(19)
(11)EP 2 696 403 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
15.04.2015 Bulletin 2015/16

(21)Application number: 13179198.0

(22)Date of filing:  05.08.2013
(51)Int. Cl.: 
H01M 4/131  (2010.01)
H01M 4/48  (2010.01)
H01M 4/36  (2006.01)
H01M 4/02  (2006.01)
H01M 4/134  (2010.01)
H01M 10/0525  (2010.01)
H01M 4/62  (2006.01)

(54)

Negative active material for a rechargeable lithium battery and method of preparing the same

Negatives Aktivmaterial für eine wiederaufladbare Lithiumbatterie und Verfahren zur Herstellung dafür

Matériau actif négatif pour batterie au lithium rechargeable et son procédé de préparation


(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: 06.08.2012 US 201261680068 P
31.07.2013 US 201313956230

(43)Date of publication of application:
12.02.2014 Bulletin 2014/07

(73)Proprietor: Samsung SDI Co., Ltd.
Gyeonggi-do (KR)

(72)Inventors:
  • KIM, Young-Ugk
    Yongin-si (KR)
  • KIM, Jae-Myung
    Yongin-si (KR)
  • JOO, Kyu-Nam
    Yongin-si (KR)
  • PARK, Sang-Eun
    Yongin si (KR)
  • KIM, Deok-Hyun
    Yongin-si (KR)
  • KIM, Yeon-Gap
    Yongin-si (KR)

(74)Representative: Gulde & Partner 
Patent- und Rechtsanwaltskanzlei mbB Wallstraße 58/59
10179 Berlin
10179 Berlin (DE)


(56)References cited: : 
EP-A1- 1 986 253
US-A1- 2010 119 948
US-A1- 2006 099 507
  
  • YAN YAO ET AL: "Interconnected Silicon Hollow Nanospheres for Lithium-Ion Battery Anodes with Long Cycle Life", NANO LETTERS, vol. 11, no. 7, 13 July 2011 (2011-07-13), pages 2949-2954, XP055046276, ISSN: 1530-6984, DOI: 10.1021/nl201470j
  
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


[0001] The present invention refers to a negative active material for a rechargeable lithium battery and a method of preparing the same.

Description of the Related Art



[0002] A lithium rechargeable battery has recently drawn attention as a power source for a small portable electronic device. It uses an organic electrolyte solution and thereby, has twice high discharge voltage as a conventional battery using an alkali aqueous solution and as a result, has high energy density.

[0003] As for positive active materials for a rechargeable lithium battery, lithium-transition element composite oxides being capable of intercalating lithium such as LiCoO2, LiMn2O4, LiNi1-xCoxO2 (0<x<1), and so on, have been researched.

[0004] As for negative active materials of a rechargeable lithium battery, various carbon-based materials such as artificial graphite, natural graphite, and hard carbon, which can intercalate and deintercalate lithium ions, have been used. However, a non-carbon-based negative active material such as Si in accordance with need for stability and high-capacity has been recently researched.

[0005] Yan You et al., Nano Lett. 2011, 11, 2949 - 2954 disclose interconnected silicon hollow nanospheres for Li-ion battery anodes. Si is deposited onto SiO2 particles and the SiO2 core is removed afterwards by HF etching. US 2006/0099507 A1, US 2010/0119948 A1 and EP 1 986 253 A1 refer to negative electrodes of Li secondary batteries including different negative active material layers disposed on current collectors, wherein the content of oxygen increases from the surface of the active material layer towards the collector.

SUMMARY OF THE INVENTION



[0006] The present invention provides a negative active material for a rechargeable lithium battery having low sheet resistance and thus, improving cycle-life as well as electrochemical properties of a rechargeable lithium battery.

[0007] The present invention provides also a method of preparing the negative active material.

[0008] According to one aspect of the present invention, there is provided a negative active material for a rechargeable lithium battery including surface modified silicon oxide particles having a bulk formula represented by SiOx (0<x<2) and having a ratio of silicon relative to oxygen (Si/O ratio) on the surface of the particles is in the range of 1.8 to 2.4, especially in the range of 2.0 to 2.3.

[0009] A content of silicon (Si) decreases from the surface toward the core of the particles, while the content of oxygen (O) increases from the surface toward the core of the particles.

[0010] Further, x may be in the range of 0.5 to 1.5, especially in the range of 0.6 to 0.95.

[0011] According to another preferred embodiment of the invention, the negative active material has a specific surface area of 10 to 500 m2/g, especially of 10 to 40 m2/g.

[0012] The negative active material may further include one or more additional element selected from the group consisting of an alkali metal, an alkaline-earth metal, an element belonging to groups 13 to 16, a transition metal and a rare earth metal. The additional element may be selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te and Po.

[0013] The negative active material may have an average particle size of 0.1 µm to 100 µm.

[0014] A coating layer may be formed on the surface of the silicon oxide particles.

[0015] The negative active material may further include a carbon-based material. Preferably, the carbon-based material is one selected of graphite, carbon black, acetylene black or ketjen black. The carbon-based material may be provided in form of particles having an average particle size which is 0.01 to 0.5 times of the average particle size of the silicon oxide particles. An amount of carbon-based material may be 1 to 50 parts by weight based on 100 parts by weight of the silicon oxide particles.

