(19)
(11)EP 2 905 831 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
20.12.2017 Bulletin 2017/51

(21)Application number: 14842619.0

(22)Date of filing:  03.09.2014
(51)Int. Cl.: 
H01M 4/38  (2006.01)
H01M 4/525  (2010.01)
H01M 4/58  (2010.01)
H01M 4/485  (2010.01)
H01M 10/052  (2010.01)
(86)International application number:
PCT/KR2014/008264
(87)International publication number:
WO 2015/034257 (12.03.2015 Gazette  2015/10)

(54)

CATHODE ADDITIVE FOR HIGH-CAPACITY LITHIUM SECONDARY BATTERY

KATHODENADDITIV FÜR EINE HOCHKAPAZITIVE LITHIUMSEKUNDÄRBATTERIE

ADDITIF DE CATHODE POUR BATTERIE SECONDAIRE AU LITHIUM À HAUTE CAPACITÉ


(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: 05.09.2013 KR 20130106746

(43)Date of publication of application:
12.08.2015 Bulletin 2015/33

(73)Proprietor: LG Chem, Ltd.
Seoul 150-721 (KR)

(72)Inventors:
  • PARK, Sun-Ju
    Daejeon 305-380 (KR)
  • YUN, Sook
    Daejeon 305-380 (KR)
  • JO, Vin-Na
    Daejeon 305-380 (KR)
  • KU, Cha-Hun
    Daejeon 305-380 (KR)
  • PARK, Pil-Kyu
    Daejeon 305-380 (KR)

(74)Representative: Cabinet Plasseraud 
66, rue de la Chaussée d'Antin
75440 Paris Cedex 09
75440 Paris Cedex 09 (FR)


(56)References cited: : 
EP-A1- 2 139 059
EP-A1- 2 584 634
KR-A- 20100 136 073
KR-A- 20110 107 718
KR-B1- 100 544 515
EP-A1- 2 246 922
WO-A1-03/081697
KR-A- 20110 058 129
KR-A- 20120 108 902
US-A1- 2012 164 533
  
     
    Remarks:
    The file contains technical information submitted after the application was filed and not included in this specification
     
    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

    TECHNICAL FIELD



    [0001] The present disclosure relates to an additive to be used in the cathode of a lithium secondary battery with high capacity, more specifically a lithium secondary battery comprising Li2NiO2 in a cathode so as to improve the phenomenon that a capacity retention ratio decreases during initial cycles when a non-carbon-based material is used as an anode active material.

    BACKGROUND ART



    [0002] Recently, there has been an increasing interest in energy storage technology. As the application fields of energy storage technologies have been extended to mobile devices such as cellular phones, camcorders and notebook computers, as well as electric motors, the demand for batteries as a power source to have high energy density has been increasing. Lithium secondary batteries are considered as the best one capable of satisfying such a demand, and the researches thereof have been actively made.

    [0003] Among secondary batteries currently used, a lithium secondary battery developed in the early 1990's comprises an anode made of carbon materials capable of intercalating or disintercalating lithium ions, a cathode made of lithium-containing oxides, and a non-aqueous electrolyte solution obtained by dissolving a suitable amount of lithium salt in a mixed organic solvent. EP 2 246 922, EP 2 139 059, EP 2 584 634, US 2012/164533, WO 03/081697 and KR 20110058129 disclose lithium secondary batteries comprising a positive electrode active material based on a mixture of a lithium transition metal oxide and Li2NiO2. As the anode active material of the lithium secondary battery, various carbon-based materials, including artificial graphite, natural graphite, and hard carbon which can intercalate and disintercalate lithium ions have been used. Among these carbon-based materials, graphite has low discharge voltage of -0.2V relative to lithium, so a battery using graphite as an anode active material exhibits high discharge voltage of 3.6V. Therefore, such a graphite active material has been the most widely used since it can provide advantages in term of the energy density of a lithium battery and also has good reversibility to ensure the long life time of the lithium secondary battery. However, the graphite active material has low density (theoretical density 2.2 g/cc) in the preparation of an electrode to provide low capacity, which is unfavorable in terms of energy density per unit volume of the electrode, and also it is apt to react with organic electrolyte adversely at high discharge voltage, which may result in ignition or explosion by the abnormal operation, overcharging of the battery and so on.

    [0004] Recently, as the use of lithium secondary batteries expands, there are gradually increasing demands for a lithium secondary battery capable of maintaining good performances under severe conditions such as high temperature and/or low temperature and being stably charged even at high voltage.

