WO2010098638A2 - Batterie rechargeable au lithium comprenant une électrode négative contenant un liant à base d'eau - Google Patents

Batterie rechargeable au lithium comprenant une électrode négative contenant un liant à base d'eau Download PDF

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Publication number
WO2010098638A2
WO2010098638A2 PCT/KR2010/001264 KR2010001264W WO2010098638A2 WO 2010098638 A2 WO2010098638 A2 WO 2010098638A2 KR 2010001264 W KR2010001264 W KR 2010001264W WO 2010098638 A2 WO2010098638 A2 WO 2010098638A2
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secondary battery
lithium secondary
carbonate
formula
negative electrode
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PCT/KR2010/001264
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English (en)
Korean (ko)
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WO2010098638A3 (fr
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전종호
Original Assignee
주식회사 엘지화학
윤수진
유성훈
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Priority to JP2011538573A priority Critical patent/JP5431494B2/ja
Priority to US13/203,061 priority patent/US8691448B2/en
Priority claimed from KR1020100017594A external-priority patent/KR101069100B1/ko
Publication of WO2010098638A2 publication Critical patent/WO2010098638A2/fr
Publication of WO2010098638A3 publication Critical patent/WO2010098638A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium secondary battery having a negative electrode using an aqueous binder.
  • Lithium secondary batteries are the batteries that can best meet these demands, and research on these is being actively conducted.
  • a lithium secondary battery has a negative electrode, a positive electrode, and a nonaqueous electrolyte that provides a migration path between lithium ions therebetween, and oxidation and reduction reactions when lithium ions are intercalated / deintercalated at the positive electrode and the negative electrode By generating electrical energy.
  • a binder As a negative electrode of the lithium secondary battery, a binder is used to bind the active material particles to maintain a molded body.
  • a solvent-based binder i.e., a binder using an organic solvent as a solvent
  • PVdF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • Aqueous binders unlike solvent binders, are economical, environmentally friendly, and harmless to the health of workers.
  • the binding effect is also greater than that of the solvent-based binder, the ratio of the active material per volume can be increased, and high capacity can be obtained.
  • the problem to be solved by the present invention is to be applied to a lithium secondary battery having a negative electrode using an aqueous binder to form a stable SEI film on the negative electrode, by controlling the amount of LiF in the formed SEI film can improve the life characteristics of the battery
  • the present invention provides a lithium secondary battery having a nonaqueous electrolyte.
  • a lithium secondary battery comprising a negative electrode, a positive electrode and a nonaqueous electrolyte
  • the negative electrode comprises an aqueous binder, the non-aqueous electrolyte, (a) a cyclic anhydride or derivatives thereof; And (b) any one anion receptor selected from the group consisting of borane compounds, borate compounds, and mixtures thereof.
  • the aqueous binder is preferably SBR (styrene-butadiene rubber).
  • the cyclic anhydride or derivative thereof is preferably any one selected from the group consisting of compounds represented by the following formulas (1) to (4) or a mixture of two or more thereof.
  • R 1 to R 11 are each independently halogen or an alkyl, alkenyl or alkoxy group having 1 to 10 carbon atoms unsubstituted or substituted with halogen.
  • the borane compound uses a compound represented by the following formula (5)
  • the borate compound uses a compound represented by the following formula (6).
  • R 12 to R 14 are each independently hydrogen or halogen, or an alkyl group or silyl group having 1 to 6 carbon atoms.
  • R 15 to R 17 are each independently hydrogen or halogen, or an alkyl or silyl group having 1 to 6 carbon atoms.
  • the content of the (a) component and (b) component may be 0.05 to 10% by weight, respectively, based on the total weight of the nonaqueous electrolyte.
  • the lithium secondary battery according to the present invention has the following effects.
  • the cyclic anhydride or derivative thereof contained in the nonaqueous electrolyte forms a stable SEI film on the surface of the negative electrode.
