CN1697239A - Non-aqueous electrolyte and secondary battery of lithium - Google Patents
Non-aqueous electrolyte and secondary battery of lithium Download PDFInfo
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- CN1697239A CN1697239A CNA2004100272036A CN200410027203A CN1697239A CN 1697239 A CN1697239 A CN 1697239A CN A2004100272036 A CNA2004100272036 A CN A2004100272036A CN 200410027203 A CN200410027203 A CN 200410027203A CN 1697239 A CN1697239 A CN 1697239A
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- phenyl
- carbon atom
- sulfone
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- 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
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- 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
Abstract
The non-aqueous electrolyte includes non-aqueous organic solvent, lithium salt and additive. The additive is selected from sulfone-based compound expressed as follows: Ar denoted as phenyl or phenyl of alkyl of possessing 1 - 2 carbon atom; R denoted as alkyl of possessing 1 - 6 carbon atoms, alkenyl of possessing chain containing 2 - 6 carbon atoms, phenyl or phenyl of alkyl of possessing 1 - 2 carbon atom. Content of the additive is 0.1 - 5 % of total weight of electrolyte. Freezing point and viscosity of the electrolyte with the said compound being added into are lowered so as to improve discharge performance of lithium ion cell in low temperature.
Description
[technical field]
The present invention relates to a kind of nonaqueous electrolytic solution and contain the lithium secondary battery of this electrolyte, more specifically, the present invention relates to a kind of nonaqueous electrolytic solution that can improve the low temperature discharge property of lithium secondary battery, and the lithium secondary battery that comprises this electrolyte.
[background technology]
Used the battery of nonaqueous electrolytic solution, owing to have high-energy-density, high voltage, pollution-free, characteristics such as cycle life is high, memory-less effect, charging rate are fast, catered to the requirement of modern electronic product development, be widely used at present in PC, mobile phone and the consumer electronic device such as portable CD player, PDA.
Lithium secondary battery is as the representative of this class battery, and the positive pole that the positive active material that negative pole, lithium and the transition metal oxide of being made up of as negative electrode active material the carbonaceous material that can embed and disengage lithium ion is combined into is formed, nonaqueous electrolytic solution of placing the barrier film between the both positive and negative polarity and containing lithium salts etc. constitute.When battery charge, lithium ion is discharged from positive active material, is embedded in the carbonaceous material of negative pole.When battery discharge, lithium ion discharges from carbon material for negative pole, is embedded in the positive active material then.This nonaqueous electrolytic solution plays the regulating action of mobile lithium ion between positive pole and negative pole.
As nonaqueous electrolytic solution; because cyclic carbonate has bigger polarity; therefore lithium fully can dissociate; but because its viscosity is bigger; has lower ionic conductance; therefore can sneak into usually and have low polarity and low viscous linear carbonate is formed mixed electrolytic solution, contain the viscosity of cyclic carbonate electrolyte with reduction.Described cyclic carbonate comprises such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) etc.Described linear carbonate comprises such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC) etc.Such as, document (J.Blectrochem.Soc.146 (2), 485,1999) disclosing a kind of nonaqueous electrolytic solution is to be mixed by ethylene carbonate (EC), diethyl carbonate (DEC) and three kinds of components of dimethyl carbonate (DMC), has improved the cryogenic property of battery system.This mixed system has become the conventional system of making lithium secondary cell electrolyte at present.
But present this non-aqueous solution electrolysis liquid system still can not satisfy the needs of lithium secondary battery to cryogenic property, under the discharge temp situation of low excessively (being less than or equal to-10 ℃), the discharge capacity of battery is lower, make troubles for user's use, also affect the use of lithium ion battery simultaneously at severe cold area.
[summary of the invention]
The objective of the invention is to, a kind of nonaqueous electrolytic solution is provided, it can improve the low temperature performance of lithium secondary battery.
Another object of the present invention is to, a kind of lithium secondary battery with good low temperature performance is provided.
The objective of the invention is to realize by following technical solution:
A kind of nonaqueous electrolytic solution, it comprises non-aqueous organic solvent; Lithium salts; And additive, described additive is selected from the sulfuryl compound shown in the following formula:
Ar represents phenyl or has the phenyl of 1-2 carbon atom alkyl in the formula, R represent to have 1-6 carbon atom alkyl, a 2-6 carbon atom alkenyl, phenyl or have the phenyl of 1-2 carbon atom alkyl, this additive level is 0.1～5 weight % with respect to the electrolyte total weight, is preferably 0.3～2 weight %.
