CN100347903C - Nonaqueous electrolytic solution and lithium secondary battery - Google Patents
Nonaqueous electrolytic solution and lithium secondary battery Download PDFInfo
- Publication number
- CN100347903C CN100347903C CNB200480000437XA CN200480000437A CN100347903C CN 100347903 C CN100347903 C CN 100347903C CN B200480000437X A CNB200480000437X A CN B200480000437XA CN 200480000437 A CN200480000437 A CN 200480000437A CN 100347903 C CN100347903 C CN 100347903C
- Authority
- CN
- China
- Prior art keywords
- carbonate
- electrolytic solution
- aqueous electrolytic
- lithium salts
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 165
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 92
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 92
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 82
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 64
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 43
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910013872 LiPF Inorganic materials 0.000 claims description 34
- 101150058243 Lipf gene Proteins 0.000 claims description 34
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 33
- -1 alkyl biphenyl Chemical compound 0.000 claims description 32
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 31
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- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 26
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 25
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 22
- 125000001118 alkylidene group Chemical group 0.000 claims description 21
- 235000010290 biphenyl Nutrition 0.000 claims description 19
- 239000004305 biphenyl Substances 0.000 claims description 19
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- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229910013075 LiBF Inorganic materials 0.000 claims description 14
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
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- 239000011149 active material Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
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- 150000002642 lithium compounds Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical group [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
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- 230000002045 lasting effect Effects 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 28
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- 238000012360 testing method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 230000010220 ion permeability Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- JCDWETOKTFWTHA-UHFFFAOYSA-N methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=CC=C1 JCDWETOKTFWTHA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
An object of the invention is to provide such a battery that has a high capacity, is excellent in storage characteristics, cycle characteristics and continuous charging characteristics, and is small in gas generation amount, whereby size reduction and improvement in performance of a lithium secondary battery can be attained. The present invention relates to a nonaqueous electrolytic solution comprising a lithium salt and a nonaqueous solvent dissolving the same, wherein the electrolytic solution contains, as the lithium salt, LiPF6 in a concentration of from 0.2 to 2 mole/L, and LiBF4 and/or a compound represented by the following formula (1) in a molar ratio of from 0.005 to 0.4 with respect to LiPF6, and the nonaqueous solvent mainly comprises (1) ethylene carbonate and/or propylene carbonate, (2-1) a symmetric linear carbonate, (2-2) an asymmetric linear carbonate, and (3) vinylene carbonate.
Description
Technical field
The present invention relates to non-aqueous electrolytic solution and adopt its lithium secondary battery.More specifically, the present invention relates to such lithium secondary battery, it has high power capacity and excellent storage characteristic, cycle characteristics and continuous discharge characteristic, and produces a spot of gas.
Background technology
In recent years, along with reducing of electrical equipment weight and size, people have the lithium secondary battery of high-energy-density always in exploitation.
Usually, used electrolyte solution mainly is made of lithium salts and nonaqueous solvents in the lithium secondary battery.The example of the main component of nonaqueous solvents comprises cyclic carbonate such as ethylene carbonate and propylene carbonate; Linear carbonate such as dimethyl carbonate and methyl ethyl carbonate; And cyclic carboxylic esters such as gamma-butyrolacton and gamma-valerolactone.
In order to improve the characteristic of secondary cell,, nonaqueous solvents and lithium salts are made a lot of researchs as load character, cycle characteristics, storage characteristic and low-temperature characteristics.
For example, patent document 1 discloses following content: utilize asymmetrical linear carbonate with the mixture of cyclic carbonate with two keys during as nonaqueous solvents, mainly be cyclic carbonate and negative reaction with two keys, form the film of high-quality in negative terminal surface, thereby prevented that asymmetrical linear carbonate from forming insulator film in negative terminal surface, and then improved cycle characteristics.
Only comprise LiPF in employing
6In the secondary cell as the electrolyte solution of lithium salts, pass through LiPF
6(the LiPF that dissociates
6→ Li
++ PF
6 -→ Li
++ F
-+ PF
5) and the PF of formation
5, cause the C-O bond fission in the carbonic ester, and then make carbonic ester decompose (self discharge), cause battery capacity when storing, to reduce thus.Yet patent document 2 but discloses following content: comprise LiPF in employing
6And LiBF
4The secondary cell of electrolyte solution in, by LiBF
4Anion (the BF that forms
4 -) suppress by LiPF
6The PF that forms
6 -Decomposition, make the electrolyte solution stabilisation, can prevent that thus battery capacity from reducing when storing.Patent document 2 also discloses the mixture of employing cyclic carbonate and linear carbonate as nonaqueous solvents, and has used the mixture of ethylene carbonate and diethyl carbonate in embodiment.
Yet the needs to lithium secondary battery of high performance increase day by day in recent years, and require this lithium secondary battery to have high power capacity and improved high-temperature storage characteristics and cycle characteristics.
As the measure that increases battery capacity, adopt the design of filling electrode active material as much as possible in limited battery volume usually, for example, the compression electrodes active material is to improve its density.Yet, other problem has appearred again when improving battery capacity.For example, in case reduce space in the battery, then the interior pressure of battery just increases significantly because of the formation of gas, even only form a spot of gas because of the decomposition of electrolyte solution.
When the back-up source when battery is used as power failure or the power supply of portable set, adopt the charging method that continues, wherein weak current is offered battery,, and then make it to keep charged state with the self discharge of balancing battery.In the charging method that continues, electrode is in the high activity state usually, thereby quickens the reduction of battery capacity, and the decomposition by electrolyte solution produces gas easily.In cylindrical battery with safety valve (it works when detecting unusual rising that inner pressure of battery causes because of overcharging), the situation that exists safety valve to open sometimes because of the formation of gases in a large number.In not having the prismatic batteries of safety valve, battery can expand because of the pressure of formed gas or break in severe case.
Therefore, the strong request lithium secondary battery suppresses the formation of gas when trickle charge, suppresses the reduction of capacity simultaneously again.
In patent document 1 disclosed lithium secondary battery, the electrolyte solution that is adopted is by with LiPF
6Be dissolved in and form in the nonaqueous solvents, described nonaqueous solvents comprises (1) ethylene carbonate, (2) methyl ethyl carbonate and (3) vinylene carbonate, yet the reduction of its capacity when preventing to continue charging and the reduction of gas production are basically without any effect, although it can improve cycle characteristics.
In addition, in patent document 2 disclosed secondary cells, adopt to comprise LiPF
6And LiBF
4As the electrolyte solution of lithium compound, yet when battery was stored under 80 ℃ or higher hot conditions, battery behavior worsened, and cycle characteristics is insufficient.
And, in patent document 3 disclosed secondary cells, employing comprises the electrolyte solution of specific cyclic imide salt as lithium compound, yet, when it is prepared into the battery with high power capacity, be not that whole storage characteristic, cycle characteristics and lasting charge characteristics all can keep high level simultaneously, especially, when battery was stored under hot conditions, battery behavior reduced, although can prevent that aluminium is corroded.
[patent document 1]
JP-A-11-185806
[patent document 2]
JP-A-8-64237
[patent document 3]
JP-W-11-512563
Summary of the invention
The present invention finishes considering under the afore-mentioned of prior art, its objective is the lithium secondary battery that provides such, and this lithium secondary battery has high power capacity, and storage characteristic, cycle characteristics and lasting charge characteristic are good, and gas production is little.
