyable metal and a metal that is inert to lithium; a composite of a lithium-alloyable metal and a metal oxide that is inert to lithium; a composite of a lithium-alloyable metal and a metal nitride that is inert to lithium; and a composite of a lithium-alloyable metal and a metal nitrate that is inert to lithium, and/or wherein the anode active material comprises at least one selected from a silicon active material, a tin active material, a silicon-tin alloy active material, and a silicon-carbon active material, and/or wherein a thickness expansion of the electrode calculated in accordance with Equation 1 is less than 54%.


 
13. A lithium battery comprising
a first electrode comprising the electrode of claim 12;
a second electrode; and
an electrolyte disposed between the first electrode and the second electrode.
 
14. A method of preparing a binder, the method comprising
preparing a third composition by mixing together a first composition comprising a non-aqueous solvent and a first polymer and a second composition comprising a second polymer and water,
wherein the first polymer is selected from at least one of a polyamic acid and a polyimide cured from the polyamic acid, wherein the polyamic acid is represented by Formula 1 or Formula 2:



wherein, in Formulae 1 and 2,

M is an alkali metal;

Ar1 and Ar3 are each independently an aromatic group selected from a substituted or unsubstituted tetravalent C6-C24 arylene group and a substituted or unsubstituted tetravalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring comprising at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-,-C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

Ar2 and Ar4 are each independently an aromatic group selected from a substituted or unsubstituted divalent C6-C24 arylene group and a substituted or unsubstituted divalent C4-C24 heteroarylene group, wherein the aromatic group is one aromatic ring, a ring having at least two aromatic rings fused to each other, or a ring comprising at least two aromatic rings linked by a single bond, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, a C1-C10 alkylene group substituted or unsubstituted with a halogen, or -C(=O)-NH-, wherein Ra and Rb are each independently a substituted or unsubstituted C1-C10 alkyl group;

X1 is -C(=O)OH, -OH, -C(=O)-NH2, or -C(=O)H; and

n and m are each a molar ratio of a repeating unit, where 0<n<1, 0<m<1, and n+m=1, and

the second polymer comprises a polyvinyl alcohol; and
heating the third composition at a temperature of 160°C or greater to prepare a third polymer, preferably wherein the first polymer further comprises an alkali metal.
 


Ansprüche

1. Binder, umfassend:

ein drittes Polymer umfassend ein vernetztes Produkt eines ersten Polymers und eines zweiten Polymers;

wobei das erste Polymer mindestens eines ist, das ausgewählt ist aus einer Polyaminsäure und einem aus der Polyaminsäure gehärteten Polyimid,

wobei die Polyaminsäure dargestellt ist durch Formel 1 oder Formel 2:



wobei, in Formeln 1 und 2, gilt:
M ist ein Alkalimetall;

Ar1 und Ar3 sind jeweils unabhängig eine aromatische Gruppe ausgewählt aus einer substituierten oder unsubstituierten tetravalenten C6-C24-Arylengruppe und einer substituierten oder unsubstituierten tetravalenten C4-C24-Heteroarylengruppe, wobei die aromatische Gruppe ein aromatischer Ring, ein Ring umfassend mindestens zwei miteinander fusionierte aromatische Ringe oder ein Ring umfassend mindestens zwei durch eine Einfachbindung verknüpfte aromatische Ringe, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH- ist, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

Ar2 und Ar4 sind jeweils unabhängig eine aromatische Gruppe ausgewählt aus einer substituierten oder unsubstituierten divalenten C6-C24-Arylengruppe und einer substituierten oder unsubstituierten divalenten C4-C24-Heteroarylengruppe, wobei die aromatische Gruppe ein aromatischer Ring, ein Ring aufweisend mindestens zwei miteinander fusionierte aromatische Ringe oder ein Ring umfassend mindestens zwei durch eine Einfachbindung verknüpfte aromatische Ringe, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH- ist, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

X1 ist -C(=O)OH, -OH, -C(=O)-NH2 oder -C(=O)H; und

n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1;

wobei das zweite Polymer ein Polyvinylalkohol ist, und

wobei das erste Polymer und das zweite Polymer durch eine Esterbindung vernetzt sind.