[0016] According to another aspect of the present invention, there is provided a method of preparing the before mentioned negative active material for a rechargeable lithium battery. The method includes the step of treating amorphous silicon oxide powder with an etchant.

[0017] Preferably, the etchant includes at least one of nitric acid, sulfuric acid, HF, NH4F and NH4HF2.

[0018] The amorphous silicon oxide powder and the etchant may be used in a mole ratio of 10 : 1 to 1 : 10.

[0019] According to still another embodiment of the present invention, provided is a rechargeable lithium battery including a negative electrode including the negative active material; a positive electrode including a positive active material; and a non-aqueous electrolyte.

[0020] The negative active material has a low sheet resistance and may improve cycle-life and electrochemical properties of the rechargeable lithium battery.

BRIEF DESCRIPTION OF THE DRAWINGS



[0021] 

FIG. 1 is a schematic view of a rechargeable lithium battery according to one embodiment of the present invention.

FIG. 2 is an XPS (X-ray photoelectron spectroscopy) analysis graph of the negative active material particle according to Comparative Example 1.

FIG. 3 is an XPS analysis graph of the negative active material particle according to Comparative Example 2.

FIG. 4 is an XPS analysis graph of the negative active material particle according to Comparative Example 3.

FIG. 5 is an XPS analysis graph of the negative active material particle according to Comparative Example 4.

FIG. 6 is an XPS analysis graph of the negative active material particle according to Example 1.

FIG. 7 is an XPS analysis graph of the negative active material particle according to Example 2.

FIG. 8 is an XPS analysis graph of the negative active material particle according to Example 3.


DETAILED DESCRIPTION



[0022] Exemplary embodiments of the present invention will hereinafter be described in detail.

[0023] Silicon oxide (SiOx) is generally used as a negative active material having high-capacity and prepared by uniformly mixing a silicon (Si) and silicon dioxide (SiO2). However, the silicon oxide has a natural layer having a high oxygen ratio on the surface and thus, a silicon ratio relative to oxygen (Si/O ratio) of less than 0.7. As a result, the high oxygen ratio on the surface of the silicon oxide may work as resistance during an insertion reaction with lithium and thus, deteriorate electrochemical properties of a rechargeable lithium battery.

[0024] The present invention provides a negative active material for a rechargeable lithium battery including surface modified silicon oxide particles having a bulk formula represented by SiOx (0<x<2) and having a ratio of silicon relative to oxygen (Si/O ratio) ranging from 1.8 to 2.4.

[0025] As used herein, the term "a surface modified silicon oxide particle" refers to a silicon oxide particle, the surface of which is modified. In embodiments, the surface of the silicon oxide particle is modified by selectively etching a substantial number of silicon dioxide molecules from the surface. For example, the surface-modified silicon oxide particles have, on their surfaces, a number of pores or recesses of a general size of silicon dioxide molecules as a result of the selective etching. Further, for example, the surface-modified silicon oxide particles include an uneven surface configuration when viewing with a scanning electron microscope (SEM).

[0026] As used herein, the term "bulk formula" refers to a chemical formula based on the average elemental content of a quantity of material in the "overall mass of the particle" rather than in a local mass or portion of the particle. In the bulk formula, the amount of one element is set as the primary integer and the other element(s) amount(s) is/are normalized to that primary integer. For example, Si (silicon) could provide 25% of a bulk material and O (oxygen) could provide 75% of the bulk material corresponding to a generic bulk formula of SiOx (the amount of silicon set as the primary integer of 1, and x is 3 normalized to the primary integer provides a bulk formula of SiO3) or a generic bulk formula of SiyO (the amount of oxygen set as the primary integer of 1, and y is 0.33 normalized to the primary integer provides a bulk formula of Si0.33O). In some embodiments, the material may be surface modified silicon oxide particles where the bulk formula is SiOx (0.5≤x≤1.5).

[0027] Herein, a ratio of silicon and oxygen on the surface of the silicon oxide may be quantitatively analyzed through XPS.

[0028] Conventionally, there are attempts to decrease an oxidation number at a surface of a Si-based negative active material. However, a negative active material having a Si/O ratio of higher than or equal to 1.8 on the surface of a silicon oxide particle has not been suggested. When negative active material having a Si/O ratio of higher than or equal to 1.8 on the surface of a silicon oxide particle, cycle-life may be remarkably improved compared with that having a Si/O ratio of less than 1.8.

[0029] According to another embodiment of the present invention, the silicon oxide particle includes silicon (Si) and oxygen in a ratio of 2.0 to 2.3 on the surface.

[0030] When negative active material having a Si/O ratio of higher than or equal to 2.0 on the surface of a silicon oxide particle, cycle-life may be more improved

[0031] The silicon oxide particles may have a concentration gradient that the silicon (Si) element has an atom% concentration decreasing from the surface toward the core while the oxygen (O) element has an atom% concentration increasing from the surface toward the core.

[0032] In addition, the silicon oxide particle may have a higher surface roughness. When a silicon oxide such as SiO2 is removed, an empty space is formed inside the particle. As a result, the silicon oxide particle have an increased specific surface area. In one embodiment of the present invention, a negative active material including the silicon oxide particle may have a specific surface area ranging from 10 to 500m2/g. In another embodiment, the negative active material may have a specific surface area ranging from 10 to 40 m2/g.