The inventor is through finding after the conscientious research, by with LiPF
6And LiBF
4And/or the lithium salts shown in the following formula (1) is dissolved in the nonaqueous solvents that comprises all kinds of solvents particular combinations and the non-aqueous electrolytic solution that forms, and it is little that the capacity when continuing charging reduces, and the gas production when continuing charging is little, and finished the present invention thus.
First aspect the present invention relates to a kind of non-aqueous electrolytic solution that comprises the nonaqueous solvents of lithium salts and dissolving lithium salts, it is characterized in that as lithium salts, this concentration of electrolyte solutions is the LiPF of 0.2～2 mole/L
6And with respect to LiPF
6Mol ratio be 0.005～0.4 LiBF
4And/or the compound shown in the following formula (1); And described nonaqueous solvents mainly comprises (1) ethylene carbonate and/or propylene carbonate, (2-1) Dui Cheng linear carbonate, (2-2) asymmetrical linear carbonate, and (3) vinylene carbonate.
Second aspect the invention still further relates to a kind of non-aqueous electrolytic solution that comprises the nonaqueous solvents of lithium salts and dissolving lithium salts, it is characterized in that as lithium salts, this concentration of electrolyte solutions is the LiPF of 0.2～2 mole/L
6And concentration is the LiBF of 0.001～0.3 mole/L
4And described nonaqueous solvents mainly comprises (1) ethylene carbonate and/or propylene carbonate, (2-1) Dui Cheng linear carbonate, (2-2) asymmetrical linear carbonate, and (3) vinylene carbonate.
The third aspect the invention still further relates to the non-aqueous electrolytic solution that comprises lithium salts and dissolve the nonaqueous solvents of lithium salts, it is characterized in that as lithium salts, this concentration of electrolyte solutions is the LiPF of 0.5～2.5 mole/L
6And concentration is the compound shown in the following formula (1) of 0.001～0.3 mole/L:
(in the formula, the R representative has the straight or branched alkylidene of 1～20 carbon atom, and it can be replaced by fluorine atom, and condition is that this alkylidene chain has no more than 12 carbon atoms except that side chain).
Description of drawings
Fig. 1 is the schematic sectional view of the cylindrical battery for preparing in an embodiment.
In the figure, numeral 1 is represented battery case, and 2 represent sealing plate, and 3 represent insulating washer, the spiral electrode assemblie of 4 representatives, and 5 represent positive terminal, and 6 represent negative terminal, and 7 represent dead ring, and 8 represent the failure of current device.
Embodiment
Mainly comprise the nonaqueous solvents of lithium salts and dissolving lithium salts according to non-aqueous electrolytic solution of the present invention, similar to common non-aqueous electrolytic solution, it first is characterised in that as lithium salts, the present invention is used in combination LiPF
6And LiBF
4And/or the lithium salts shown in the following formula (1); The LiPF that comprises specific concentrations
6And comprise with respect to LiPF
6LiBF for special ratios
4And/or the lithium salts shown in the following formula (1).
In this non-aqueous electrolytic solution, LiPF
6Concentration be 0.2～2 mole/L.If LiPF
6Concentration too high or too low, then exist the conductivity of electrolyte solution to reduce and then worsen the situation of battery behavior.Preferred LiPF
6Concentration be 0.3 mole/L or bigger, 0.6 mole/L or bigger particularly, and be preferably 1.8 moles/L or littler, particularly 1.5 moles/L or littler.At aforesaid LiPF
6In the concentration range, described upper and lower bound can combination in any.
If LiPF
6Be used in combination with the lithium salts shown in the following formula (1), then LiPF in the non-aqueous electrolytic solution
6Concentration can be 0.5～2.5 mole/L.LiPF under preferred this situation
6Concentration be 0.6 mole/L or bigger, 0.7 mole/L or bigger particularly, and be preferably 1.8 moles/L or littler, particularly 1.5 moles/L or littler.At aforesaid LiPF
6In the concentration range, described upper and lower bound can combination in any.
In formula (1), the R representative has the straight or branched alkylidene of 1～20 carbon atom, preferred 2～12 carbon atoms, and it can be replaced by fluorine atom, and condition is to have 1～12 carbon atom, preferred 2～8 carbon atoms in this alkylidene except that side chain.The alkyl that constitutes this alkylidene side chain generally has 1～8 carbon atom, preferred 1～4 carbon atom, and this alkyl can be a straight or branched.
The example of straight-chain alkyl-sub-comprises ethylidene, trimethylene, tetramethylene and pentamethylene.The example of branched alkylidene comprises 1-methyl-ethylidene (propylidene), 2-methyl-trimethylene and new pentylidene.Any hydrogen atom of fluorine atom in can substituted alkylene, for alkylidene by the situation that fluorine atom replaced, the preferred perfluorinated alkylidene that all replaced of its whole hydrogen atoms by fluorine atom.
The instantiation of the lithium salts shown in the following formula (1) comprises 1 of ring-type, 2-second disulfonyl imidization lithium, 1 of ring-type, the 3-third disulfonyl imidization lithium, 1 of ring-type, 2-perfluor second disulfonyl imidization lithium, 1 of ring-type, the 3-perfluor third disulfonyl imidization lithium reaches 1 of ring-type, 4-perfluor fourth disulfonyl imidization lithium.Wherein, 1 of preferred ring-type, 1 of 2-perfluor second disulfonyl imidization lithium and ring-type, the 3-perfluor third disulfonyl imidization lithium.
LiBF
4Or the lithium salts shown in the following formula (1) is with respect to LiPF
6Mol ratio be generally 0.005 or bigger, be preferably 0.01 or bigger, be preferably 0.05 or bigger especially, and be generally 0.4 or littler, be preferably 0.2 or littler, more preferably 0.15 or littler.In aforesaid molar ratio range, described upper and lower bound can combination in any.
If mol ratio is too big, the trend that then exists battery behavior to be lowered; If mol ratio is too little, the gas when then being difficult to suppress to continue charging produces and capacity worsens.If comprise LiBF simultaneously
4With the lithium salts shown in the following formula (1), then its total amount satisfies aforementioned range.
LiBF
4Or the concentration of lithium salts in non-aqueous electrolytic solution shown in the following formula (1) is generally 0.001～0.3 mole/L.If LiBF
4Or the concentration of the lithium salts shown in the following formula (1) is too low, and the gas when then being difficult to suppress to continue charging produces and capacity worsens.
If this concentration is too high, then there is the trend of high temperature storage battery behavior reduction afterwards.Preferred LiBF
4Or the concentration of the lithium salts shown in the following formula (1) is 0.01 mole/L or bigger, is preferably 0.02 mole/L or bigger especially, most preferably is 0.05 mole/L or bigger.Its upper limit is preferably 0.25 mole/L or littler, most preferably is 0.18 mole/L or littler.If comprise LiBF simultaneously
4With the lithium salts shown in the following formula (1), then its total amount satisfies aforementioned range.
If electrolyte solution comprises LiPF
6With the lithium salts shown in the following formula (1) as lithium salts, then below the lithium salts shown in the formula (1) with respect to LiPF
6The lower limit of mol ratio can determine arbitrarily, be preferably 0.005 or bigger.If described mol ratio is lower than this lower limit, the situation that then exists aerogenesis when being difficult to suppress fully to continue charging and capacity to worsen sometimes, therefore, preferably this mol ratio is 0.01 or bigger, particularly 0.02 or bigger.Equally, the upper limit of this mol ratio also can determine arbitrarily, if but this mol ratio is too big, then there is the trend that battery behavior reduces after the high temperature storage, and therefore, preferably this mol ratio is 0.5 or littler, particularly 0.2 or littler.