Further described R represent to have 1-4 carbon atom alkyl, a 2-4 carbon atom alkenyl, phenyl or to have 1-2 carbon former in the phenyl of alkyl, Ar represents phenyl.
Preferred described additive comprises at least a in methyl phenyl sulfone, ethylphenyl sulfone, 1-butyl phenyl sulfone, vinyl phenyl sulfone, 1-propenyl phenylsulfone, butadienyl phenylsulfone, diphenyl sulphone (DPS), 3-methyldiphenyl sulfone and the p-methylphenyl vinyl sulfone.
Described lithium salts has no particular limits, and can use the conventional lithium salts that uses in the prior art, is selected from LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiSbF
6, LiClO
4, LiCl, LiBr and LiCF
2SO
3In at least a, the concentration of described lithium salts in nonaqueous electrolytic solution is 0.6～1.8M.
Described non-aqueous organic solvent has no particular limits, can use the conventional non-aqueous organic solvent that uses in the prior art, be selected from dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, propylene carbonate, ethylene carbonate, 1,1-or 1,2-dimethoxy ethane, 1, at least a in the inferior butene esters of 2-diethoxy ethane, carbonic acid, vinylene carbonate, methyl acetate, methyl propionate, methyl formate and the ethyl acetate.
A kind of lithium secondary battery comprises positive pole, negative pole and places barrier film and nonaqueous electrolytic solution between described positive pole and the negative pole that wherein said nonaqueous electrolytic solution adopts the nonaqueous electrolytic solution of the invention described above, comprises non-aqueous organic solvent; Lithium salts; And additive, described additive is selected from the sulfuryl compound shown in the following formula:
Ar represents phenyl or has the phenyl of 1-2 carbon atom alkyl in the formula, R represent to have 1-6 carbon atom alkyl, a 2-6 carbon atom alkenyl, phenyl or have the phenyl of 1-2 carbon atom alkyl, this additive level is 0.1～5 weight % with respect to the electrolyte total weight.
Described positive pole is according to known technology, is coated on the positive electrode collector and is formed by the composite anode sizing agent of lithium positive active material, conductive agent, adhesive and stirring solvent that contains that can inlay with the removal lithium embedded ion.Wherein, described positive active material has no particular limits, and can use the conventional Li that uses in the prior art
xNi
1-yCo
yO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
xMn
2-yB
yO
2In (wherein, B is a transition metal, 0.9≤x≤1.1,0≤y≤1.0) one or several.
Described negative pole is according to known technology, is coated on the negative electrode collector and forms by inlaying the cathode size that becomes with material with carbon element, adhesive and the solvent of removal lithium embedded ion.Wherein, described negative active core-shell material has no particular limits, can use the conventional material that can embed/disengage lithium ion that uses in the prior art, as native graphite, the product of roasting of Delanium, coke, carbon black, RESEARCH OF PYROCARBON, carbon fiber and organic polymer etc.
Compared with prior art, the invention has the advantages that, the present invention has adopted the sulfuryl compound of band phenyl as additive, be added with this compound and can improve the ionic conductance of electrolyte, reach the effect that its freezing point and viscosity reduce, thereby lithium ion also can be moved at low temperatures with fast speeds, the added sulfuryl compound of the present invention simultaneously allows lithium ion or electronics to propagate in the formed conjugated system of added sulfuryl compound, thereby the phenomenon of having avoided lithium ion under the freezing point of traditional electrolyte, can't propagate, thereby effectively improve the low temperature performance of lithium ion battery.
Also by following detailed description, the features and advantages of the present invention will be more apparent in conjunction with the accompanying drawings.
[description of drawings]
Fig. 1 is the comparison diagram of the lithium battery low temperature discharge rate of the embodiment of the invention 1～embodiment 6 and Comparative Examples.
Fig. 2 is the partial cutaway schematic of the lithium rechargeable battery of embodiment of the present invention.
Among the figure: positive plate 1 negative plate 2 barrier films 3 electrode groups 4 battery cases 5
[embodiment]
Below in conjunction with embodiment the present invention is described in further detail, should be appreciated that drawing and description are illustrative and not restrictive in essence.