[0033] The silicon oxide particle (SiOx) may have an x value ranging from 0.5 to 1.5. Specifically, the silicon oxide particle (SiOx) may have an x value ranging from about 0.6 to about 0.95. When the silicon oxide particle includes a silicon (Si) element within the range, capacity and efficiency of a lithium battery may be appropriately improved.

[0034] The negative active material may further include crystalline Si.

[0035] The negative active material including the silicon oxide particle may further include one (beside or instead of crystalline Si) selected from an alkali metal, an alkaline-earth metal, an element belonging to Groups 13 to 16, a transition element, a rare earth element, and a combination thereof and specifically, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.

[0036] The negative active material may have an average particle diameter of about 0.9 µm to about 100 µm.

[0037] In addition, the negative active material may further include barrier coating or deposit layer on the surface of the silicon oxide particle.

[0038] The negative active material, especially the coating or deposit layer, may include a carbon-based material such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, and the like.

[0039] The carbon-based material may have a 0.01 to 0.5 times bigger particle size than the silicon oxide particle.

[0040] In addition, the carbon-based material may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the silicon oxide particles. When the carbon-based material is included within the range, oxidation may be well prevented without deteriorating capacity.

[0041] The coating or deposit layer may be less than or equal to 100 nm thick on the surface of the silicon oxide particle. When the coating or deposit layer has a thickness within the range, oxidation may be effectively prevented without deteriorating capacity.

[0042] The negative active material may realize high-capacity and improve cycle-life characteristic of a rechargeable lithium battery.

[0043] Hereinafter, a method of preparing the negative active material is illustrated.

[0044] According to one embodiment of the present invention, the method of preparing a negative active material includes a reaction of amorphous silicon oxide powder and an etchant.

[0045] In one embodiment, the amorphous silicon oxide and the etchant are used in a mole ratio of 10 : 1 to 1 : 10. Specifically, the amorphous silicon oxide and the etchant may be used in a mole ratio ranging from 1 : 1.1 to 1 : 2.1. When the amorphous silicon oxide and the etchant are used within the weight ratio range, the oxidation number of silicon on the surface of the silicon oxide may be lowered within the above range.

[0046] As described above, conventionally, there are attempts to decrease an oxidation number at a surface of a Si-based negative active material. However, there is no method to provide a negative active material comprising a silicon oxide particle having a Si/O ratio of higher than or equal to 1.8 on the surface of a silicon oxide particle. According to the method of the embodiment of the invention, only SiO2 is selectively removed from the surface of the silicon oxide particles by simply contacting silicon oxide powder with the etchant. Particularly, the negative active material comprising a silicon oxide particle having a Si/O ratio of higher than or equal to 1.8 on the surface of a silicon oxide particle may be easily prepared by controlling the ratio between the silicon oxide powder and etchant. That is, in accordance with the desired Si/O ratio on the surface of a silicon oxide particle, appropriate concentration of the etchant should be selected and employed to react with the silicon oxide particles to obtain the negative active material comprising a silicon oxide particle having a desired Si/O ratio on the surface of the silicon oxide particles.

[0047] The amorphous silicon oxide may be prepared in a common method or commercially available.

[0048] The etchant may be a material used for a commonly-known etching solution without any limit and for example, include an acid such as nitric acid, sulfuric acid, and the like or an F ion-containing compound such as HF, NH4F, NH4HF2, and the like. In one embodiment, the F ion-containing compound as an etchant may more rapidly promote an etching process.

[0049] The etchant may be dissolved in a solvent such as water and the like.

[0050] Herein, the etchant-containing solution may have a concentration determined to realize an appropriate etching speed. For example, the etchant-containing solution may have an F ion concentration ranging from 0.5M to 12M. A different etchant may change an etching speed depending on concentration and for example, have a concentration bringing about the same etching speed as the etchant-containing solution having the 0.5M to 12M F ion concentration. In general, an acid solution may have a higher concentration to accomplish the same etching speed and effect as the F ion-containing compound solution.

[0051] When the amorphous silicon oxide powder and the etchant are reacted to prepare a negative active material including a silicon oxide having a low oxidation number of silicon on the surface, the negative active material may be further washed or dried in a common method. For example, the washing may be performed using alcohol such as methanol, ethanol, isopropanol, and the like. In addition, the drying may be performed at a temperature ranging from 80 to 120°C under an inert gas atmosphere.

[0052] The preparing method may further include formation of an oxidation barrier layer by surface-treating the negative active material with a carbon-based material to prevent surface oxidation of the negative active material.

[0053] Herein, the carbon-based material may include a carbon or metal conductive agent and the like.

[0054] The surface treatment may include any common method of forming a layer without a particular limitation and for example, coating, impregnation, spraying, and the like.

[0055] According to another embodiment of the present invention, provided is a rechargeable lithium battery including a negative electrode including the negative active material; a positive electrode including a positive active material; and a non-aqueous electrolyte.

[0056] Rechargeable lithium batteries may be classified as lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the presence of a separator and the kind of electrolyte used in the battery. The rechargeable lithium batteries may have a variety of shapes and sizes, and include cylindrical, prismatic, or coin-type batteries, and may be thin film batteries or may be rather bulky in size. The structure and the manufacturing method of these batteries are well known in a related field and will not be described in detail.