Work as electrolyte solution,, comprise LiPF as lithium salts
6During with lithium salts shown in the following formula (1), LiPF
6Be preferably 0.7～1.7 mole/L with the total amount of lithium salts in non-aqueous electrolytic solution shown in the following formula (1), their concentration and mol ratio can be aforementioned range simultaneously.
In non-aqueous electrolytic solution of the present invention, remove LiPF
6, LiBF
4Outside the lithium salts shown in the following formula (1), can also use other lithium salts for this reason.The example of other lithium salts comprises inorganic lithium salt, as LiClO
4And fluorine-containing organic lithium salt, as LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiCF
3SO
3, LiC (CF
3SO
2)
3, LiPF
4(CF
3)
2, LiPF
4(C
2F
5)
2, LiPF
4(CF
4SO
2)
2, LiPF
4(C
2F
5SO
2)
2, LiBF
2(CF
3)
2, LiBF
2(C
2F
5)
2, LiBF
2(CF
3SO
2)
2And LiBF
2(C
2F
5SO
2)
2
If add other lithium salts, the then preferred concentration of other lithium salts in electrolyte solution is 0.5 mole/L or littler, is preferably 0.2 mole/L or littler especially.Its lower limit can determine arbitrarily, and in order to bring into play certain effect by this interpolation, general preferably is limited to 0.01 mole/L or bigger under this, particularly 0.05 mole/L or bigger.
Comprise concentration be 0.001～0.2 mole/L be selected from LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3Other lithium salts, particularly LiN (CF
3SO
2)
2Situation under, the gas in the time of can further suppressing to continue charging generates.If this concentration is too low, then can not play a role.Preferred this concentration is 0.003 mole/L or bigger, is preferably 0.005 mole/L or bigger especially, most preferably is 0.008 mole/L or bigger.Its upper limit is preferably 0.15 mole/L or littler, is preferably 0.1 mole/L or littler especially.
Of the present invention second is characterised in that described nonaqueous solvents mainly comprises (1) ethylene carbonate and/or propylene carbonate, (2-1) Dui Cheng linear carbonate, (2-2) asymmetrical linear carbonate, and (3) vinylene carbonate.
(1) ethylene carbonate and/or propylene carbonate
Ethylene carbonate and propylene carbonate can use the use that also can be mixed with each other separately, and preferred ethylene carbonate uses separately or mixes use with propylene carbonate.
If ethylene carbonate mixes use with propylene carbonate, then ethylene carbonate (EC) is generally 99/1 or littler with the volume ratio (EC/PC) of propylene carbonate (PC), is preferably 95/5 or littler, and is generally 40/60 or bigger, is preferably 50/50 or bigger.
If the amount of propylene carbonate is too big, then be not preferred especially with graphite in the battery that is negative electrode active material, because propylene carbonate is easy to be decomposed at graphite surface.In this manual, the volume of nonaqueous solvents is the volume under 25 ℃, and the volume of ethylene carbonate then is the volume at its fusing point.
(2) linear carbonate
(2-1) Dui Cheng linear carbonate
The example of the linear carbonate of symmetry comprises dimethyl carbonate, diethyl carbonate and carbonic acid di-n-propyl ester.Wherein preferred carbon number is 5 or carbonic ester still less, preferred especially dimethyl carbonate and diethyl carbonate.These carbonic esters can use separately, also can use by its two or more mixture.
(2-2) asymmetrical linear carbonate
The example of asymmetrical linear carbonate comprises methyl ethyl carbonate, carbonic acid methyl n-pro-pyl ester and carbonic acid ethyl n-pro-pyl ester.Wherein, wherein preferred carbon number is 5 or carbonic ester still less, preferred especially methyl ethyl carbonate.These carbonic esters can use separately, also can use by its two or more mixture.
In non-aqueous electrolytic solution, the volume ratio of the linear carbonate of the total amount of ethylene carbonate and propylene carbonate and symmetry and the total amount of asymmetrical linear carbonate is generally 10/90 to 70/30, be preferably 10/90 to 50/50, be preferably 10/90 to 45/55 especially, most preferably be 15/85 to 40/60.If the linear carbonate of symmetry and the total amount of asymmetrical linear carbonate are too little, then the viscosity of electrolyte solution increases; On the contrary, if this total amount is too big, then the degree of dissociation of lithium salts reduces, in both cases, and the possibility that all exists the conductivity of electrolyte solution to be lowered.
The example of the combination of ethylene carbonate and linear carbonate comprises the combination of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, the combination of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the combination of ethylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, these combinations provide electrolyte solution harmonious good between cycle characteristics and the heavy-current discharge characteristic.In preferred combination, also comprise the various combinations that obtain to the combination of aforementioned ethylene carbonate and linear carbonate by further interpolation propylene carbonate.
(3) vinylene carbonate
The ratio of vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts is generally 0.01% weight or bigger, be preferably 0.1% weight or bigger, be preferably 0.3% weight or bigger especially, most preferably be 0.5% weight or bigger, and be generally 8% weight or littler, be preferably 5% weight or littler, be preferably 3% weight or littler especially.In the ratio of aforesaid vinylene carbonate, the described lower limit and the upper limit can combination in any.
It is believed that vinylene carbonate has in negative terminal surface and forms film and then improve the function of cycle characteristics, and if the ratio of vinylene carbonate too little, then can not improve cycle characteristics fully.On the other hand, if this ratio is too big, the situation that the gas that then exists inner pressure of battery to be produced when at high temperature storing sometimes raises.
In non-aqueous electrolytic solution of the present invention, the principal component of preferred nonaqueous solvents is by the mixed carbonic acid ethyl, propylene carbonate, and the linear carbonate and the asymmetrical linear carbonate of symmetry, and vinylene carbonate forms.
Ethylene carbonate, propylene carbonate, the linear carbonate and the asymmetrical linear carbonate of symmetry, and the total amount of vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts is preferably 80% weight or bigger.Further preferred this total amount is 90% weight or bigger, is preferably 93% weight or bigger especially.Preferred described total amount is the non-aqueous electrolytic solution of aforementioned range, because can realize the good harmony between cycle characteristics and the heavy-current discharge characteristic like this.
Except that the linear carbonate of carbonic acid vinylene, ethylene carbonate, propylene carbonate, symmetry and other examples of non-aqueous the asymmetrical linear carbonate comprise the cyclic carbonate with 5 or more a plurality of carbon atoms, as butylene carbonate; Cyclic ethers is as oxolane and 2-methyltetrahydrofuran; Chain ether is as dimethoxy-ethane and dimethoxymethane; Cyclic carboxylic esters is as gamma-butyrolacton and gamma-valerolactone; And the chain carboxylate, as methyl acetate, methyl propionate, ethyl propionate and methyl butyrate.These nonaqueous solventss can use separately, also can use by its two or more mixture.If non-aqueous electrolytic solution comprises these nonaqueous solventss, its ratio in the non-aqueous electrolytic solution except that lithium salts is generally 20% weight or littler.
Can expect that non-aqueous electrolytic solution of the present invention is as follows to the mechanism that flash-over characteristic produces less deterioration effect, although this mechanism is not fully clearly.