Non-water electrolytic solution additive of the present invention is to join in the non-aqueous organic solvent that contains lithium salts, and non-aqueous organic solvent plays the medium effect, and migration can participate in the ion of chemical reaction.Lithium salts and non-aqueous organic solvent can adopt nonaqueous electrolytic solution lithium salts and organic solvent commonly used.Consider from the oxidation stability angle, preferably select LiClO for use
4, LiPF
6, LiBF
4, LiAsF
6, that adopt in the example of the present invention is lithium hexafluoro phosphate LiPF
6The concentration of preferred lithium salts is 0.6～1.8M, when lithium salt during less than 0.6M, the performance of electrolyte is because of the conductibility variation of lithium ion, when lithium salt during greater than 1.8M, the migration performance of lithium ion reduces because of the viscosity increase of electrolyte, and that adopt in the example of the present invention is lithium hexafluoro phosphate LiPF
6Concentration is 1M.The preferred mixture that uses cyclic carbonate and linear carbonate is as solvent, wherein when cyclic carbonate and linear carbonate during with volume ratio mixing in 1: 1～1: 6, uses the electrical property of the electrolyte of this solvent to be enhanced.Adopting organic solvent in the example of the present invention is the mixture of ethylene carbonate (EC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and four kinds of volume of organic solvent percentages are 2: 3: 1: 1.
By the total amount of electrolyte, the weight percent concentration of the sulfuryl compound of interpolation is 0.1～5 weight %, the DeGrain if the concentration of additive is too little, and concentration then exerts an influence to the capacity and the cycle life of battery too greatly.The preferred additives weight percent concentration is 0.3～2 weight %.Described sulfuryl compound can prepare by known method, or obtains by commercially available approach.
A kind of lithium secondary battery of the present invention, except above-mentioned electrolyte and additive, it also comprises positive pole, negative pole, places the barrier film between described positive pole and the negative pole.Described positive pole is according to known technology, is coated on the positive electrode collector and is formed by the composite anode sizing agent of lithium positive active material, conductive agent, adhesive and stirring solvent that contains that can inlay with the removal lithium embedded ion.
The positive active material that adopts in the example of the present invention is cobalt acid lithium LiCoO
2Can strengthen the conductive agent of battery conductive, can be carbon black, graphite-like material with carbon element etc., and what adopt in the example of the present invention is acetylene black.Adhesive can be fluorine resin such as polytetrafluoroethylene, Kynoar and polyethylene, polyvinyl alcohol etc., as long as this adhesive can be dissolved in the employed solvent, what adopt in the example of the present invention is polyvinylidene fluoride.Organic solvent can be selected from N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol etc., and what adopt in the example of the present invention is the N-N-methyl-2-2-pyrrolidone N-.As what be used for that anodal collector body, example of the present invention adopt is aluminium foil.
Described negative pole is according to known technology, is coated on the negative electrode collector and forms by inlaying the cathode size that becomes with material with carbon element, adhesive and the solvent of removal lithium embedded ion.The material with carbon element that adopts in the example of the present invention is a native graphite.The negative pole adhesive can be fluorine resins such as polytetrafluoroethylene, Kynoar and polyethylene, polyvinyl alcohol, and what adopt in the example of the present invention is polytetrafluoroethylene PTFE; Solvent can be N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol, deionized water, and what adopt in the example of the present invention is deionized water.As the collector body that is used for negative pole, can be Copper Foil, stainless steel foil, nickel foil, what adopt in the example of the present invention is Copper Foil.
Described barrier film can be nonwoven fabrics, synthetic resin microporous barrier, the preferential synthetic resin microporous barrier that uses, be excellent with polyolefin microporous film again wherein, polyethene microporous membrane, microporous polypropylene membrane, polyethylene polypropylene composite micro porous film are specifically arranged, and what adopt in the example of the present invention is polyethylene, polypropylene composite diaphragm paper.
Above-mentioned positive pole, negative pole and barrier film by stacked or lithium rechargeable battery that takeup type is assembled into and inject nonaqueous electrolytic solution of the present invention, had advantages such as superior low temperature discharge property energy.
Fig. 2 shows and prepares lithium rechargeable battery according to an embodiment of the present invention.Comprise that electrode group 4 and nonaqueous electrolytic solution that positive pole 1, negative pole 2, barrier film 3 constitute are accommodated in the battery case 5 jointly, by battery cover 6 sealings, electrode 1 has a leading-out terminal 7 and is connected with battery cover 6, and negative pole 2 has a leading-out terminal 8 and is connected with battery case 5, to carry out the output of electric current.But, should be appreciated that the positive pole 1 that can use embodiment of the present invention constitutes other lithium batteries.
The present invention is further illustrated below in conjunction with example.
[embodiment 1]
With ethylene carbonate (EC)/ethylmethyl carbonate (EMC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) with 2: 3: 1: 1 volume ratio is mixed, and makes the organic solvent of mixing.LiPF with 1M
6Join in the solvent, and in solvent, further add the electrolysis additive that contains the vinyl phenyl sulfone of 1 weight % according to electrolyte total weight meter, make the composition of electrolyte.