[0057] FIG. 1 is an exploded perspective view of a rechargeable lithium battery in accordance with an embodiment of the present invention. Referring to FIG. 1, the rechargeable lithium battery 100 is formed with a cylindrical shape and includes a negative electrode 112, a positive electrode 114, a separator 113 disposed between the a positive electrode 114 and negative electrode 112, an electrolyte (not shown) impregnated in the negative electrode 112, the positive electrode 114, and the separator 113, a battery case 120, and sealing member 140 sealing the battery case 120. The rechargeable lithium battery 100 is fabricated by sequentially stacking a negative electrode 112, a positive electrode 114, and separator 113, and spiral-winding them and housing the wound product in the battery case 120.

[0058] The negative electrode includes a current collector and a negative active material layer formed on the current collector, and the negative active material layer includes the negative active material. The negative active material is the same as described above. The negative active material layer may include a binder, and optionally may further include a conductive material.

[0059] The binder improves binding properties of the negative active material particles to each other and to a current collector. Examples of the binder include at least one selected from the group consisting of polyvinylalcohol, carboxylmethylcellulose, hydroxypropylcellulose, polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an epoxy resin, nylon and the like, but are not limited thereto.

[0060] The conductive material provides an electrode with conductivity. Any electrically conductive material may be used as a conductive material unless it causes a chemical change. Examples of the conductive material include: carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber, and the like; a metal-based material of a metal powder or a metal fiber including copper, nickel, aluminum, silver, and the like; a conductive polymer such as a polyphenylene derivative; and mixtures thereof.

[0061] The current collector may be a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, or combinations thereof.

[0062] The positive electrode includes a current collector and a positive active material layer disposed on the current collector.

[0063] The positive active material includes lithiated intercalation compounds that reversibly intercalate and deintercalate lithium ions. The positive active material may include a composite oxide including at least one selected from the group consisting of cobalt, manganese, and nickel, as well as lithium. In particular, the following lithium-containing compounds may be used:

LiaA1-bRbD2 (wherein, in the above formula, 0.90 ≤ a ≤ 1.8 and 0 ≤ b ≤ 0.5); LiaE1-bRbO2. cDc (wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5 and 0 ≤ c ≤ 0.05); LiE2-bRbO4-cDc (wherein, in the above formula, 0 ≤ b ≤ 0.5, 0 ≤ c s 0.05); LiaNi1-b-cCobRcDα (wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α ≤ 2); LiaNi1-b-cCobRcO2-αZα(wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α < 2); LiaNi1-b-cCobRcO2-αZ2(wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b s 0.5, 0 ≤ c s 0.05 and 0 < α < 2); LiaNi1-b-cMnbRcDα(wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α ≤ 2); LiaNi1-b-cMnbRcO2-α7α(wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α < 2); LiaNi1-b-cMnbRcO2-αZ2(wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 < α < 2); LiaNibEcGdO2(wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5 and 0.001 ≤ d ≤ 0.1); LiaNibCocMndGeO2 (wherein, in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤0.5 and 0.001 ≤ e ≤ 0.1); LiaNiGbO2(wherein, in the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤0.1); LiaCoGbO2(wherein, in the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); LiaMnGbO2(wherein, in the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); LiaMn2GbO4(wherein, in the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiTO2; LiNiVO4; Li(3-f)J2(PO4)3 (0 ≤ f ≤ 2); Li(3-f)Fe2(PO4)3 (0 ≤ f ≤ 2); and LiFePO4.



[0064] In the above chemical formulae, A is Ni, Co, Mn, or a combination thereof; R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; Z is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; T is Cr, V, Fe, Sc, Y, or a combination thereof; and J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

[0065] The compound can have a coating layer on the surface, or can be mixed with a compound having a coating layer. The coating layer may include an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxyl carbonate of a coating element. The compounds for a coating layer can be amorphous or crystalline. The coating element for a coating layer may include Ag, Au, Pt, Pd, Cu, Ni, Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. The coating layer can be formed in a method having no negative influence on properties of a positive active material by including these elements in the compound. For example, the method may include any coating method such as spray coating, dipping, and the like, but is not illustrated in more detail, since it is well-known to those who work in the related field.

[0066] The positive active material layer may include a binder and a conductive material.

[0067] The binder improves binding properties of the positive active material particles to each other and to a current collector. Examples of the binder include at least one selected from the group consisting of polyvinyl alcohol, carboxylmethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinylchloride, carboxylated polyvinyl chloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylated styrene-butadiene rubber, an epoxy resin, nylon, and the like, but are not limited thereto.

[0068] The conductive material is used to provide conductivity to an electrode. In the battery including the same, it may include any electronic conductive material as long as causing no chemical change. For example, it may include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber or the like such as copper, nickel, aluminum, silver or the like, or one or at least one kind mixture of conductive material such as polyphenylene derivative or the like.

[0069] The current collector may be Al but is not limited thereto.

[0070] The negative and positive electrodes may be fabricated by a method including mixing the active material, a conductive material, and a binder into an active material composition, and coating the composition on a current collector, respectively. The electrode manufacturing method is well known and thus, is not described in detail in the present specification. The solvent includes N-methylpyrrolidone and the like but is not limited thereto.

[0071] The electrolyte includes a non-aqueous organic solvent and a lithium salt.

[0072] The non-aqueous organic solvent serves as a medium for transmitting ions taking part in the electrochemical reaction of a battery.