Vinylene carbonate forms stable film in negative terminal surface, and then improves cycle characteristics.Yet, because vinylene carbonate is easy to the positive electrode reaction with charged state, and the anodal height active state that when constant voltage continues charging, is in all the time, so between vinylene carbonate and positive electrode, react, cause positive active material may quicken to worsen, and gas production increase.In addition, the constituent that is formed at the film of negative terminal surface partly is dissolved in the electrolyte solution, and institute's dissolved substances and anodal surface reaction, causes anodal active material to quicken the generation of deterioration and gas.
On the other hand, come from LiBF
4Analyte suppress aforementioned reaction on positive pole, and this material does not suppress vinylene carbonate and forms film in negative terminal surface.In addition, Bu Fen LiBF
4Be reduced in negative terminal surface, on negative pole, form vinylene carbonate and LiBF
4Composite membrane.This composite membrane is heat-staple, and lithium ion permeability excellence.Moreover this composite membrane is difficult to dissolved, suppresses the dissolving of film constituent, thereby suppresses the side reaction of inside battery, and then suppresses the degeneration of electrode active material, keeps good flash-over characteristic thus.
With LiPF
6Compare LiBF
4Be easy to react, and under the situation that does not contain the carbonic acid vinylene, promote and the side reaction of negative material, still work as LiBF with the negative material of charged state
4When coexisting with vinylene carbonate, it forms stable film in negative terminal surface, and this film suppresses and the side reaction of negative material.
As described above, by vinylene carbonate and LiBF
4Between interaction, the deterioration of flash-over characteristic in the time of can improving cycle characteristics and prevent to continue charging.
Particularly, preferred vinylene carbonate is 0.3% weight or bigger in the ratio of the non-aqueous electrolytic solution except that lithium salts, and preferred LiBF
4Concentration in non-aqueous electrolytic solution is 0.02 mole/L or bigger, because effect of the present invention like this is significant.
Although the mechanism of action of lithium salts is still not fully aware of shown in the following formula (1), but the lithium salts shown in the following formula (1) or come from the analyte of this lithium salts, by absorption or be coated with anodal active site, suppress anodal reactivity, and then suppress the side reaction of other component on positive pole of vinylene carbonate and electrolyte solution.In addition, can also think, lithium salts shown in the following formula (1) does not suppress vinylene carbonate and forms film in negative terminal surface, but promote to have the formation of the infiltrative stable film of excellent lithium ion, therefore, can improve cycle characteristics, the gas when suppressing to continue charging produces, and improves the flash-over characteristic when continuing charging.
Non-aqueous electrolytic solution of the present invention can comprise other component as required, for example known assistant, as overcharge and prevent agent, dehydrating agent and plumper.
The example that prevents agent that overcharges comprises aromatic compounds, as biphenyl, and alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran; The partially fluorinated product of aforementioned aromatic compounds, as 2-fluorine biphenyl, neighbour-cyclohexyl fluorobenzene and to the cyclohexyl fluorobenzene; And fluorine-containing anisole compound, as 2,4-two fluoroanisoles, 2,5-two fluoroanisoles and 2,6-two fluoroanisoles.Wherein, the preferred floride-free aromatic compounds that replaces.
These aromatic compounds can be used separately, also can use by its two or more mixture.If use its two or more mixture, then be preferably selected from partial hydrogenation product, cyclohexyl benzene, tert-butyl benzene and the tert-amyl benzene of oxygen-free aromatic compounds such as biphenyl, alkyl biphenyl, terphenyl, terphenyl especially, mix use with oxygen containing aromatic compounds such as diphenyl ether and dibenzofuran.Prevent agent if non-aqueous electrolytic solution comprises to overcharge, then its concentration is generally 0.1～5% weight.Comprising in non-aqueous electrolytic solution overcharges prevents that agent from being preferred, breaks because of overcharging with on fire because can prevent battery like this, and then improves the fail safe of battery.
Usually, prevent that owing to overcharge agent from reacting on anodal and negative pole than the nonaqueous solvents that constitutes non-aqueous electrolytic solution is easier, so, its when continuing charging and high temperature storage and the high activity position of electrode react, the internal resistance that increases battery also produces gas, and then causes that flash-over characteristic significantly worsens when continuing charging and high temperature storage.Yet, add to overcharge preventing agent in the still preferred non-aqueous electrolytic solution of the present invention, because can suppress the deterioration of flash-over characteristic like this.
The example that improves the assistant of capacity retention characteristic and cycle characteristics behind the high temperature storage comprises carbonate products, as vinylethylene carbonate, fluorine ethylene carbonate, trifluoro propylene carbonate, the phenyl-carbonic acid ethyl, carbonic acid erythritan ester and carbonic acid spiral shell-dimethylene ester; Carboxylic acid anhydrides, as succinyl oxide, glutaric anhydride, maleic anhydride, citraconic anhydride, the glutaconate acid anhydrides, itaconic anhydride, the diglycolic acid acid anhydrides, cyclohexyl dicarboxylic acid's acid anhydrides encircles penta tetrabasic carboxylic acid dicarboxylic anhydride and phenyl succinyl oxide; Sulfur-containing compound, as glycol sulfite, 1,3-third sultone, 1,4-fourth sultone, methyl mesylate, busulfan, sulfolane, ring fourth sulfoxide (sulfolene), dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyl two sulphur, tetra methylthiuram monosulfide, N, N-dimethyl methyl sulfonamide and N, N-diethyl Methanesulfomide; Nitrogen-containing compound, as 1-Methyl-2-Pyrrolidone, 1-methyl-2-piperidones, 3-methyl-2-oxazolidone, 1,3-dimethyl-2-imidazolidinone and N methyl succinimide; Hydrocarbon compound, as heptane, octane and cycloheptane; And fluorochemical, as fluorobenzene, two fluorobenzene, phenyl-hexafluoride and benzotrifluoride.These compounds can use separately, also can use by its two or more mixture.If non-aqueous electrolytic solution comprises this assistant, then its concentration is generally 0.1～5% weight.
Non-aqueous electrolytic solution of the present invention can pass through LiPF
6, LiBF
4And/or the lithium salts shown in the following formula (1) and other compound when needing are dissolved in the nonaqueous solvents and prepare, described nonaqueous solvents mainly comprises (1) ethylene carbonate and/or propylene carbonate, (2-1) Dui Cheng linear carbonate, (2-2) asymmetrical linear carbonate, and (3) vinylene carbonate.Preparation is during non-aqueous electrolytic solution, and preferred feedstock is dewatered in advance, and general preferred they dewater in advance to 50ppm or littler, more preferably to 30ppm or littler.
Non-aqueous electrolytic solution of the present invention is suitable as the electrolyte solution of secondary cell, particularly lithium secondary battery.The lithium secondary battery of the present invention that adopts this electrolyte solution will be described below.
Lithium secondary battery of the present invention is identical with known lithium secondary battery except electrolyte solution, and has anodal and negative pole and be contained in structure in the shell by the perforated membrane that is impregnated with electrolyte solution of the present invention.Therefore, this secondary cell can have arbitrary shape, as cylindrical shape, prismatic, thin slice shape, coin shape and large-sized shape.
As mentioned above, adopt the lithium secondary battery of electrolyte solution of the present invention to form a spot of gas in lasting charged state.Therefore, if electrolyte solution of the present invention is used to have the battery of tie breaker, and this circuit breaker then can prevent at the abnormal operation that continues to take place under the charged state tie breaker because of the rising of inner pressure of battery under the abnormality (as overcharging) plays a role.