 
2. Binder nach Anspruch 1, wobei das erste Polymer ferner ein Alkalimetall umfasst, bevorzugt, wobei eine Menge des Alkalimetalls in dem ersten Polymer in einem Bereich von 0,2 Äquivalenten bis 1,0 Äquivalenten bei einem Äquivalentverhältnis mit Bezug auf eine Carboxylgruppe oder eine Amidgruppe ist.
 
3. Binder nach Anspruch 1 oder 2,
wobei die Polyaminsäure dargestellt ist durch Formel 3 oder Formel 4:



wobei, in Formel 3 und 4, gilt:

M ist Lithium oder Natrium;

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, und R16 sind jeweils unabhängig ein Wasserstoff, ein Halogen, -C(=O)OH, -OH, -C(=O)-NH2, -C(=O)H, eine C1-C10-Alkylgruppe substituiert oder unsubstituiert mit einem Halogen, eine C6-C20-Arylgruppe substituiert oder unsubstituiert mit einem Halogen oder eine C2-C20-Heteroarylgruppe substituiert oder unsubstituiert mit einem Halogen;

Y1 ist eine Einfachbindung, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH-, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind und R eine C1-C10-Alkylgruppe ist;

mindestens eine aus R3, R4, R5 und R6 ausgewählte ist -C(=O)OH, -OH, -C(=O)-NH2 oder -C(=O)H; und

n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1.


 
4. Binder nach einem der Ansprüche 1 bis 3, wobei das Polyimid dargestellt ist durch Formel 5 oder Formel 6:



wobei, in Formeln 5 und 6, gilt:

M ist ein Alkalimetall;

Ar1 und Ar3 sind jeweils unabhängig eine aromatische Gruppe ausgewählt aus einer substituierten oder unsubstituierten tetravalenten C6-C24-Arylengruppe und einer substituierten oder unsubstituierten tetravalenten C4-C24-Heteroarylengruppe, wobei die aromatische Gruppe ein aromatischer Ring, eine Gruppe umfassend mindestens zwei miteinander fusionierte aromatische Ringe oder ein Ring umfassend zwei durch eine Einfachbindung verknüpfte aromatische Ringe, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH- ist, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

Ar2 und Ar4 sind jeweils unabhängig eine aromatische Gruppe ausgewählt aus einer substituierten oder unsubstituierten divalenten C6-C24-Arylengruppe und einer substituierten oder unsubstituierten divalenten C4-C24-Heteroarylengruppe, wobei die aromatische Gruppe ein aromatischer Ring, ein Ring umfassend mindestens zwei miteinander fusionierte aromatische Ringe oder ein Ring umfassend mindestens zwei durch eine Einfachbindung verknüpfte aromatische Ringe, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH- ist, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

X1 ist -C(=O)OH, -OH, -C(=O)-NH2 oder -C(=O)H; und

n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1, oder

wobei das Polyimid dargestellt ist durch Formel 7 oder Formel 8:



wobei, in Formeln 7 und 8, gilt:

M ist Lithium oder Natrium;

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, und R16 sind jeweils unabhängig ein Wasserstoff, ein Halogen, -C(=O)OH, -OH, -C(=O)-NH2, -C(=O)H, eine C1-C10-Alkylgruppe substituiert oder unsubstituiert mit einem Halogen, eine C6-C20-Arylgruppe substituiert oder unsubstituiert mit einem Halogen oder eine C2-C20-Heteroarylgruppe substituiert oder unsubstituiert mit einem Halogen;

Y1 ist eine Einfachbindung, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH-, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

mindestens eine aus R3, R4, R5 und R6 ausgewählte ist -C(=O)OH, -OH, -C(=O)-NH2 oder -C(=O)H; und

n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1.


 
5. Binder nach einem der Ansprüche 1 bis 4, wobei die Polyaminsäure dargestellt ist durch Formel 9 oder Formel 10 und das Polyimid dargestellt ist durch Formel 11 oder Formel 12:







wobei, in Formeln 9 bis 12, gilt:
n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1, bevorzugt, wobei 0<n<0,5, 0,5<m<1 und n+m=1.
 
6. Binder nach einem der Ansprüche 1 bis 5, wobei ein Verseifungsgrad des Polyvinylalkohols in einem Bereich von 60 % bis 99 % ist und/oder wobei ein Gewichtsmittel des Molekulargewichts des Polyvinylalkohols in einem Bereich von 10.000 Dalton bis 500.000 Dalton ist.
 