[0073] The non-aqueous organic solvent may include a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent. The carbonate-based solvent may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), or the like. The ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, methylpropionate, ethylpropionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, or the like. The ether-based solvent includes dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or the like, and examples of the ketone-based solvent include cyclohexanone, or the like. The alcohol-based solvent include ethyl alcohol, isopropyl alcohol, and the like, and examples of the aprotic solvent include nitriles such as R-CN (wherein R is a C2 to C20 linear, branched, or cyclic hydrocarbon group including a double bond, an aromatic ring, or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, or the like.

[0074] The non-aqueous organic solvent may be used singularly or in a mixture. When the organic solvent is used in a mixture, the mixture ratio can be controlled in accordance with a desirable battery performance.

[0075] The carbonate-based solvent is prepared by mixing a cyclic carbonate and a linear carbonate. The cyclic carbonate and the linear carbonate are mixed together in the volume ratio of about 1:1 to about 1:9. Within this range, performance of electrolyte may be improved.

[0076] In addition, the non-aqueous organic electrolyte may be further prepared by mixing a carbonate-based solvent with an aromatic hydrocarbon-based solvent. The carbonate-based and the aromatic hydrocarbon-based solvents may be mixed together in a volume ratio ranging from about 1:1 to about 30:1.

[0077] The aromatic hydrocarbon-based organic solvent may be represented by the following Chemical Formula 1.



[0078] In Chemical Formula 1, R1 to R6 are each independently hydrogen, a halogen, a C1 to C10 ° alkyl group, a C1 to C10 haloalkyl group, or a combination thereof.

[0079] The aromatic hydrocarbon-based organic solvent may include benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene, 1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4-trichlorotoluene, iodotoluene, 1,2-diiodotoluene, 1,3-diiodotoluene, 1,4-diiodotoluene, 1,2,3-triiodotoluene, 1,2,4-triiodotoluene, xylene, or a combination thereof.

[0080] The non-aqueous electrolyte may further include vinylene carbonate, an ethylene carbonate-based compound represented by the following Chemical Formula 2, or a combination thereof to improve cycle-life as an additive.



[0081] In Chemical Formula 2, R7 and R8 are independently hydrogen, hydrogen, a halogen, a cyano group (CN), a nitro group (NO2), or a C1 to C5 fluoroalkyl group, provided that at least one of R7 and R8 is a halogen, a cyano group (CN), a nitro group (NO2), or a C1 to C5 fluoroalkyl group.

[0082] Examples of the ethylene carbonate-based compound include difluoro ethylenecarbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, and the like. The amount of the vinylene carbonate or the ethylene carbonate-based compound used to improve cycle life may be adjusted within an appropriate range.

[0083] The lithium salt is dissolved in an organic solvent, supplies lithium ions in a battery, operates a basic operation of the rechargeable lithium battery, and improves lithium ion transportation between positive and negative electrodes therein. Examples of the lithium salt include LiPF6, LiBF4, LiSbF6, LiAsF6, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2), (where x and y are natural numbers), LiCl, Lil, LiB(C2O4)2 (lithium bis(oxalato) borate, LiBOB), or a combination thereof, as a supporting electrolytic salt. The lithium salt may be used in a concentration ranging from about 0.1M to about 2.0M. When the lithium salt is included at the above concentration range, an electrolyte may have excellent performance and lithium ion mobility due to optimal electrolyte conductivity and viscosity.

[0084] A separator 113 may include any materials commonly used in the conventional lithium battery as long as separating a negative electrode 112 from a positive electrode 114 and providing a transporting passage of lithium ion. In other words, it may have a low resistance to ion transport and an excellent impregnation for electrolyte. For example, it may be selected from glass fiber, polyester, TEFLON (tetrafluoroethylne), polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof. It may have a form of a non-woven fabric or a woven fabric. For example, for the lithium ion battery, polyolefin-based polymer separator such as polyethylene, polypropylene or the like is mainly used. In order to ensure the heat resistance or mechanical strength, a coated separator including a ceramic component or a polymer material may be used. Selectively, it may have a mono-layered or multi-layered structure.

[0085] The following examples illustrate the present invention in more detail. These examples, however, should not in any sense be interpreted as limiting the scope of the present invention.

Example 1: Preparation of negative active material



[0086] 100g of amorphous silicon oxide powder (ShinEtsu Co. Ltd.) was dispersed in 350 ml of an aqueous solution including 40 volume% of ethanol. While the dispersed solution was agitated at a speed of 300 RPM, 80 mL of a 49 volume% HF aqueous solution was added thereto in an amount of 1 ml/min. The resulting mixture was allowed to stand and additionally reacted for 30 minutes. When the reaction was complete, the reactant was transmitted and cleaned by 5 l of distilled water using a reduced pressure filtering device, obtaining a negative active material.

Example 2: Preparation of negative active material



[0087] 100g of amorphous silicon oxide powder (ShinEtsu Co. Ltd.) was dispersed in 350 ml of an aqueous solution including 40 volume% of ethanol. While the dispersed solution was agitated at a speed of 300 RPM, 100 mL of a 49 volume% HF aqueous solution was added thereto in an amount of 1 mf/min. The resulting mixture was allowed to stand and additionally reacted for 30 minutes. When the reaction was complete, the reactant was transmitted and cleaned by 5 l of distilled water using a reduced pressure filtering device, obtaining a negative active material.