Inner pressure of battery raises and causes the problem of cell expansion, occur in shell easily and be in the battery that forms by 0.5mm metal aluminum or aluminum alloy thick or littler, that particularly 0.4mm is thick or littler, and volume capacity density is 110mAh/cc or bigger, especially 130mAh/cc or bigger, particularly in 140mAh/cc or the bigger battery, but adopt electrolyte solution of the present invention can prevent cell expansion.
The example of negative electrode active material comprises carbonaceous material and can embed and deviate from metallic compound, lithium metal and the lithium alloy of lithium.These materials can use separately, also can use by its two or more mixture.
Wherein, preferred carbonaceous material, preferred especially graphite or its surface scribble the graphite material of amorphous (comparing with graphite) carbon.
The d value (interlamellar spacing) of graphite character face (002 face) is measured by the X-ray diffraction method according to the JSPS method, and the d value of graphite is preferably 0.335～0.338nm, is preferably 0.335～0.337nm especially.The crystallite size of measuring by the X-ray diffraction method according to JSPS (Lc) is preferably 30nm or bigger, and more preferably 50nm or bigger is preferably 100nm or bigger especially.Ash content is preferably 1% weight or littler, and more preferably 0.5% weight or littler is preferably 0.1% weight or littler especially.
The graphite material that its surface of preferred surface scribbles amorphous carbon has such structure: the d value of wherein using lattice plane under the X-ray diffraction (002 face) be 0.335～0.338nm graphite as nuclear core material, and adhere to the carbonaceous material of the d value of lattice plane under the X-ray diffraction (002 face) greater than the nuclear core material on the nuclear core material, the d value of lattice plane (002 face) is 99/1～80/20 greater than the weight ratio of the carbonaceous material of nuclear core material under nuclear core material and the X-ray diffraction.Utilize this material to prepare to have high power capacity and be difficult to negative pole with the electrolyte solution reaction.
For the median diameter that obtains by laser diffraction and scattering method, the particle diameter of carbonaceous material is preferably 1 μ m or bigger, and more preferably 3 μ m or bigger are preferably 5 μ m or bigger especially, most preferably are 7 μ m or bigger.Its upper limit is preferably 100 μ m or littler, and more preferably 50 μ m or littler are preferably 40 μ m or littler especially, most preferably are 30 μ m or littler.
The BET method specific area of carbonaceous material is preferably 0.3m
2/ g or bigger, more preferably 0.5m
2/ g or bigger is preferably 0.7m especially
2/ g or bigger most preferably is 0.8m
2/ g or bigger.Its upper limit is preferably 25.0m
2/ g or littler, more preferably 20.0m
2/ g or littler is preferably 15.0m especially
2/ g or littler most preferably is 10.0m
2/ g or littler.
Carbonaceous material preferably has 0.01～0.7 R value (=I
B/ I
A), R value representation peak P
APeak intensity I
AWith peak P
BPeak intensity I
BRatio, peak P wherein
ABe to utilize argon laser to obtain being positioned in the Raman spectrum 1570～1620cm
-1The peak of scope, peak P
BBe to be positioned at 1300～1400cm in the spectrum
-1The peak of scope.It is positioned at 1570～1620cm
-1The half breadth at the peak of scope is preferably 26cm
-1Or littler, be preferably 25cm especially
-1Or it is littler.
The example that can embed and deviate from the metallic compound of lithium comprises the compound that contains such as metals such as Ag, Zn, Al, Ga, In, Si, Ge, Sn, Pb, P, Sb, Bi, Cu, Ni, Sr and Ba, and these metals can simple substance, oxide or use with the form of the alloy of lithium.In the present invention, preferably comprise the compound of the element that is selected from Si, Sn, Ge and Al, more preferably be selected from the oxide or the lithium alloy of the metal of Si, Sn and Al.
Can embed and deviate from metallic compound or its oxide or the lithium alloy of lithium, generally have the Unit Weight capacity bigger than the carbonaceous material that with graphite is representative, therefore, for the lithium secondary battery that requires to have higher capacity, it is preferred.
The example of positive active material comprises the material that can embed and deviate from lithium, for example, lithium-transition metal composite oxide such as lithium-cobalt/cobalt oxide, lithium-nickel oxide and lithium-Mn oxide, and by replace the composite oxides that the part transition metal in the aforementioned composite oxides obtains with other metal.These examples for compounds comprise Li
xCoO
2, Li
xNiO
2, Li
xMnO
2, Li
xCo
1-yM
yO
2, Li
xNi
1-yM
yO
2And Li
xMn
1-yM
yO
2, M representative is selected from least a among Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, V, Sr and the Ti, 0.4≤x≤1.2, and 0≤y≤0.6 in the formula.
Particularly, preferably by replacing the compound that cobalt, nickel or manganese partly obtains, as Li with other metal
xCo
1-yM
yO
2, Li
xNi
1-yM
yO
2And Li
xMn
1-yM
yO
2, because its Stability Analysis of Structures.Described positive active material can use separately, and form that also can its multiple mixture is used.
The binding agent of active material of being used to bond can be a solvent for use and to the stable any material of electrolyte solution during to the preparation electrode.The example comprises fluororesin, as polyvinylidene fluoride and polytetrafluoroethylene; Polyolefin is as polyethylene and polypropylene; Polymer and copolymer thereof with unsaturated bond, as styrene butadiene rubbers, isoprene rubber and butadiene rubber; And acrylate copolymer and copolymer thereof, as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer.
In order to improve mechanical strength and conductivity, electrode can comprise thickener, electric conducting material, filler etc.
The example of thickener comprises carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, starch phosphate and casein.
Examples of conductive materials comprises metal material, as copper and mickel, and material with carbon element, as graphite and carbon black.
Electrode can prepare according to conventional methods.For example, binding agent, thickener, electric conducting material, solvent etc. are added in negative pole or the positive active material, form slurry; Slurry is coated on the collector body, and dry then and compacting makes electrode.
After drying and the compacting, the density of negative electrode active material layer is generally 1.45g/cm
3Or bigger, be preferably 1.55g/cm
3Or bigger, be preferably 1.60g/cm especially
3Or it is bigger.The density of preferred negative electrode active material layer is high as much as possible, because the capacity of battery is higher like this.It is dry that the density of positive electrode active material layer is generally 3.0g/cm with suppressing afterwards
3Or it is bigger.
Can be like this: by roll extrusion, will wherein add the active material moulded-in-place of binding agent, electric conducting material etc., to form pellet electrode; Perhaps make it form pellet electrode by pressing mold; Perhaps by on collector body, form the film of electrode material such as methods such as vapour deposition, sputter or plating.
Can use various collector bodies, generally adopt metal or alloy.The example of negative electrode collector comprises copper, nickel and stainless steel, preferably uses copper.The example of positive electrode collector comprises metal such as aluminium, titanium and tantalum and alloy thereof, preferably uses aluminium and alloy thereof.
Perforated membrane generally is inserted between positive pole and the negative pole, to prevent short circuit.In this case, electrolyte solution uses by the form that impregnated in the perforated membrane.Material and shape to perforated membrane do not have special restriction, as long as it is stable to electrolyte solution, and the fixing ability excellence of liquid, are the porous chips that forms of raw material, non-woven fleece etc. with polyolefin such as polyethylene and polypropylene preferably.