    [0005] Meanwhile, it is possible to improve the capacity characteristic of a lithium secondary battery by changing carbon-based anode active materials with non-carbon-based materials such as silicon oxide. However, some anode materials including silicon oxide are irreversible. Therefore, some anode materials intercalate lithium ions at the first chargee and cannot disintercalate about 20% of the lithium ions in the later discharge. Accordingly, about 20% of cathode active materials used in the first charge cannot be involved in the following charge and discharge after the first charge, and eventually the efficiency of the lithium secondary battery is lowered.

    [0006] In order to solve this problem, there has been attempted to prepare a nanoparticle composite consisting of a carbon-based material and a silicon-based material and use it as an anode active material. Such a nanoparticle composite can improve the capacity retention ratio of a battery to a degree by means of the carbon-based material acting as an electrical conductor. However, the carbon-based material should be excessively present in an amount more than 50 wt% in the nanoparticle composite in order to provide relatively good capacity retention to the battery, which reduces a capacity of the battery. Further, although the carbon-based material present in an excessive amount as disclosed in the above, there is still a problem that a capacity on or after the 50th cycle is lowered less than 1500 mAh/g.

    [0007] Therefore, there is a need to develop a lithium secondary battery that can improve the capacity retention ratio during initial cycles when a non-carbon-based material is used as an anode material.

    DISCLOSURE


    Technical Problem



    [0008] The present disclosure is designed to solve the above-mentioned problems, and therefore it is an object of the present disclosure to provide a lithium secondary battery that can improve the capacity retention ratio during initial cycles when a non-carbon-based material is used as an anode material.

    [0009] For this, the present disclosure provides a lithium secondary battery that can supply sufficient lithium in an anode at the first charge and supplement lithium being consumed in the anode during cycling.

    Technical Solution



    [0010] In order to achieve the above object, in accordance with one aspect of the present disclosure, there is provided a lithium secondary battery as defined in claim 1. Besides Li2NiO2, the cathode active material may further contain any one selected from the group consisting of LixCoO2(0.5<x<1.3), LixNiO2(0.5<x<1.3), LixMnO2(0.5<x<1.3), LixMn2O4(0.5<x<1.3), Lix(NiaCobMnc)O2(0.5<x<1.3, 0<a<1, 0<b<1, 0<c<1, a+b+c=1), LixNi1-yCoyO2(0.5<x<1.3, 0<y<1), LixCo1-yMnyO2(0.5<x<1.3, 0≤y<1), LixNi1-yMnyO2(0.5<x<1.3, 0≤y<1), Lix(NiaCobMnc)O4(0.5<x<1.3, 0<a<2, 0<b<2, 0<c<2, a+b+c=2), LixMn2-zNizO4(0.5<x<1.3, 0<z<2), LixMn2-zCozO4(0.5<x<1.3, 0<z<2), LixCoPO4(0.5<x<1.3), LixFePO4(0.5<x<1.3) and a mixture thereof.

    [0011] The lithium secondary battery can have a capacity retention ratio of 90% or more after 50 cycles.

    Advantageous Effects



    [0012] The lithium secondary battery according to the present disclosure can remarkably improve the capacity retention ratio during initial cycles and, therefore, show a high capacity retention ratio.

    DESCRIPTION OF DRAWINGS



    [0013] The accompanying drawings illustrate preferred embodiments of the present disclosure. However, the present disclosure is not to be construed as being limited to the drawings.

    [0014] FIG. 1 is a graph showing capacity retention ratio (%) over cycles of batteries (cells) prepared in the Example 1 and the Comparative Example 1of the present disclosure.

    BEST MODE



    [0015] Hereinafter, the present disclosure will be described in detail. Prior to the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present disclosure on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.

    [0016] The cathode of the present disclosure comprises lithium nickel oxide expressed by Li2NiO2. Li2NiO2 can disintercalate lithium ion in an amount of 1 mol or more on the first charge, and then can intercalate and disintercalate lithium ion in an amount of 1 mol or less on and after the first discharge. Accordingly, Li2NiO2 added to the cathode can provide lithium ions enough to supplement the irreversibility of an anode, and thus the great irreversibility of the anode on the first discharge can be supplemented.

    [0017] Li2NiO2 is contained in an amount of 1 to 10 wt% of the cathode active material. When the amount of Li2NiO2 satisfies such range, the charging and discharging processes can be made without battery damage and the cycle characteristics of the battery may not deteriorate. More specifically, the lithium secondary battery can exhibit a capacity retention ratio of 90% or more on or after the 50th cycle. If Li2NiO2 is used in an amount exceeding the upper limit, Li2NiO2 is subject to a phase change into LiNiO2 after the first charge, thereby battery safety unfavorably deteriorates. Generally, LiNiO2 has a lower stability than that of LiCoO2.