Example 3: Preparation of negative active material



[0088] A negative active material was prepared according to the same method as Example 1 except for adding 150 ml of a 49 volume% HF aqueous solution.

Comparative Example 1: Preparation of negative active material



[0089] Amorphous silicon oxide powder (ShinEtsu Co. Ltd.) itself was used as a negative active material.

Comparative Example 2: Preparation of negative active material



[0090] 100g of amorphous silicon oxide powder (ShinEtsu Co. Ltd.) was dispersed in 350 ml of an aqueous solution including 40 volume% of ethanol. While the dispersed solution was agitated at a speed of 300 RPM, 10 mL of a 49 volume% HF aqueous solution was added thereto in an amount of 1 ml/min. The resulting mixture was allowed to stand and additionally reacted for 30 minutes. When the reaction was complete, the reactant was transmitted and cleaned by 5 l of distilled water using a reduced pressure filtering device, obtaining a negative active material.

Comparative Example 3: Preparation of negative active material



[0091] A negative active material was prepared according to the same method as Comparative Example 2 except for adding 30 ml of a 49 volume% HF aqueous solution.

Comparative Example 4: Preparation of negative active material



[0092] A negative active material was prepared according to the same method as Comparative Example 2 except for adding 50 ml of a 49 volume% HF aqueous solution.

Experimental Example 1: Internal concentration measurement using X-ray photoelectron spectroscopy (XPS)



[0093] The amorphous silicon oxide according to Comparative Example 1 and the negative active material particle according to Comparative Example 2 were analyzed using X-ray photoelectron spectroscopy (XPS). The results are provided in FIGS. 2 and 3.

[XPS analysis condition]



[0094] 
  • Analysis equipment: ESCA 250 spectrometer
  • Pressure in an analysis chamber: 8*10-10mbar
  • Used radioactive ray: monochromatic Al
  • X-ray activation energy: 1486.8eV
  • Analysis area: 500µm2
  • About thickness of a surface layer in XPS analysis: about 5nm
  • Depth condition: depth profile was obtained by Ar+ ion beam sputtering (3keV). The sputtering speed for SiO2 was 10nm/min.


[0095] FIG. 2 shows analysis results of the amorphous silicon oxide particle according to Comparative Example 1, in which the surface of the amorphous silicon oxide particle was oxidized and abundantly included oxygen.

[0096] FIGS. 3 to 5 show analysis results of the negative active materials according to Comparative Examples 2 to 4, which show that the Si/O ratios on the surfaces of the silicon oxide particles are different in proportion to the concentration of the etchant. That is, the higher the concentration of the etchant, the higher the Si ratio on the surface of the silicon oxide particles. In all results, the silicon oxide particles had higher Si ratio on the surface but a smooth concentration gradient of silicon (Si) toward the core of the silicon oxide particles.

[0097] FIGS. 6 to 8 show analysis results of the negative active materials according to Examples 1 to 3, which also show that the Si/O ratios on the surfaces of the silicon oxide particles are different in proportion to the concentration of the etchant. The negative active materials according to Examples 1 to 3 have much higher Si ratios on the surfaces of the silicon oxide particles than those according to Comparative Examples 2 to 4, as being reacted with the etchants of much higher concentrations. In all results, the silicon oxide particles had higher Si ratio on the surface but a smooth concentration gradient of silicon (Si) toward the core of the silicon oxide particles.

(Experimental Example 2: Capacity characteristic evaluation)



[0098] The negative active materials according to Examples 1 to 3 and Comparative Examples 1 to 4 were respectively used to fabricate a 2016 coin-type half-cells. Herein, a substrate had a composition having an active material: a conductive material: a binder = 80:10:10 in a weight ratio. The conductive material was Denka black, the binder was Pl (polyimide), and a solvent was NMP (N-methyl-2-pyrrolidone). Then, a battery cell was fabricated by using a lithium metal as a counter electrode, inserting a separator between the substrate and the counter electrode, injecting an electrolyte solution therein, and sealing the battery case. The electrolyte solution was prepared by adding 5 volume% of FEC (fluorinated ethyl carbonate) as an additive to a mixed solvent prepared by mixing EC (ethylenecarbonate) / EMC (ethylmethylcarbonate) / DMC (dimethylcarbonate) in a volume ratio of 3/3/4.

(Experimental Example 3: Cycle-life characteristic evaluation)



[0099] Each rechargeable lithium battery cell was 50 times charged and discharged at 25°C in a range of 3.0 to 4.2V with current density of 0.5C. As a result, initial capacity and capacity retention obtained as a ratio of the 50th cycle discharge capacity relative to the initial capacity are provided in Table 1.
Table 1
 [Si] / [O] ratio1st charge capacity [mAh/g]1st discharge capacity [mAh/g]First cycle efficiency (%)Capacity retention (%)
Example 1 1.8 2387 1545 64.7 95.7
Example 2 2.0 2395 1554 64.9 96.8
Example 3 2.4 2394 1488 62.2 85.7
Comparative Example 1 0.8 2330 1337 57.4 72.9
Comparative Example 2 1.0 2350 1497 63. 7 90.2
Comparative Example 3 1.3 2382 1538 64.6 92.5
Comparative Example 4 1.6 2388 1541 64.5 93.6


[0100] As shown in Table 1, when negative active material comprising a silicon oxide having a Si/O ratio of higher than or equal to 1.8 on the surface of a silicon oxide particle, both the 1st charge capacity and capacity retention have been remarkably improved compared with that having a Si/O ratio of less than 1.8.