7. Binder nach einem der Ansprüche 1 bis 6, wobei ein Gewichtsverhältnis des ersten Polymers und des zweiten Polymers in einem Bereich von 1:99 bis 50:50 ist.
 
8. Binder nach einem der Ansprüche 1 bis 7, wobei die Vernetzung bei einer Temperatur von 160 °C oder mehr erfolgt.
 
9. Binder nach einem der Ansprüche 1 bis 8, wobei ein Eindringmodul des dritten Polymers größer ist als jedes eines Moduls des ersten Polymers und eines Moduls des zweiten Polymers, und/oder wobei eine Eindringhärte des dritten Polymers größer ist als jede einer Eindringhärte des ersten Polymers und einer Eindringhärte des zweiten Polymers.
 
10. Binder nach einem der Ansprüche 1 bis 9, wobei das dritte Polymer eine Netzstruktur umfassend das vernetzte Produkt des ersten Polymers und des zweiten Polymers aufweist, und/oder wobei ein Gewichtsmittel des Molekulargewichts des dritten Polymers in einem Bereich von 10.000 Dalton bis 1.000.000 Dalton ist.
 
11. Binder nach einem der Ansprüche 1 bis 10, wobei das dritte Polymer dargestellt ist durch eine von Formeln 13 bis 16:









wobei, in Formeln 13 bis 16, gilt:

n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1; und

p ist ein Polymerisationsgrad, der in einem Bereich von 250 bis 12.500 ist.


 
12. Elektrode, umfassend
den Binder nach einem der Ansprüche 1 bis 11; und
ein kathodenaktives Material oder ein anodenaktives Material, bevorzugt, wobei das anodenaktive Material mindestens eines umfasst, das ausgewählt ist aus einem Lithiummetall; einem lithiumlegierbaren Metall; einem Verbund aus einem lithiumlegierbaren Metall und Kohlenstoff; einem Verbund aus einem lithiumlegierbaren Metall und Stickstoff; einem Verbund aus einem lithiumlegierbaren Metall, Stickstoff und Kohlenstoff; einem Verbund aus einem lithiumlegierbaren Metall und einem Metall, das gegenüber Lithium inert ist; einem Verbund aus einem lithiumlegierbaren Metall und einem Metalloxid, das gegenüber Lithium inert ist; einem Verbund aus einem lithiumlegierbaren Metall und einem Metallnitrid, das gegenüber Lithium inert ist; und einem Verbund aus einem lithiumlegierbaren Metall und einem Metallnitrat, das gegenüber Lithium inert ist, und/oder wobei das anodenaktive Material mindestens eines umfasst, das ausgewählt ist aus einem Silizium-aktiven Material, einem Zinn-aktiven Material, einem Silizium-Zinn-Legierungs-aktiven Material und einem Silizium-Kohlenstoff-aktiven Material, und/oder wobei eine Dickenexpansion der Elektrode, berechnet gemäß Gleichung 1, weniger als 54 % ist.


 
13. Lithiumbatterie, umfassend
eine erste Elektrode umfassend die Elektrode nach Anspruch 12;
eine zweite Elektrode; und
einen Elektrolyten, der zwischen der ersten Elektrode und der zweiten Elektrode angeordnet ist.
 
14. Methode zur Herstellung eines Binders, wobei die Methode umfasst
Herstellen einer dritten Zusammensetzung durch Zusammenmischen einer ersten Zusammensetzung umfassend ein nicht-wässriges Lösungsmittel und ein erstes Polymer und einer zweiten Zusammensetzung umfassend ein zweites Polymer und Wasser,
wobei das erste Polymer ausgewählt ist aus mindestens einer/einem von einer Polyaminsäure und einem aus der Polyaminsäure gehärteten Polyimid, wobei die Polyaminsäure dargestellt ist durch Formel 1 oder Formel 2:





wobei, in Formeln 1 und 2, gilt:

M ist ein Alkalimetall;