Sheathing material used in battery of the present invention also can be selected arbitrarily, can use iron, stainless steel, aluminium or its alloy, nickel, titanium of nickel plating etc.
Embodiment
Now be described more specifically the present invention with reference to the following examples and Comparative Examples, under the situation that does not deviate from its essence, the present invention is not limited to these embodiment.
[preparation of negative pole (1)]
With the graphite of 94 weight portions and polyvinylidene fluoride (the trade name KF-1000 of 6 weight portions, KurehaChemical Industry Co., Ltd makes) mix, the d value of the lattice plane that described graphite records according to X-ray diffraction (002 face) is 0.336nm, crystallite size (Lc) is 652nm, ash content is 0.07% weight, the median diameter that records by laser diffraction and scattering method is 12 μ m, and the BET specific area is 7.5m
2/ g is positioned at 1570～1620cm in the Raman spectrum that adopts argon laser to obtain
-1The peak P of scope
APeak intensity I
ABe positioned at 1300～1400cm in the spectrum
-1The peak P of scope
BPeak intensity I
BStrength ratio R=I
B/ I
ABe 0.12, and be positioned at 1570～1620cm in the spectrum
-1The half breadth at the peak of scope is 19.9cm
-1, and to wherein adding the N-N-methyl-2-2-pyrrolidone N-, and then form slurry.This slurry is coated on the surface of Copper Foil that thickness is 18 μ m equably and dry, compacting then, making density is 1.5g/cm
3Negative electrode active material layer, thereby make negative pole (1).
[preparation of negative pole (2)]
By preparing negative pole (2) with the identical mode of preparation negative pole (1), different is to use thickness is the Copper Foil of 12 μ m, this slurry is coated on two surfaces of Copper Foil that thickness is 18 μ m equably and dry, and compacting then, making density is 1.55g/cm
3Negative electrode active material layer.
[preparation of anodal (1)]
LiCoO with 85 weight portions
2, 6 parts by weight of carbon black and 9 weight portions polyvinylidene fluoride mix, to wherein adding the N-N-methyl-2-2-pyrrolidone N-, form slurry, this slurry is coated on two surfaces of aluminium foil that thickness is 20 μ m equably and dry, compacting then, making density is 3.0g/cm
3Positive electrode active material layer, thereby make positive pole (1).
[preparations of anodal (2)]
Prepare positive pole (2) by the mode identical with preparation anodal (1), different is to use thickness is the aluminium foil of 14 μ m.
[preparation of cylindrical shape lithium secondary battery]
Positive pole (2) and negative pole (2) are coiled together with polyethylene separator, contact with each other, outmost circumferentia is fixed with adhesive tape, obtain spiral helicine electrode assemblie to prevent positive pole and negative pole.Then, by shown in Figure 1, dead ring 7 be placed on the top and the bottom of spiral electrode assembly 4, and be inserted in the stainless battery case, described battery case is shaped to cylindrical shape, serves as negative terminal.Thereafter, the negative terminal 6 that will link to each other with the negative pole of spiral electrode assembly 4 is welded to the inside of battery case 1, the positive terminal 5 that will link to each other with the positive pole of electrode assemblie is welded to the bottom of tie breaker 8, and described tie breaker 8 plays a role when gas pressure reaches predetermined pressure in battery.Tie breaker and explosion-proof valve are attached to the bottom of sealing plate 2.After treating to be added to following electrolyte solution in the battery case 1, use the open end sealing of sealing plate and polypropylene insulation packing ring 3, make the cylindrical battery that volume capacity density is 133mAh/cc battery case 1.
[the capacity evaluation of cylindrical battery]
With cylindrical battery under 25 ℃ with the constant current charge that is equivalent to 0.2C to 4.2V, be discharged to 3V with the constant current that is equivalent to 0.2C then.Repeat 3 circulations of this operation, so that the battery stabilisation, and in the 4th circulation, with battery with the constant current charge of 0.5C to 4.2V, and further charge to current value with the constant voltage of 4.2V and reach 0.05C, then the constant current with 0.2C is discharged to 3V, obtains initial discharge capacity.
Term 1C used herein is meant the current value that made the discharge of battery rated capacity in 1 hour, and 0.2C then is meant 1/5 of this current value.
[evaluation of the lasting charge characteristic of cylindrical battery]
Finish after the capacity evaluation, with cylindrical battery under 60 ℃ with the constant current charge of 0.5C to 4.2V, further continue 2 weeks of charging with constant voltage then.
Treat after the battery cooling battery constant current with 0.2C under 25 ℃ to be discharged to 3V, then after the lasting test of charging, measure reserve capacity, thereby obtain continuing charging reserve capacity afterwards, suppose that the discharge capacity before the lasting charging test is 100.
[evaluation of the cycle characteristics of cylindrical battery]
Finish after the capacity evaluation, make cylindrical battery stand cyclic test, wherein battery under 25 ℃ with the constant current charge of 1C to 4.2V, and further charge with the constant voltage of 4.2V, reach 0.05C until current value, then battery is discharged to 3V with the constant current of 1C.Obtain the discharge capacity after the circulation 100 times, suppose that the discharge capacity before the cyclic test is 100.
Under the argon atmospher of drying, the vinylene carbonate of 2 weight portions is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 98 weight portions with the LiPF of intensive drying
6LiBF
4Be dissolved in wherein, make its ratio separately be respectively 1.0 moles/L and 0.05 mole/L, thereby make electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
The vinylene carbonate of 2 weight portions is added to the ethylene carbonate of 98 weight portions and methyl ethyl carbonate (volume ratio: in the mixture 2/8), with the LiPF of intensive drying
6LiBF
4Be dissolved in wherein, make its ratio separately be respectively 1.0 moles/L and 0.05 mole/L, thereby make electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
The vinylene carbonate of 2 weight portions is added to the ethylene carbonate of 98 weight portions and diethyl carbonate (volume ratio: in the mixture 2/8), with the LiPF of intensive drying
6LiBF
4Be dissolved in wherein, make its ratio separately be respectively 1.0 moles/L and 0.05 mole/L, thereby make electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Comparative Examples 1
With the LiPF of intensive drying
6(volume ratio: in the mixture 2/4/2/2), making its ratio is 1.0 moles/L, thereby makes electrolyte solution to be dissolved in ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and diethyl carbonate.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Comparative Examples 2
The vinylene carbonate of 2 weight portions is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 98 weight portions with the LiPF of intensive drying
6Be dissolved in wherein, making its ratio is 1.0 moles/L, thereby makes electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Cylindrical battery has stood the operation of tie breaker at lasting charging duration of test because of the increase of interior pressure, thereby can not discharge.
The cyclohexyl benzene of the vinylene carbonate of 2 weight portions and 1 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 97 weight portions with the LiPF of intensive drying
6And LiBF
4Be dissolved in wherein, make its ratio separately be respectively 1.0 moles/L and 0.05 mole/L, thereby make electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Comparative Examples 3
The cyclohexyl benzene of the vinylene carbonate of 2 weight portions and 1 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 97 weight portions with the LiPF of intensive drying
6Be dissolved in wherein, making its ratio is 1.0 moles/L, thereby makes electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Cylindrical battery has stood the operation of tie breaker at lasting charging duration of test because of the increase of interior pressure, thereby can not discharge.