[0101] Accordingly, a lithium rechargeable battery comprising a negative active material including the silicon oxide particles having a Si/O ratio between 1.8 to 2.4 on the surface of a silicon oxide particle, electrochemical properties, such as cycle-life, may improve.


Claims

1. A negative active material for a rechargeable lithium battery including surface modified silicon oxide particles having a bulk formula represented by SiOx (0<x<2) and having a ratio of silicon relative to oxygen (Si/O ratio) on the surface of the particles in the range of 1.8 to 2.4, characterized in that a content of silicon (Si) decreases from the surface toward the core of the particles, while the content of oxygen (O) increases from the surface toward the core of the particles
 
2. The negative active material of claim 1, wherein the Si/O ratio on the surface of the particles is in the range of 2.0 to 2.3.
 
3. The negative active material of claim 1, wherein x is in the range of 0.5 to 1.5, especially in the range of 0.6 to 0.95.
 
4. The negative active material of any of the preceding claims, wherein the negative active material has a specific surface area of 10 to 500 m2/g, especially of 10 to 40 m2/g.
 
5. The negative active material of any of the preceding ciaims, wherein the negative active material further includes one or more additional element selected from the group consisting of an alkali metal, an alkaline-earth metal, an element belonging to groups 13 to 16, a transition metal and a rare earth metal.
 
6. The negative active material of claim 5, wherein the additional element is selected from the group consisting of Mg, Ca, Sr, Ba, Ra, 8c Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te and Po.
 
7. The negative active material of any of the preceding claims, wherein the negative active material has an average particle size of 0.1 µm to 100 µm.
 
8. The negative active material of any of the preceding claims, wherein the negative active material further includes a carbon-based material.
 
9. The negative active material of any of the preceding wherein a coating or deposit layer is formed on the surface of the silicon oxide particles.
 
10. The negative active material of claim 8 or 9, wherein the carbon-based material is one selected of graphite, carbon black, acetylene black or ketjen black.
 
11. The negative active material of one of claims 8 through 10, wherein the carbon-based material is provided in form of particles having an average particle size which is 0.01 to 0.5 times of the average particle size of the silicon oxide particles.
 
12. The negative active material of one of claims 8 through 11, wherein the amount of carbon-based material is 1 to 50 parts by weight based on 100 parts by weight of the silicon oxide particles.
 
13. A method of preparing a negative active material for a rechargeable lithium battery according to one of the preceding claims, method including the step of treating amorphous silicon oxide powder with an etchant.
 
14. The method of claim 13, wherein the etchant includes at least one of nitric acid, sulfuric acid, HF, NH4F and NH4HF2.
 
15. The method of claim 13 or 14, wherein the amorphous silicon oxide powder and the etchant are used in a mole ratio of 10 : 1 to 1 : 10.
 


Ansprüche

1. Negatives Aktivmaterial für eine wiederaufladbare Lithiumbatterie, enthaltend oberflächenmodifizierte Siliziumoxidpartikel, die eine Massenformel von SiOx (0<x<2) zeigen und ein Verhältnis von Silizium zu Sauerstoff (Si/O-Verhältnis) auf der Oberfläche der Partikel im Bereich von 1,8 bis 2,4 aufweisen, dadurch gekennzeichnet, dass ein Silizium (Si)-Gehalt von der Oberfläche zum Kern der Partikel hin abnimmt, während der Sauerstoff (O)-Gehalt von der Oberfläche zum Kern der Partikel hin zunimmt.
 
2. Negatives Aktivmaterial nach Anspruch 1, wobei das Si/O-Verhältnis auf der Oberfläche der Partikel im Bereich von 2,0 bis 2,3 liegt.
 
3. Negatives Aktivmaterial nach Anspruch 1, wobei x im Bereich von 0,5 bis 1,5, insbesondere im Bereich von 0,6 bis 0,95, liegt.
 
4. Negatives Aktivmaterial nach einem der vorhergehenden Ansprüche, wobei das negative Aktivmaterial eine spezifische Oberfläche von 10 bis 500 m2/g, insbesondere von 10 bis 40 m2/g aufweist.
 
5. Negatives Aktivmaterial nach einem der vorhergehenden Ansprüche, wobei das negative Aktivmaterial ferner ein oder mehrere zusätzliche Elemente aufweist, das/die aus der Gruppe bestehend aus einem Alkalimetall, einem Erdalkalimetall, einem Element, das zu den Gruppen 13 bis 16 gehört, einem Übergangsmetall und einem Metall der Seltenen Erden ausgewählt ist/sind.
 
6. Negatives Aktivmaterial nach Anspruch 5, wobei das zusätzliche Element aus der Gruppe bestehend aus Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te und Po ausgewählt ist.
 
7. Negatives Aktivmaterial nach einem der vorhergehenden Ansprüche, wobei das negative Aktivmaterial eine mittlere Partikelgröße von 0,1 µm bis 100 µm aufweist.
 