    [0018] Other cathode active materials which may be used together with lithium nickel oxide are not particularly limited if they have been conventionally used in the art. Non-limiting examples of the usable cathode active materials may include lithium-containing transition metal oxides, for example, LixCoO2(0.5<x<1.3), LixNiO2(0.5<x<1.3), LixMnO2(0.5<x<1.3), LixMn2O4(0.5<x<1.3), Lix(NiaCobMnc)O2(0.5<x<1.3, 0<a<1, 0<b<1, 0<c<1, a+b+c=1), LixNi1-yCoyO2(0.5<x<1.3, 0<y<1), LixCo1-yMnyO2(0.5<x<1.3, 0≤y<1), LixNi1-yMnyO2(0.5<x<1.3, 0≤y<1), Lix(NiaCobMnc)O4(0.5<x<1.3, 0<a<2, 0<b<2, 0<c<2, a+b+c=2), LixMn2-zNizO4(0.5<x<1.3, 0<z<2), LixMn2-zCozO4(0.5<x<1.3, 0<z<2), LixCoPO4(0.5<x<1.3), LixFePO4(0.5<x<1.3) and a mixture thereof. These lithium-containing transition metal oxides may be coated with a metal such as aluminum (Al) or a metal oxide. Also, besides the lithium-containing transition metal oxides, sulfides, selenides and halides of lithium-containing transition metals may also be used.

    [0019] The anode of the present disclosure comprises an anode active material containing a carbon-based material and SiOx (0 < x < 2).

    [0020] Generally, batteries may be prepared considering design factors, which include an electrochemical balance between a cathode and an anode. That is, even though the batteries are designed to adopt a cathode with high capacity and an anode with high capacity, it does not mean that such batteries necessarily exhibit a high capacity. In this aspect, in order to prepare a battery with high capacity, the anode active material containing SiOx (0 < x < 2)in an amount of 1 to 15 wt% of the total anode active materials. It is difficult to supplement the irreversibility of lithium ions even though Li2NiO2 is used in the cathode active material in case that the anode active material is used in an amount exceeding the upper limit. If the anode active material is used in an amount less than the lower limit, the effect of capacity increase is insufficient.

    [0021] Non-limiting examples of other anode active materials which have been conventionally used in the art may include metallic lithium and so on which can intercalate and disintercalate lithium ions. The carbon-based material is selected from soft carbon and hard carbon, natural graphite, Kish graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches, and petroleum or coal tar pitch derived cokes, and a mixture thereof.

    [0022] The cathode and/or the anode may comprise a binder, and various kinds of binder polymers including vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile and polymethylmethacrylate may be used as the binder.

    [0023] The above-mentioned lithium secondary battery of the present disclosure is prepared by introducing a non-aqueous electrolyte solution in an electrode assembly consisting of a cathode, an anode, and a separator interposed therebetween. As the cathode, anode, and separator constituting the electrode assembly, those which have been conventionally used in the preparation of lithium secondary batteries may be used.

    [0024] Also, the separator may be obtained from a porous polymer film which is conventionally used alone or in the form of lamination in conventional separators, for example, porous polymer films made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer and ethylene/methacrylate copolymer. Also, as the separator, conventional porous non-woven fabrics such as a non-woven fabric made of glass fiber having a high melt point or polyethylene terephthalate fiber may be used, but is not limited thereto.

    [0025] The non-aqueous electrolyte solution used in the present disclosure comprises a lithium salt as an electrolyte salt. The lithium salt may be any one which is conventionally used in an electrolyte solution for a lithium secondary battery. For example, an anion of the lithium salt may be any one selected from the group consisting of F-, Cl-, Br-, I-, NO3-, N(CN)2-, BF4-, ClO4-, PF6-, (CF3)2PF4-, (CF3)3PF3-, (CF3)4PF2-, (CF3)5PF-, (CF3)6P-, CF3SO3-, CF3CF2SO3-, (CF3SO2)2N-, (FSO2)2N-, CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3-, CF3CO2-, CH3CO2-, SCN- and (CF3CF2SO2)2N-.

    [0026] The non-aqueous electrolyte solution used in the present disclosure comprises an organic solvent which is conventionally used in an electrolyte solution for a lithium secondary battery, for example, ethers, esters, amides, linear carbonates, cyclic carbonates, and a mixture thereof.

    [0027] Among these, a carbonate compound such as a linear carbonate, a cyclic carbonate, or a mixture thereof is representatively used. Specific examples of the cyclic carbonate may include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, a halide thereof and a mixture thereof. Specific examples of the linear carbonate may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate and a mixture thereof, but are not limited thereto.