Ar1 und Ar3 sind jeweils unabhängig eine aromatische Gruppe ausgewählt aus einer substituierten oder unsubstituierten tetravalenten C6-C24-Arylengruppe und einer substituierten oder unsubstituierten tetravalentem C4-C24-Heteroarylengruppe, wobei die aromatische Gruppe ein aromatischer Ring, ein Ring umfassend mindestens zwei miteinander fusionierte aromatische Ringe mindestens zwei durch eine Einfachbindung verknüpfte aromatische Ringe, -O-, -S-, - C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH- ist, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

Ar2 und Ar4 sind jeweils unabhängig eine aromatische Gruppe ausgewählt aus einer substituierten oder unsubstituierten divalenten C6-C24-Arylengruppe und einer substituierten oder unsubstituierten divalenten C4-C24-Heteroarylengruppe, wobei die aromatische Gruppe ein aromatischer Ring, ein Ring aufweisend mindestens zwei miteinander fusionierte aromatische Ringe oder ein Ring umfassend mindestens zwei durch eine Einfachbindung verknüpfte aromatische Ringe, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, eine C1-C10-Alkylengruppe substituiert oder unsubstituiert mit einem Halogen oder -C(=O)-NH- ist, wobei Ra und Rb jeweils unabhängig eine substituierte oder unsubstituierte C1-C10-Alkylgruppe sind;

X1 ist -C(=O)OH, -OH, -C(=O)-NH2 oder -C(=O)H; und

n und m sind jeweils ein Molverhältnis einer Wiederholeinheit, wobei 0<n<1, 0<m<1 und n+m=1, und

das zweite Polymer umfasst einen Polyvinylalkohol; und

Erhitzen der dritten Zusammensetzung bei einer Temperatur von 160 °C oder mehr, um ein drittes Polymer herzustellen, bevorzugt, wobei das erste Polymer ferner ein Alkalimetall umfasst.
 


Revendications

1. Liant comprenant :

un troisième polymère comprenant un produit réticulé d'un premier polymère et d'un deuxième polymère ;

dans lequel le premier polymère est au moins l'un choisi parmi un acide polyamique et un polyimide durci à partir de l'acide polyamique,

dans lequel l'acide polyamique est représenté par la formule 1 ou la formule 2 :



dans lequel, dans les formules 1 et 2,

M représente un métal alcalin ;

Ar1 et Ar3 représentent chacun indépendamment un groupe aromatique choisi parmi un groupe arylène en C6-C24 tétravalent substitué ou non substitué et un groupe hétéroarylène en C4-C24 tétravalent substitué ou non substitué, dans lequel le groupe aromatique est un noyau aromatique, un noyau comprenant au moins deux noyaux aromatiques fusionnés l'un à l'autre, ou un noyau comprenant au moins deux noyaux aromatiques liés par une liaison simple, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, dans lequel Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

Ar2 et Ar4 représentent chacun indépendamment un groupe aromatique choisi parmi un groupe arylène en C6-C24 divalent substitué ou non substitué et un groupe hétéroarylène en C4-C24 divalent substitué ou non substitué, dans lequel le groupe aromatique est un noyau aromatique, un noyau ayant au moins deux noyaux aromatiques fusionnés l'un à l'autre, ou un noyau comprenant au moins deux noyaux aromatiques liés par une liaison simple, -O-, -S-, - C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, dans lequel Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

X1 représente -C(=O)OH, -OH, -C(=O)-NH2, ou -C(=O)H ; et n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1 ;

dans lequel le deuxième polymère est un alcool polyvinylique, et

dans lequel le premier polymère et le deuxième polymère sont réticulés par une liaison ester.


 
2. Liant selon la revendication 1, dans lequel le premier polymère comprend en outre un métal alcalin, de préférence dans lequel une quantité du métal alcalin dans le premier polymère se situe dans une plage allant de 0,2 équivalents à 1,0 équivalent à un rapport d'équivalence par rapport à un groupe carboxyle ou un groupe amide.
 