  • the anion receptor of the borane compound or the borate compound elutes the LiF in the SEI film which increases with the use of the aqueous binder and the cyclic anhydride (or derivative thereof) to control the LiF content in the SEI film. Accordingly, the resistance of the SEI film is controlled to improve the life characteristics of the battery.
  • Example 1 is an XPS graph obtained from a surface of a negative electrode after charging a battery according to Example 1 and Comparative Example 1 at 0.1C, respectively.
  • a lithium secondary battery comprising a negative electrode, a positive electrode, and a nonaqueous electrolyte
  • the negative electrode comprises an aqueous binder, the nonaqueous electrolyte, (a) a cyclic anhydride or derivatives thereof; And (b) any one anion receptor selected from the group consisting of borane compounds, borate compounds, and mixtures thereof.
  • the lithium secondary battery of the present invention is manufactured economically and environmentally friendly by using an aqueous binder as the binder of the negative electrode.
  • an aqueous binder is preferably SBR (styrene-butadiene rubber), and, as is well known, may be applied to a negative electrode by dispersing it in water together with a thickener such as carboxymethyl cellulose (CMC).
  • SBR styrene-butadiene rubber
  • a nonaqueous electrolyte solution contains (a) cyclic anhydride or its derivative (s).
  • the cyclic anhydride or its derivatives ring-open at a potential lower than the solvent at the time of initial charge to form an SEI film on the surface of the cathode.
  • Such cyclic anhydrides or derivatives thereof are preferably any one selected from the group consisting of compounds represented by the following formulas (1) to (4) or mixtures of two or more thereof.
  • R 1 to R 11 are each independently halogen or an alkyl, alkenyl or alkoxy group having 1 to 10 carbon atoms unsubstituted or substituted with halogen.
  • the SEI film formed from the above-mentioned component (a) has high stability, it contains a large amount of LiF and acts as a large resistance during charge and discharge.
  • the reason why the LiF content in the SEI film is greatly increased is that in addition to the cause of using the component (a), an aqueous binder is used as the negative electrode binder.
  • an aqueous binder is used as the negative electrode binder.
  • the negative electrode using the aqueous binder has a high water content.
  • the hydrofluoric acid content in the nonaqueous electrolytic solution is significantly increased, so that the amount of LiF is also increased when the SEI film is formed by the component (a).
  • the lithium secondary battery of the present invention solves this problem by adding any one anion receptor selected from the group consisting of (b) a borane compound, a borate compound, and a mixture thereof to the nonaqueous electrolyte. That is, an anion receptor made of a borane compound or a borate compound contained in the nonaqueous electrolyte elutes LiF in the SEI film increased with the use of an aqueous binder and a cyclic anhydride (or a derivative thereof). Accordingly, since the LiF content in the SEI film is controlled to be low, the resistance of the SEI film is lowered, thereby improving the life characteristics of the battery.
  • the lithium secondary battery of the present invention it is preferable to use a compound represented by the following formula (5) as the borane compound added to the nonaqueous electrolyte and a compound represented by the following formula (6) as the borate compound.
  • R 12 to R 14 are each independently hydrogen or halogen, or an alkyl group or silyl group having 1 to 6 carbon atoms.
  • R 15 to R 17 are each independently hydrogen or halogen, or an alkyl or silyl group having 1 to 6 carbon atoms.
  • the above-mentioned components (a) and (b) are preferably added in an amount of 0.05 to 10% by weight, for example, based on the total weight of the nonaqueous electrolyte, in consideration of the life improvement effect and performance of the battery.
  • the nonaqueous electrolyte contains an organic solvent.
  • the organic solvent is not particularly limited as long as it is usually used as an organic solvent for nonaqueous electrolyte, and cyclic carbonate, linear carbonate, lactone, ether, ester, acetonitrile, lactam, and / or ketone can be used.
  • Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC), and the like.
  • Examples of the linear carbonate include diethyl carbonate (DEC) and dimethyl carbonate. (DMC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), and the like, and these may be used alone or in combination of two or more thereof.