    [0028] In particular, among the above carbonate-based organic solvents, the cyclic carbonates such as ethylene carbonate and propylene carbonate are preferably used since they have a high viscosity and a high dielectric constant to more easily dissociate a lithium salt in an electrolyte. More preferably, such a cyclic carbonate can be mixed with a linear carbonate with low viscosity and low dielectric constant such as dimethyl carbonate and diethyl carbonate in a suitable ratio to provide an electrolyte solution with a high electric conductivity.

    [0029] Also, the ether which may be used as the organic solvent is any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether and a mixture thereof, but is not limited thereto.

    [0030] In addition, the ester which may be used as the organic solvent is any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone, ε-caprolactone and a mixture thereof, but is not limited thereto.

    [0031] In addition, the electrochemical device of the present disclosure is not limited to its shape. For example, the shape of the electrochemical device may be cylindrical such as a can, prismatic, pouch, or coin.

    [0032] Hereinafter, preferred examples of the present disclosure will be described in detail for better understanding. However, the examples of the present disclosure may be modified in various ways, and they should not be interpreted as limiting the scope of the invention. The examples of the present disclosure are just for better understanding of the invention to persons having ordinary skill in the art.

    Example 1



    [0033] A cathode active material consisting of Al-doped LiNiCoO2 (LiNi0.80Co0.15Al0.05O2) and Li2NiO2 in a weight ratio of 95:5 was provided. Subsequently, the cathode active material, polyvinylidene fluoride as a binder, and carbon as a conductive material were mixed in the weight ratio of 8:1:1, and the mixture was dispersed in N-methyl-pyrrolidone to obtain a cathode slurry. The slurry was coated on a current collector made of aluminum, followed by drying and compressing, to prepare a cathode.

    [0034] Also, an anode active material consisting of graphite and SiO in the weight ratio of 9:1 was provided. Subsequently, the anode active material, styrene butadiene rubber (SBR), and carboxyl methyl cellulose (CMC) were mixed in a weight ratio of 90:5:5, and the mixture was dispersed in water to obtain an anode slurry. The slurry was coated on a current collector made of copper, followed by drying and compressing, to prepare an anode.

    [0035] 1M LiPF6 solution comprising ethylene carbonate and ethylmethyl carbonate in the volume ratio of 1:2 was used as an electrolyte solution.

    [0036] Then, the cathode and the anode obtained above were assembled with a polyethylene(PE) separator by a conventional method to prepare a coin-type full cell, in which the electrolyte solution was introduced. Thereby, the coin-type full cell was finally prepared.

    Comparative Example 1



    [0037] The procedures of Example 1 were repeated except that Li2NiO2 was not used, to prepare a coin-type full cell.

    Test Example: Measurement of Capacity Retention ratio per Cycle



    [0038] The coin-type full cells prepared in Example 1 and Comparative Example 1 were tested on charge and discharge cycles under the conditions of 0.5C charge and 1C discharge, and the results thereof are shown in FIG. 1.

    [0039] As shown in FIG. 1, the lithium secondary battery of Example 1 exhibited and maintained a remarkable improvement of phenomenon that a capacity retention ratio (%) decreases at the initial cycles, as compared with that of Comparative Example 1.


    Claims

    1. A lithium secondary battery comprising a cathode comprising a cathode active material, an anode comprising an anode active material and a separator, wherein:

    - the cathode active material contains a compound of Li2NiO2 in an amount of 1 to 10 wt% of the cathode active material, and

    - the anode active material containing:

    ∘ a carbon-based material selected from the group consisting of soft carbon, hard carbon, natural graphite, Kish graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches, petroleum derived cokes, coal tar pitch derived cokes and a mixture thereof, and

    ∘ SiOx (0 < x < 2) in an amount of 1 to 15 wt% of the total anode active material.


     
    2. The lithium secondary battery of claim 1, wherein the cathode active material further contains any one selected from the group consisting of LixCoO2(0.5<x<1.3), LixNiO2(0.5<x<1.3), LixMnO2(0.5<x<1.3), LixMn2O4(0.5<x<1.3), Lix(NiaCobMnc)O2(0.5<x<1.3, 0<a<1, 0<b<1, 0<c<1, a+b+c=1), LixNi1-yCoyO2(0.5<x<1.3, 0<y<1), LixCo1-yMnyO2(0.5<x<1.3, 0≤y<1), LixNi1-yMnyO2(0.5<x<1.3, 0≤y<1), Lix(NiaCobMnc)O4(0.5<x<1.3, 0<a<2, 0<b<2, 0<c<2, a+b+c=2), LixMn2-zNizO4(0.5<x<1.3, 0<z<2), LixMn2-zCozO4(0.5<x<1.3, 0<z<2), LixCoPO4(0.5<x<1.3), LixFePO4(0.5<x<1.3) and a mixture thereof.
     