3. Liant selon la revendications 1 ou la revendication 2,
dans lequel l'acide polyamique est représenté par la formule 3 ou la formule 4 :



dans lequel, dans les formules 3 et 4,

M représente le lithium ou le sodium ;

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, et R16 représentent chacun indépendamment un hydrogène, un halogène, -C(=O)OH, -OH, -C(=O)-NH2, -C(=O)H, un groupe alkyle en C1-C10 substitué ou non substitué par un halogène, un groupe aryle en C6-C20 substitué ou non substitué par un halogène, ou un groupe hétéroaryle en C2-C20 substitué ou non substitué par un halogène ;

Y1 représente une liaison simple, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, où Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué, et R représente un groupe alkyle en C1-C10 ;

au moins l'un choisi parmi R3, R4, R5, et R6 est -C(=O)OH, -OH, -C(=O)-NH2, ou-C(=O)H ; et

n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1.


 
4. Liant selon l'une quelconque des revendications 1 à 3, dans lequel le polyimide est représenté par la formule 5 ou la formule 6 :



dans lequel, dans les formules 5 et 6,

M représente un métal alcalin ;

Ar1 et Ar3 représentent chacun indépendamment un groupe aromatique choisi parmi un groupe arylène en C6-C24 tétravalent substitué ou non substitué et un groupe hétéroarylène en C4-C24 tétravalent substitué ou non substitué, dans lequel le groupe aromatique est un noyau aromatique, un groupe comprenant au moins deux noyaux aromatiques fusionnés l'un à l'autre, ou un noyau comprenant au moins deux noyaux aromatiques liés par une liaison simple, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, où Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

Ar2 et Ar4 représentent chacun indépendamment un groupe aromatique choisi parmi un groupe arylène en C6-C24 divalent substitué ou non substitué et un groupe hétéroarylène en C4-C24 divalent substitué ou non substitué, dans lequel le groupe aromatique est un noyau aromatique, un noyau comprenant au moins deux noyaux aromatiques fusionnés l'un à l'autre, ou un noyau comprenant au moins deux noyaux aromatiques liés par une liaison simple, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, où Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

X1 représente -C(=O)OH, -OH, -C(=O)-NH2, ou -C(=O)H ; et n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1, or

dans lequel le polyimide est représenté par la formule 7 ou la formule 8 :



dans lequel, dans les formules 7 et 8,

M représente le lithium ou le sodium ;

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, et R16 représentent chacun indépendamment un hydrogène, un halogène, -C(=O)OH, -OH, -C(=O)-NH2, -C(=O)H, un groupe alkyle en C1-C10 substitué ou non substitué par un halogène, un groupe aryle en C6-C20 substitué ou non substitué par un halogène, ou un groupe hétéroaryle en C2-C20 substitué ou non substitué par un halogène ;

Y1 représente une liaison simple, -O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, où Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

au moins l'un choisi parmi R3, R4, R5, et R6 est -C(=O)OH, -OH, -C(=O)-NH2, ou-C(=O)H ; et

n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1.


 
5. Liant selon l'une quelconque des revendications 1 à 4, dans lequel l'acide polyamique est représenté par la formule 9 ou la formule 10, et le polyimide est représenté par la formule 11 ou la formule 12 :







dans lequel, dans les formules 9 à 12,
n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1, de préférence dans lequel 0<n<0,5, 0,5<m<1, et n + m = 1.
 
6. Liant selon l'une quelconque des revendications 1 à 5, dans lequel un degré de saponification de l'alcool polyvinylique se situe dans la plage allant de 60 % à 99 %, et/ou dans lequel un poids moléculaire moyen en poids de l'alcool polyvinylique se situe dans la plage allant de 10,000 Daltons à 500,000 Daltons.
 
7. Liant selon l'une quelconque des revendications 1 à 6, dans lequel un rapport massique du premier polymère et du deuxième polymère se situe dans la plage allant de 1:99 à 50:50.
 
8. Liant selon l'une quelconque des revendications 1 à 7, dans lequel la réticulation se produit à une température supérieure ou égale à 160° C.
 
9. Liant selon l'une quelconque des revendications 1 à 8, dans lequel un module d'indentation du troisième polymère est supérieur à chacun des modules du premier polymère et à chacun des modules du deuxième polymère, et/ou dans lequel une dureté d'indentation du troisième polymère est supérieure à chaque dureté d'indentation du premier polymère et à chaque dureté d'implantation du deuxième polymère.
 
10. Liant selon l'une quelconque des revendications 1 à 9, dans lequel le troisième polymère présente une structure en réseau comprenant le produit réticulé du premier polymère et du deuxième polymère, et/ou dans lequel un poids moléculaire moyen poids du troisième polymère se situe dans la plage allant de 10,000 Daltons à 1,000,000 Daltons.
 