  • Examples of the lactone include gamma-butyrolactone (GBL), and examples of the ether include dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane And 1,2-diethoxyethane.
  • Examples of such esters include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl pivalate and the like.
  • the lactam includes N-methyl-2-pyrrolidone (NMP) and the like
  • the ketone includes polymethylvinyl ketone.
  • a halogen derivative of the organic solvent may be used, but is not limited thereto. These organic solvents can be used individually or in mixture of 2 or more types.
  • the nonaqueous electrolyte includes an electrolyte salt
  • the electrolyte salt is not particularly limited as long as it is usually used as an electrolyte salt for nonaqueous electrolyte.
  • the electrolyte salt is (i) Li +, Na + , a cation and (ii) selected from the group consisting of K + PF 6 -, BF 4 -, Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2) 3 - , but can be configured with a combination of an anion selected from the group consisting of, but not always limited thereto.
  • These electrolyte salts can be used individually or in mixture of 2 or more types.
  • the electrolyte salt is LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , CF 3 SO 3 Li and LiC ( It is preferable to use lithium salts such as CF 3 SO 2 ) 3 and LiC 4 BO 8 .
  • the lithium secondary battery of the present invention includes all conventional lithium secondary batteries, such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • the lithium secondary battery of the present invention can be prepared according to conventional methods known in the art.
  • a porous separator may be placed between the positive electrode and the negative electrode to prepare a nonaqueous electrolyte.
  • the electrode of a lithium secondary battery can be manufactured by conventional methods known in the art.
  • a slurry may be prepared by mixing and stirring a solvent, a binder, a conductive material, and a dispersant in an electrode active material, and then applying (coating) to a current collector of a metal material, compressing, and drying the electrode to prepare an electrode.
  • Lithium cobalt oxides such as lithium nickel oxide, LiCoO 2 , and manganese, nickel, and cobalt in which some of these oxides are substituted with other transition metals, or vanadium oxide containing lithium, etc.), but are not limited thereto. .
  • the negative electrode active material may be a conventional negative electrode active material that can be used in the negative electrode of a conventional lithium secondary battery, non-limiting examples of lithium metal, lithium alloy, carbon, petroleum coke that can occlude and release lithium ions ), Activated carbon, graphite, carbon fiber, and the like.
  • lithium oxide may be occluded and released, and metal oxides such as TiO 2 , SnO 2, and the like having a potential of less than 2 V may be used, but are not limited thereto.
  • carbon materials such as graphite, carbon fiber and activated carbon are preferable.
  • the current collector of the metal material is a metal having high conductivity, and any metal can be used as long as the slurry of the electrode active material can be easily adhered and is not reactive in the voltage range of the battery.
  • Non-limiting examples of the positive electrode current collector is a foil produced by aluminum, nickel or a combination thereof, and non-limiting examples of the negative electrode current collector is produced by copper, gold, nickel or copper alloy or a combination thereof Foil and the like.
  • Examples of the positive electrode binder that can be used include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and the like, and styrene butadiene rubber (SBR) is used as the negative electrode binder.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • SBR styrene butadiene rubber
  • the conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical change in the electrochemical device.
  • carbon black, graphite, carbon fiber, carbon nanotubes, metal powder, conductive metal oxide, organic conductive materials, and the like can be used, and currently commercially available products as acetylene black series (Chevron Chemical) Chevron Chemical Company or Gulf Oil Company, etc., Ketjen Black EC series (Armak Company), Vulcan XC-72 (Cabot Company) (Cabot Company) and Super P (MMM).
  • Solvents for forming the electrode include organic solvents such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents are used alone or in combination of two or more. It can be mixed and used. However, when forming a cathode, water is used as a solvent. The amount of the solvent used is sufficient to dissolve and disperse the electrode active material, the binder, and the conductive material in consideration of the coating thickness of the slurry and the production yield.