The vinylene carbonate of 1 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 99 weight portions with the LiPF of intensive drying
6And LiBF
4Be dissolved in wherein, make its ratio separately be respectively 1.0 moles/L and 0.05 mole/L, thereby make electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
The vinylene carbonate of 0.5 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 99.5 weight portions with the LiPF of intensive drying
6And LiBF
4Be dissolved in wherein, make its ratio separately be respectively 1.0 moles/L and 0.05 mole/L, thereby make electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Comparative Examples 4
The vinylene carbonate of 1 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 99 weight portions with the LiPF of intensive drying
6Be dissolved in wherein, making its ratio is 1.0 moles/L, thereby makes electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Cylindrical battery has stood the operation of tie breaker at lasting charging duration of test because of the increase of interior pressure, thereby can not discharge.
Comparative Examples 5
The vinylene carbonate of 0.5 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 99.5 weight portions with the LiPF of intensive drying
6Be dissolved in wherein, making its ratio is 1.0 moles/L, thereby makes electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
Cylindrical battery has stood the operation of tie breaker at lasting charging duration of test because of the increase of interior pressure, thereby can not discharge.
Comparative Examples 6
The vinylene carbonate of 0.1 weight portion is added to ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and the diethyl carbonate (volume ratio: in the mixture 2/4/2/2), of 99.9 weight portions with the LiPF of intensive drying
6Be dissolved in wherein, making its ratio is 1.0 moles/L, thereby makes electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the cylindrical shape lithium secondary battery, and estimate characteristic and cycle characteristics after the lasting charging.The results are shown in the table 1.
In table 1, LiBF has wherein been added in comparison shows that between embodiment 1～3 and Comparative Examples 1 and 2
4 Embodiment 1～3 have excellent lasting charge characteristic and cycle characteristics.In Comparative Examples 2, owing to do not add LiBF
4, thereby can not suppress the gas generation, thus have the lasting charge characteristic of deterioration, although cycle characteristics is improved because of having added vinylene carbonate.
Comparison shows that between embodiment 1 and embodiment 2 and 3 has the linear carbonate of symmetry and the embodiment 1 of asymmetrical linear carbonate and has lasting charge characteristic and cycle characteristics than embodiment 2 and 3 excellences.
Comparison shows that between embodiment 4 and the Comparative Examples 3 is even prevent from wherein to have added LiBF under the situation of agent as overcharging comprising cyclohexyl benzene
4Embodiment 4 also have excellent lasting charge characteristic and cycle characteristics.
Table 1
| The concentration of lithium salts (mole/L) | Solvent types | ||
| The LiPF of intensive drying 6 | LiBF 4 | ||
| Embodiment 1 | 1.0 | 0.05 | EC/EMC，DMC，DEC/ |
| Embodiment | |||
| 2 | 1.0 | 0.05 | EC/EMC/ |
| Embodiment | |||
| 3 | 1.0 | 0.05 | EC/DEC/VC |
| Comparative Examples 1 | 1.0 | ～ | EC/EMC，DMC，DEC |
| Comparative Examples 2 | 1.0 | ～ | EC/EMC，DMC，DEC/ |
| Embodiment | |||
| 4 | 1.0 | 0.05 | EC/EMC，DMC，DEC/VC |
| Comparative Examples 3 | 1.0 | ～ | EC/EMC，DMC，DEC/ |
| Embodiment | |||
| 5 | 1.0 | 0.05 | EC/EMC，DMC，DEC/ |
| Embodiment | |||
| 6 | 1.0 | 0.05 | EC/EMC，DMC，DEC/VC |
| Comparative Examples 4 | 1.0 | ～ | EC/EMC，DMC，DEC/VC |
| Comparative Examples 5 | 1.0 | ～ | EC/EMC，DMC，DEC/VC |
| Comparative Examples 6 | 1.0 | ～ | EC/EMC，DMC，DEC/VC |
In last table, EC represents ethylene carbonate, and EMC represents methyl ethyl carbonate, and DMC represents dimethyl carbonate, and DEC represents diethyl carbonate, and VC represents vinylene carbonate.
Table 1 (continuing)
| Continue the reserve capacity (%) after charging is tested | Discharge capacity (%) after 100 | |
| Embodiment | ||
| 1 | 97 | 85 |
| | 95 | 83 |
| | 91 | 81 |
| Comparative Examples 1 | 82 | 77 |
| Comparative Examples 2 | Circuit breaker work | 82 |
| | 93 | 85 |
| Comparative Examples 3 | Circuit breaker work | 81 |
| | 97 | 84 |
| | 95 | 81 |
| Comparative Examples 4 | Circuit breaker work | 81 |
| Comparative Examples 5 | Circuit breaker work | 80 |
| Comparative Examples 6 | 83 | 78 |
[preparation of sheet lithium secondary battery]
Press the order of negative pole, dividing plate, positive pole, dividing plate and negative pole, pile up anodal (1), negative pole (1) and polyethylene separator, make element cell, this element cell is packed in the bag, this bag is that (thickness: 40 μ m) form, load mode is that the terminal of anodal and negative pole is exposed by the two-sided aluminium lamination press mold that scribbles resin bed.Subsequently, to wherein adding following electrolyte solution, then vacuum seal makes the sheet battery.
[the capacity evaluation of sheet battery]
The sheet battery is fixed between the glass plate improving interelectrode contact, with this battery with the constant current charge that is equivalent to 0.2C to 4.2V, be discharged to 3V with the constant current that is equivalent to 0.2C then.Should operate and repeat 3 circulations, so that the battery stabilisation, and in the 4th circulation, with battery with the constant current charge of 0.5C to 4.2V, and further charge with the constant voltage of 4.2V, reach 0.05C until electric current, then the constant current with 0.2C is discharged to 3V, obtains initial discharge capacity.
[continuing the evaluation of charge characteristic]
(1) gas production
After finishing the capacity evaluation, with battery under 60 ℃ with the constant current charge of 0.5C to 4.25V, further continuous and constant pressure charged for 1 week then.
After treating battery cooling, battery is immersed in the ethanol bath, measuring its volume, and obtains gas production by the change in volume that continues before and after the charging.
(2) reserve capacity after the lasting charging
Measure after the gas production, battery constant current with 0.2C under 25 ℃ is discharged to 3V, measuring the reserve capacity that continues after the charging test, and obtain continuing the reserve capacity of charging, supposing that the discharge capacity that continues before the charging test is 100.
The vinylene carbonate of 1 weight portion is added to ethylene carbonate, methyl ethyl carbonate and the dimethyl carbonate (volume ratio: in the mixture 3/5/2), of 99 weight portions with the LiPF of intensive drying
6With 1 of ring-type, the 3-perfluor third disulfonyl imidization lithium is dissolved in wherein, makes its ratio separately respectively shown in following table 2, thereby makes electrolyte solution.
Utilize the electrolyte solution of so preparation to prepare the sheet battery, and estimate lasting charge characteristic.The results are shown in the following table 2.
As can be seen from Table 2, the battery that comprises the lithium salts shown in the following formula (1) of special ratios is being excellent aspect aerogenesis and the lasting charge characteristic.
Table 2
| The concentration of lithium salts | Gas production (mL) | Reserve capacity (%) | ||
| The LiPF of intensive drying 6 | Formula (1) | |||
| | 0.8 | 0.2 | 0.24 | 75 |
| Comparative Examples 7 | 1 | ～ | 0.57 | 75 |
| Comparative Examples 8 | 0.5 | 0.5 | 0.44 | 74 |
| Comparative Examples 9 | 0.2 | 0.8 | 0.58 | 68 |
| Comparative Examples 10 | ～ | 1 | 1.01 | 0 |
In this table, 1 of formula (1) expression ring-type, the 3-perfluor third disulfonyl imidization lithium.