11. Liant selon l'une quelconque des revendications 1 à 10, dans lequel le troisième polymère est représenté par l'une des formules 13 à 16 :









dans lequel, dans les formules 13 à 16,

n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1 ; et

p est un degré de polymérisation qui se situe dans la plage allant de 250 à 12,500.


 
12. Électrode comprenant
le liant selon l'une quelconque des revendications 1 à 11 ; et
un matériau actif de cathode ou un matériau actif d'anode, de préférence dans lequel le matériau actif d'anode comprend au moins l'un choisi parmi un métal lithium ; un métal alliable au lithium ; un composite d'un métal alliable au lithium et de carbone ; un composite d'un métal alliable au lithium et d'azote ; un composite d'un métal alliable au lithium, d'azote, et de carbone ; un composite d'un métal alliable au lithium et d'un métal qui est inerte au lithium ; un composite d'un métal alliable au lithium et d'un oxyde métallique qui est inerte au lithium ; un composite d'un métal alliable au lithium et d'un nitrure métallique qui est inerte au lithium ; et un composite d'un métal alliable au lithium et d'un nitrate métallique qui est inerte au lithium, et/ou dans lequel le matériau actif d'anode comprend au moins l'un choisi parmi un matériau actif de silicium, un matériau actif d'étain, un matériau actif d'alliage de silicium et d'étain, et un matériau actif de silicium-carbone, et/ou dans lequel une expansion d'épaisseur de l'électrode calculée conformément à l'équation 1 est inférieure à 54 %.


 
13. Batterie au lithium comprenant
une première électrode comprenant l'électrode de la revendication 12 ;
une seconde électrode ; et
un électrolyte disposé entre la première électrode et la seconde électrode.
 
14. Procédé de préparation d'un liant, le procédé comprenant
la préparation d'une troisième composition en mélangeant ensemble une première composition comprenant un solvant non aqueux et un premier polymère et une deuxième composition comprenant un deuxième polymère et de l'eau,
dans lequel le premier polymère est choisi parmi au moins l'un parmi un acide polyamique et un polyimide durci à partir de l'acide polyamique, dans lequel l'acide polyamique est représenté par la formule 1 ou la formule 2 :





dans lequel, dans les formules 1 et 2,

M représente un métal alcalin ;

Ar1 et Ar3 représentent chacun indépendamment un groupe aromatique choisi parmi un groupe arylène en C6-C24 tétravalent substitué ou non substitué et un groupe hétéroarylène en C4-C24 tétravalent substitué ou non substitué, dans lequel le groupe aromatique est un noyau aromatique, un noyau comprenant au moins deux noyaux aromatiques fusionnés l'un à l'autre,

ou un noyau comprenant au moins deux noyaux aromatiques liés par une liaison simple,-O-, -S-, -C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, dans lequel Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

Ar2 et Ar4 représentent chacun indépendamment un groupe aromatique choisi parmi un groupe arylène en C6-C24 divalent substitué ou non substitué et un groupe hétéroarylène en C4-C24 divalent substitué ou non substitué, dans lequel le groupe aromatique est un noyau aromatique, un noyau ayant au moins deux noyaux aromatiques fusionnés l'un à l'autre, ou un noyau comprenant au moins deux noyaux aromatiques liés par une liaison simple, -O-, -S-,-C(=O)-, -S(=O)2-, -Si(Ra)(Rb)-, un groupe alkylène en C1-C10 substitué ou non substitué par un halogène, ou -C(=O)-NH-, dans lequel Ra et Rb représentent chacun indépendamment un groupe alkyle en C1-C10 substitué ou non substitué ;

X1 représente -C(=O)OH, -OH, -C(=O)-NH2, ou -C(=O)H ; et n et m sont chacun un rapport molaire d'une unité de répétition, où 0<n<1, 0<m<1, et n + m = 1, et

le deuxième polymère comprend un alcool polyvinylique ; et

chauffage de la troisième composition une température supérieure ou égale à 160 °C afin de préparer un troisième polymère, de préférence dans lequel le premier polymère comprend en outre un métal alcalin.


 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description