    Ansprüche

    1. Lithiumsekundärbatterie umfassend eine Kathode umfassend ein aktives Kathodenmaterial, eine Anode umfassend ein aktives Anodenmaterial und einen Separator, wobei:

    - das aktive Kathodenmaterial eine Verbindung von Li2NiO2 in einer Menge von 1 bis 10 Gew.-% des aktiven Kathodenmaterials enthält, und

    - das aktive Anodenmaterial enthält:

    ∘ ein kohlenstoffbasiertes Material ausgewählt aus der Gruppe bestehend aus weichem Kohlenstoff, hartem Kohlenstoff, Naturgraphit, Kishgraphit, Pyrokohlenstoff, Mesophasepechbasierter Kohlenstofffaser, Mesokohlenstoffmikrobeads, Mesophasepech, Mineralölkoks, Steinkohlenteerpechkoks und einer Mischung davon, und

    ∘ SiOx (0 < x < 2) in einer Menge von 1 bis 15 Gew.-% des gesamten aktiven Anodenmaterials.


     
    2. Lithiumsekundärbatterie nach Anspruch 1, wobei das aktive Kathodenmaterial ferner eines ausgewählt aus der Gruppe bestehend aus LixCoO2(0,5<x<1,3), LixNiO2(0,5<x<1,3), LixMnO2(0,5<x<1,3), LixMn2O4(0,5<x<1,3), Lix(NiaCobMnc)O2(0,5<x<1,3, 0<a<1, 0<b<1, 0<c<1, a+b+c=1), LixNi1-yCoyO2(0,5<x<1,3, 0<y<1), LixCo1-yMnyO2(0,5<x<1,3, 0≤y<1), LixNi1-yMnyO2(0,5<x<1,3, 0≤y<1), Lix(NiaCobMnc)O4(0,5<x<1,3, 0<a<2, 0<b<2, 0<c<2, a+b+c=2), LixMn2-zNizO4(0,5<x<1,3, 0<z<2), LixMn2-zCozO4(0,5<x<1,3, 0<z<2), LixCoPO4(0,5<x<1,3), LixFePO4(0,5<x<1,3) und einer Mischung davon ist.
     


    Revendications

    1. Batterie secondaire au lithium comprenant une cathode comprenant un matériau actif de cathode, une anode comprenant un matériau actif d'anode et un séparateur, dans laquelle :

    - le matériau actif de cathode contient un composé de Li2NiO2 dans une quantité de 1 à 10 % en poids du matériau actif de cathode, et

    - le matériau actif d'anode contenant :

    ∘ un matériau à base de carbone choisi dans le groupe constitué du carbone doux, du carbone dur, du graphite naturel, du graphite de sursaturation, du carbone pyrolytique, d'une fibre de carbone à base de brai en mésophase, de microbilles de carbone méso, de braies en mésophase, de cokes dérivés du pétrole, de cokes dérivés du brai de goudron de houille et d'un mélange de ceux-ci, et

    ∘ du SiOx (0 < x < 2) dans une quantité de 1 à 15 % en poids du matériau actif d'anode total.


     
    2. Batterie secondaire au lithium selon la revendication 1, dans laquelle le matériau actif de cathode contient en outre l'un quelconque choisi dans le groupe constitué de LixCoO2(0,5 < x < 1,3), LixNiO2(0,5 < x < 1,3), LixMnO2(0,5 < x < 1,3), LixMn2O4(0,5 < x < 1,3), Lix(NiaCobMnc)O2(0,5 < x < 1,3, 0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1), LixNi1-yCoyO2(0,5 < x < 1,3, 0 < y < 1), LixCo1-yMnyO2(0,5 < x < 1,3, 0 ≤ y < 1), LixNi1-yMnyO2(0,5 < x < 1,3, 0 ≤ y < 1), Lix(NiaCobMnc)O4(0,5 < x < 1,3, 0 < a< 2,0 < b < 2,0 < c < 2, a + b + c = 2), LixMn2-zNizO4(0,5 < x < 1,3, 0 < z < 2), LixMn2-zCozO4(0,5 < x < 1,3, 0 < z <2), LixCoPO4(0,5 < x < 1,3), LixFePO4(0,5 < x < 1,3) et un mélange de ceux-ci.
     




    Drawing






    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description