8. Negatives Aktivmaterial nach einem der vorhergehenden Ansprüche, wobei das negative Aktivmaterial ferner ein kohlenstoffbasiertes Material aufweist.
 
9. Negatives Aktivmaterial nach einem der vorhergehenden Ansprüche, wobei eine Beschichtungs- oder Ablagerungsschicht auf der Oberfläche der Siliziumoxidpartikel ausgebildet ist.
 
10. Negatives Aktivmaterial nach Anspruch 8 oder 9, wobei das kohlenstoffbasierte Material eines ausgewählt aus Graphit, Ruß, Acetylenruß oder Ketjen-Ruß ist.
 
11. Negatives Aktivmaterial nach einem der Ansprüche 8 bis 10, wobei das kohlenstoffbasierte Material in Form von Partikeln bereitgestellt wird, die eine mittlere Partikelgröße, die 0,01 bis 0,5 mal die mittlere Partikelgröße der Siliziumoxidpartikel ist, aufweisen.
 
12. Negatives Aktivmaterial nach einem der Ansprüche 8 bis 11, wobei die Menge des kohlenstoffbasierten Materials 1 bis 50 Gewichtsteile mit Bezug auf 100 Gewichtsteile der Siliziumoxidpartikel beträgt.
 
13. Verfahren zur Herstellung eines negativen Aktivmaterials für eine wiederaufladbare Lithiumbatterie nach einem der vorhergehenden Ansprüche, wobei das Verfahren den Schritt der Behandlung von amorphem Siliziumoxidpulver mit einem Ätzmittel aufweist.
 
14. Verfahren nach Anspruch 13, wobei das Ätzmittel zumindest eines von Salpetersäure, Schwefelsäure, HF, NH4F und NH4HF2 aufweist.
 
15. Verfahren nach Anspruch 13 oder 14, wobei das amorphe Siliziumoxidpulver und das Ätzmittel in einem Molverhältnis von 10 : 1 bis 1 : 10 verwendet werden.
 


Revendications

1. Matière active négative pour une batterie au lithium rechargeable, comprenant des particules d'oxyde de silicium modifiées en surface ayant une formule brute représentée par SiOx (0 < x < 2) et ayant un rapport du silicium à l'oxygène (rapport Si/O) sur la surface des particules dans l'intervalle de 1,8 à 2,4, caractérisée en ce que la quantité de silicium (Si) diminue de la surface vers le centre des particules, tandis que la quantité d'oxygène (O) augmente de la surface vers le centre des particules.
 
2. Matière active négative suivant la revendication 1, dans laquelle le rapport Si/O sur la surface des particules est dans l'intervalle de 2,0 à 2,3.
 
3. Matière active négative suivant la revendication 1, dans laquelle x est dans l'intervalle de 0,5 à 1,5, notamment dans l'intervalle de 0,6 à 0,95.
 
4. Matière active négative suivant l'une quelconque des revendications précédentes, ladite matière active négative ayant une surface spécifique de 10 à 500 m2/g, notamment de 10 à 40 m2/g.
 
5. Matière active négative suivant l'une quelconque des revendications précédentes, ladite matière active négative comprenant en outre un ou plusieurs éléments supplémentaires choisis dans le groupe consistant en un métal alcalin, un métal alcalinoterreux, un élément appartenant aux Groupes 13 à 16, un métal de transition et un métal faisant partie des terres rares.
 
6. Matière active négative suivant la revendication 5, dans laquelle l'élément supplémentaire est choisi dans le groupe consistant en Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te et Po.
 
7. Matière active négative suivant l'une quelconque des revendications précédentes, ladite matière active négative ayant un diamètre moyen de particule de 0,1 µm à 100 µm.
 
8. Matière active négative suivant l'une quelconque des revendications précédentes, ladite matière active négative comprenant en outre une matière à base de carbone.
 
9. Matière active négative suivant l'une quelconque des revendications précédentes, dans laquelle un revêtement ou une couche déposée est formé sur la surface des particules d'oxyde de silicium.
 
10. Matière active négative suivant la revendication 8 ou 9, dans laquelle la matière à base de carbone est une matière choisie entre le graphite, le noir de carbone, le noir d'acétylène et le noir Ketjen.
 
11. Matière active négative suivant une des revendications 8 à 10, dans laquelle la matière à base de carbone est fournie sous forme de particules ayant un diamètre moyen de particule qui est de 0,01 à 0,5 fois le diamètre moyen de particule des particules d'oxyde de silicium.
 
12. Matière active négative suivant une des revendications 8 à 11, dans laquelle la quantité de matière à base de carbone est de 1 à 50 parties en poids sur la base de 100 parties en poids des particules d'oxyde de silicium.
 
13. Procédé de préparation d'une matière active négative pour une batterie au lithium rechargeable suivant une des revendications précédentes, le procédé comprenant l'étape de traitement d'une poudre d'oxyde de silicium amorphe avec un agent d'attaque chimique.
 
14. Procédé suivant la revendication 13, dans lequel l'agent d'attaque chimique comprend au moins un de l'acide nitrique, de l'acide sulfurique, de HF, de NH4F et de NH4HF2.
 
15. Procédé suivant la revendication 13 ou 14, dans lequel la poudre d'oxyde de silicium amorphe et l'agent d'attaque chimique sont utilisés en un rapport molaire de 10:1 à 1:10.
 




Drawing


















REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description