  • organic solvents such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents are used alone or in combination of two or more. It can be mixed and used. However, when forming a cathode, water is used as a solvent. The amount of the solvent used is sufficient to dissolve and disperse the electrode active material, the binder, and the conductive material in consideration of the coating thickness of
  • the lithium secondary battery of the present invention may include a separator.
  • the separator is not particularly limited, but it is preferable to use a porous separator, and non-limiting examples include a polypropylene-based, polyethylene-based, or polyolefin-based porous separator.
  • the lithium secondary battery of the present invention is not limited in appearance, but may be cylindrical, square, pouch type, or coin type using a can.
  • Ethylene carbonate (EC): Ethyl methyl carbonate (EMC) 3: 7 (v: v) to dissolve LiPF 6 in an organic solvent to a concentration of 1M, and then to the solution succinic anhydride and tripropyl borate of the formula
  • the nonaqueous electrolyte was prepared by adding 0.5% by weight and 0.1% by weight, respectively, based on the total weight of the nonaqueous electrolyte.
  • An electrode was prepared using LiCoO 2 as the positive electrode, artificial graphite as the negative electrode, and SBR as the negative electrode binder.
  • a bicell type pouch battery was manufactured by a conventional method of injecting the nonaqueous electrolyte prepared by the above-described method.
  • a nonaqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that tripropyl borane was used instead of tripropyl borate.
  • a nonaqueous electrolyte solution and a lithium secondary battery were manufactured in the same manner as in Example 1, except that 1% by weight of fluoroethylene carbonate represented by Formula 8 was further added.
  • a nonaqueous electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1, except that Tris (trimethyl silyl) borate was used instead of tripropyl borate.
  • a nonaqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that Maleic anhydride was used instead of Succinic anhydride.
  • a nonaqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that Phthalic anhydride was used instead of Succinic anhydride.
  • a nonaqueous electrolyte solution and a lithium secondary battery were manufactured in the same manner as in Example 1, except that tripropyl borate was not added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 3, except that tripropyl borate was not added.
  • a nonaqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that succinic anhydride was not added.
  • a nonaqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 2, except that succinic anhydride was not added.
  • a nonaqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 4, except that succinic anhydride was not added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 5, except that tripropyl borate was not added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 6, except that tripropyl borate was not added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that succinic anhydride and tripropyl borate were not added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were manufactured in the same manner as in Example 1, except that PVdF was used instead of SBR as a negative electrode binder in preparing a lithium secondary battery.
  • Example 1 Succinic anhydride 0.5 wt% tripropyl borate 0.1wt% 85.7
  • Example 2 Succinic anhydride 0.5 wt% tripropyl borane 0.1 wt% 82.7
  • Example 3 Succinic anhydride 0.5 wt% Fluoro-ethylene carbonate 1wt% tripropyl borate 0.1 wt% 86.3
  • Example 4 Succinic anhydride 0.5 wt% Tris (trimethyl silyl) borate 0.1 wt% 81.3
  • Example 5 Maleic anhydride 0.5 wt% tripropyl borate 0.1 wt% 77.8
  • Example 6 Phthalic anhydride 0.5 wt% tripropyl borate 0.1 wt% 72.7 Comparative
  • Example 1 Succinic anhydride 0.5 wt% 62.3
  • Example 2 Succinic anhydride 0.5 wt% Fluoro-ethylene carbonate 1wt% 65.6 Comparative Example 3 triprop
  • the lithium secondary battery of Comparative Example 9 which used PVdF as a solvent-based binder as a negative electrode binder, was found to have a significantly reduced lifespan. Since the negative electrode using the solvent-based binder has a lower specific surface area than the negative electrode using the aqueous binder, the increase in resistance per unit area due to both additives of the present invention is estimated to have shown this result.
  • the lithium secondary battery of Example 1 in which a nonaqueous electrolyte including a cyclic anhydride derivative and an anion receptor is applied to a negative electrode using an aqueous binder according to the present invention the nonaqueous electrolyte containing only a cyclic anhydride derivative alone is an aqueous binder.