Cobalt acid lithium LiCoO with 95% weight
2Powder, the polyvinylidene fluoride PVDF that adopts 2% weight is an adhesive, and the acetylene black of 3% weight is conductive agent, and N-N-methyl-2-2-pyrrolidone N-NMP is a solvent, mixes, and makes the used anode sizing agent of coating.Adopt the mode of slurry to be uniformly coated on the aluminium foil mixed slurry that makes, oven dry, compressing tablet, be cut into the anode pole piece of 610 * 55mm size.
With the native graphite of 95% weight, the adhesive polytetrafluoroethylene PTFE of 5% weight, solvent deionized water mixes, and makes the used cathode size of coating.Adopt the mode of slurry to be uniformly coated on the Copper Foil cathode size that makes, oven dry, compressing tablet are cut into the cathode pole piece of 660 * 57mm size.
With positive plate, diaphragm paper, negative plate be lamination and winding successively, includes in f18 * 65mm cylindrical housings, injects the electrolyte of the above-mentioned preparation of 6g, ageing in a conventional manner then, seals, and has finished the preparation of lithium secondary battery thus.
[embodiment 2]
In the present embodiment, in solvent, add and contain the 1-propenyl phenylsulfone of 0.5 weight % as additive according to electrolyte total weight meter.In addition, other compositions, technical process and condition and
[embodiment 3]
In the present embodiment, in solvent, add and contain the butadienyl phenylsulfone of 0.3 weight % as additive according to electrolyte total weight meter.In addition, other compositions, technical process and condition are identical with embodiment 1.
[embodiment 4]
In the present embodiment, in solvent, add and contain the diphenyl sulphone (DPS) of 0.1 weight % as additive according to electrolyte total weight meter.In addition, other compositions, technical process and condition are identical with embodiment 1.
[embodiment 5]
In the present embodiment, in solvent, add and contain the tolyl vinyl sulfone of 3 weight % as additive according to electrolyte total weight meter.In addition, other compositions, technical process and condition are identical with embodiment 1.
[embodiment 6]
In the present embodiment, in solvent, add and contain the 3-methyldiphenyl sulfone of 5 weight % as additive according to electrolyte total weight meter.In addition, other compositions, technical process and condition are identical with embodiment 1.
[Comparative Examples]
In this example, what adopted is existing conventional electrolysis liquid, does not promptly add any additives in electrolyte.In addition, other compositions, technical process and condition are identical with embodiment 1 respectively.
[test]
Battery to embodiment and Comparative Examples carries out performance test, and is as follows:
Testing equipment: BS-9300 ability meter, climatic chamber etc.
The normal temperature discharge capacity: under 25 ℃, with the current charges of 1C speed (charging and discharge rate) to 4.2V then under 25 ℃ with the current discharge of 0.5C speed to the discharge capacity that 3.0V was obtained, unit is mAh;
Low temperature discharge capacity: under 25 ℃, with the current charges of 1C speed (charging and discharge rate) to 4.2V, then after shelving 2 hours under-10 ℃ the cryogenic conditions, under-10 ℃ with the current discharge of 0.2C speed to the discharge capacity that 3.0V was obtained, unit is mAh;
-10 ℃ of low temperature discharge capability retention=(low temperature discharge capacity/normal temperature discharge capacity) * 100%, unit is %;
Test result is seen Fig. 1.
As can be seen from the figure: before using achievement of the present invention lithium ion battery is carried out-10 ℃ of following 0.2C discharge performance tests, its capability retention is below 80%.After having used achievement of the present invention, lithium ion battery is carried out-10 ℃ of following 0.2C discharge performance tests, its capability retention is all more than 80%, and its optimum efficiency can remain on more than 95%.As can be seen from Figure 1, the weight percent concentration of the sulfuryl compound of interpolation is preferably 0.1～5 weight %, and preferred weight of additive percent concentration is 0.3～2 weight %.
Claims (12)
1. nonaqueous electrolytic solution, it comprises: non-aqueous organic solvent; Lithium salts; And additive, described additive is selected from the sulfuryl compound shown in the following formula:
Ar represents phenyl or has the phenyl of 1-2 carbon atom alkyl in the formula, R represent to have 1-6 carbon atom alkyl, a 2-6 carbon atom alkenyl, phenyl or have the phenyl of 1-2 carbon atom alkyl, this additive level is 0.1～5 weight % with respect to the electrolyte total weight.
2. nonaqueous electrolytic solution according to claim 1, described R represent to have the alkyl of 1-4 carbon atom, the alkenyl of a 2-4 carbon atom.
3. nonaqueous electrolytic solution according to claim 2, described additive comprise at least a in methyl phenyl sulfone, ethylphenyl sulfone, 1-butyl phenyl sulfone, vinyl phenyl sulfone, 1-propenyl phenylsulfone, butadienyl phenylsulfone, diphenyl sulphone (DPS), 3-methyldiphenyl sulfone and the p-methylphenyl vinyl sulfone.
4. according to each described nonaqueous electrolytic solution among the claim 1-3, described additive level is 0.3～2 weight % with respect to the electrolyte total weight.
5. nonaqueous electrolytic solution according to claim 1, described lithium salts is selected from LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiSbF
6, LiClO
4, LiCl, LiBr and LiCF
2SO
3In at least a, the concentration in nonaqueous electrolytic solution is 0.6～1.8M.
6. nonaqueous electrolytic solution according to claim 1, described non-aqueous organic solvent is selected from dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, propylene carbonate, ethylene carbonate, 1,1-or 1,2-dimethoxy ethane, 1, at least a in the inferior butene esters of 2-diethoxy ethane, carbonic acid, vinylene carbonate, methyl acetate, methyl propionate, methyl formate and the ethyl acetate.
7. lithium secondary battery comprises: anodal, negative pole and place barrier film and electrolyte between described positive pole and the negative pole, and wherein, described electrolyte comprises: non-aqueous organic solvent; Lithium salts; And additive, described additive is selected from the sulfuryl compound shown in the following formula:
Ar represents phenyl or has the phenyl of 1-2 carbon atom alkyl in the formula, R represent to have 1-6 carbon atom alkyl, a 2-6 carbon atom alkenyl, phenyl or have the phenyl of 1-2 carbon atom alkyl, this additive level is 0.1～5 weight % with respect to the electrolyte total weight.
8. lithium secondary battery according to claim 7, described R represent to have the alkyl of 1-4 carbon atom, the alkenyl of a 2-4 carbon atom.
9. lithium secondary battery according to claim 8, described additive comprise at least a in methyl phenyl sulfone, ethylphenyl sulfone, 1-butyl phenyl sulfone, vinyl phenyl sulfone, 1-propenyl phenylsulfone, butadienyl phenylsulfone, diphenyl sulphone (DPS), 3-methyldiphenyl sulfone and the p-methylphenyl vinyl sulfone.
10. according to each described lithium secondary battery among the claim 7-9, described additive level is 0.3～2 weight % with respect to the electrolyte total weight.
11. lithium secondary battery according to claim 7, described lithium salts is selected from LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiSbF
6, LiClO
4, LiCl, LiBr and LiCF
2SO
3In at least a, concentration is 0.6～1.8M.
12. lithium secondary battery according to claim 7, described non-aqueous organic solvent is selected from dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, propylene carbonate, ethylene carbonate, 1,1-or 1,2-dimethoxy ethane, 1, at least a in the inferior butene esters of 2-diethoxy ethane, carbonic acid, vinylene carbonate, methyl acetate, methyl propionate, methyl formate and the ethyl acetate.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008146862A (en) * | 2006-12-06 | 2008-06-26 | Samsung Sdi Co Ltd | Lithium secondary battery and nonaqueous electrolyte for lithium secondary battery |
| CN110233292A (en) * | 2015-07-08 | 2019-09-13 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte for lithium ion cell and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60134203D1 (en) * | 2000-10-20 | 2008-07-10 | Ube Industries | Non-aqueous electrolyte containing secondary battery with improved Entladekapazitätspeicherung |
| JP4187959B2 (en) * | 2001-10-24 | 2008-11-26 | 三井化学株式会社 | Non-aqueous electrolyte and secondary battery using the same |
| KR100458568B1 (en) * | 2002-04-03 | 2004-12-03 | 삼성에스디아이 주식회사 | An electrolyte for a lithium battery and a lithium battery comprising the same |
| KR100527827B1 (en) * | 2003-03-13 | 2005-11-09 | 삼성에스디아이 주식회사 | A non-aqueous electrolyte and a lithium secondary battery comprising the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008146862A (en) * | 2006-12-06 | 2008-06-26 | Samsung Sdi Co Ltd | Lithium secondary battery and nonaqueous electrolyte for lithium secondary battery |
| CN110233292A (en) * | 2015-07-08 | 2019-09-13 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte for lithium ion cell and lithium ion battery |
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| CN100444456C (en) | 2008-12-17 |
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