  • the LiF content in the SEI film is significantly reduced compared to the battery of Comparative Example 1 applied to the negative electrode using. This is because the anion receptor eluted LiF among the components of the SEI film on the surface of the cathode, thereby confirming that an SEI film is easily formed.

Abstract

L'invention concerne une batterie rechargeable au lithium comprenant une électrode négative, une électrode positive et un électrolyte non aqueux. L'électrode négative contient un liant à base d'eau, et l'électrolyte non aqueux contient : (a) un anhydride cyclique ou un de ces dérivés; et (b) un récepteur d'anion sélectionné dans le groupe comprenant des composés borane, des composés borate, et un mélange de ceux-ci. Selon l'invention, l'électrode négative présente un film SEI stable, et la quantité de LiF présente dans le film SEI est contrôlée, ce qui permet de prolonger la durée de vie de la batterie.
PCT/KR2010/001264 2009-02-26 2010-02-26 Batterie rechargeable au lithium comprenant une électrode négative contenant un liant à base d'eau WO2010098638A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2011538573A JP5431494B2 (ja) 2009-02-26 2010-02-26 水系バインダーを含む負極を備えたリチウム二次電池
US13/203,061 US8691448B2 (en) 2009-02-26 2010-02-26 Lithium secondary battery with anode containing aqueous binder

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20090016358 2009-02-26
KR10-2009-0016358 2009-02-26
KR1020100017594A KR101069100B1 (ko) 2009-02-26 2010-02-26 수계 바인더를 포함하는 음극을 구비한 리튬 이차전지
KR10-2010-0017594 2010-02-26

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WO2010098638A3 WO2010098638A3 (fr) 2010-11-25

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0814523A2 (fr) * 1993-10-22 1997-12-29 Fuji Photo Film Co., Ltd. Pile secondaire non-aqueuse
US6168885B1 (en) * 1998-08-21 2001-01-02 Sri International Fabrication of electrodes and devices containing electrodes
US6991874B1 (en) * 1998-05-04 2006-01-31 Basf Aktiengesellschaft Compositions suitable for electrochemical cells
US20070212615A1 (en) * 2004-04-20 2007-09-13 Degussa Ag Electrolyte Composition in Addition to the Use Thereof as an Electrolyte Material for Electrochemical Energy Storage Systems
US20070287070A1 (en) * 2004-07-20 2007-12-13 Takefumi Okumura Electrode for Polymer Electrolyte Secondary Battery and Polymer Electrolyte Secondary Battery
KR20080053399A (ko) * 2005-10-05 2008-06-12 메드트로닉 인코포레이티드 리튬 이온 전지
US20090017386A1 (en) * 2007-07-11 2009-01-15 Ferro Corporation Non-Aqueous Electrolytic Solutions And Electrochemical Cells Comprising The Same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0814523A2 (fr) * 1993-10-22 1997-12-29 Fuji Photo Film Co., Ltd. Pile secondaire non-aqueuse
US6991874B1 (en) * 1998-05-04 2006-01-31 Basf Aktiengesellschaft Compositions suitable for electrochemical cells
US6168885B1 (en) * 1998-08-21 2001-01-02 Sri International Fabrication of electrodes and devices containing electrodes
US20070212615A1 (en) * 2004-04-20 2007-09-13 Degussa Ag Electrolyte Composition in Addition to the Use Thereof as an Electrolyte Material for Electrochemical Energy Storage Systems
US20070287070A1 (en) * 2004-07-20 2007-12-13 Takefumi Okumura Electrode for Polymer Electrolyte Secondary Battery and Polymer Electrolyte Secondary Battery
KR20080053399A (ko) * 2005-10-05 2008-06-12 메드트로닉 인코포레이티드 리튬 이온 전지
US20090017386A1 (en) * 2007-07-11 2009-01-15 Ferro Corporation Non-Aqueous Electrolytic Solutions And Electrochemical Cells Comprising The Same

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