With reference to its specific embodiments in detail the present invention has been described in detail, still, those of ordinary skill in the art it is evident that, can make various substitutions and modifications and not break away from its design and scope the present invention.
The application's basis is: Japanese patent application (the number of patent application 2003-51684 that on February 27th, 2003 submitted to, the Japanese patent application (number of patent application 2003-134694) that on May 13rd, 2003 submitted to, and the Japanese patent application (number of patent application 2003-174756) of submission on June 19th, 2003, whole disclosures of these applications are incorporated herein by reference.
Industrial applicibility
According to the present invention, can prepare such battery: it has high power capacity, excellent storage characteristic, cycle characteristics and lasting charge characteristic, and also gas production is little, can obtain size reduction thus and the lithium secondary battery of performance raising.
Claims (47)
1. a non-aqueous electrolytic solution comprises lithium salts and the nonaqueous solvents that dissolves lithium salts, and wherein this electrolyte solution comprises the LiPF that concentration is 0.2～2 mole/L
6, and with respect to LiPF
6Mol ratio be 0.005～0.4 LiBF
4And/or the compound shown in the following formula (1) is as lithium salts; Described nonaqueous solvents mainly comprises:
(1) ethylene carbonate and/or propylene carbonate,
(2-1) Dui Cheng linear carbonate,
(2-2) asymmetrical linear carbonate, and
(3) vinylene carbonate:
In the formula, the R representative has the straight or branched alkylidene of 1～20 carbon atom, and condition is that this alkylidene chain has no more than 12 carbon atoms except that side chain.
2. according to the non-aqueous electrolytic solution of claim 1, wherein the straight or branched alkylidene with 1～20 carbon atom of R representative is replaced by fluorine atom.
3. according to the non-aqueous electrolytic solution of claim 1 or 2, wherein this electrolyte solution comprises the LiBF that concentration is 0.001～0.3 mole/L
4And/or the lithium salts shown in the formula (1).
4. non-aqueous electrolytic solution comprises the nonaqueous solvents of lithium salts and dissolving lithium salts, and wherein this electrolyte solution comprises the LiPF that concentration is 0.2～2 mole/L
6And concentration is the LiBF of 0.001～0.3 mole/L
4As lithium salts; And described nonaqueous solvents mainly comprises:
(1) ethylene carbonate and/or propylene carbonate,
(2-1) Dui Cheng linear carbonate,
(2-2) asymmetrical linear carbonate, and
(3) vinylene carbonate.
5. according to the non-aqueous electrolytic solution of claim 4, wherein comprise with respect to LiPF
6Mol ratio be 0.005～0.4 LiBF
4
6. a non-aqueous electrolytic solution comprises lithium salts and the nonaqueous solvents that dissolves lithium salts, and wherein this electrolyte solution comprises the LiPF that concentration is 0.5～2.5 mole/L
6And concentration is the lithium salts shown in the following formula (1) of 0.001～0.3 mole/L, as lithium salts:
In the formula, the R representative has the straight or branched alkylidene of 1～20 carbon atom, and condition is that this alkylidene chain has no more than 12 carbon atoms except that side chain.
7. according to the non-aqueous electrolytic solution of claim 6, wherein the straight or branched alkylidene with 1～20 carbon atom of R representative is replaced by fluorine atom.
8. according to the non-aqueous electrolytic solution of claim 6 or 7, wherein said nonaqueous solvents mainly comprises:
(1) ethylene carbonate and/or propylene carbonate,
(2-1) Dui Cheng linear carbonate,
(2-2) asymmetrical linear carbonate, and
(3) vinylene carbonate.
9. according to the non-aqueous electrolytic solution of one of claim 1-2,4-5, wherein linear carbonate, asymmetrical linear carbonate and the total amount of vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts of ethylene carbonate, propylene carbonate, symmetry are 80% weight or bigger.
10. according to the non-aqueous electrolytic solution of claim 3, wherein linear carbonate, asymmetrical linear carbonate and the total amount of vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts of ethylene carbonate, propylene carbonate, symmetry are 80% weight or bigger.
11. non-aqueous electrolytic solution according to Claim 8, wherein linear carbonate, asymmetrical linear carbonate and the total amount of vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts of ethylene carbonate, propylene carbonate, symmetry are 80% weight or bigger.
12. according to the non-aqueous electrolytic solution of one of claim 1-2,4-5, the ratio of wherein said vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts is 0.01～8% weight.
13. according to the non-aqueous electrolytic solution of claim 3, the ratio of wherein said vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts is 0.01～8% weight.
14. non-aqueous electrolytic solution according to Claim 8, the ratio of wherein said vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts is 0.01～8% weight.
15. according to the non-aqueous electrolytic solution of claim 9, the ratio of wherein said vinylene carbonate in the non-aqueous electrolytic solution except that lithium salts is 0.01～8% weight.
16. according to the non-aqueous electrolytic solution of one of claim 1-2,4-5, the linear carbonate of wherein said symmetry is selected from dimethyl carbonate and diethyl carbonate, described asymmetrical linear carbonate is selected from methyl ethyl carbonate.
17. according to the non-aqueous electrolytic solution of claim 3, the linear carbonate of wherein said symmetry is selected from dimethyl carbonate and diethyl carbonate, described asymmetrical linear carbonate is selected from methyl ethyl carbonate.
18. non-aqueous electrolytic solution according to Claim 8, the linear carbonate of wherein said symmetry is selected from dimethyl carbonate and diethyl carbonate, and described asymmetrical linear carbonate is selected from methyl ethyl carbonate.
19. according to the non-aqueous electrolytic solution of claim 9, the linear carbonate of wherein said symmetry is selected from dimethyl carbonate and diethyl carbonate, described asymmetrical linear carbonate is selected from methyl ethyl carbonate.
20. according to the non-aqueous electrolytic solution of claim 12, the linear carbonate of wherein said symmetry is selected from dimethyl carbonate and diethyl carbonate, described asymmetrical linear carbonate is selected from methyl ethyl carbonate.
21. according to the non-aqueous electrolytic solution of one of claim 1-2,4-5, the volume ratio of the linear carbonate (2-1) of the total amount of wherein said ethylene carbonate and propylene carbonate (1) and described symmetry and the total amount of asymmetrical linear carbonate (2-2) is 10/90 to 70/30.
22. according to the non-aqueous electrolytic solution of claim 3, the volume ratio of the linear carbonate (2-1) of the total amount of wherein said ethylene carbonate and propylene carbonate (1) and described symmetry and the total amount of asymmetrical linear carbonate (2-2) is 10/90 to 70/30.
23. non-aqueous electrolytic solution according to Claim 8, the volume ratio of the linear carbonate (2-1) of the total amount of wherein said ethylene carbonate and propylene carbonate (1) and described symmetry and the total amount of asymmetrical linear carbonate (2-2) is 10/90 to 70/30.
24. according to the non-aqueous electrolytic solution of claim 9, the volume ratio of the linear carbonate (2-1) of the total amount of wherein said ethylene carbonate and propylene carbonate (1) and described symmetry and the total amount of asymmetrical linear carbonate (2-2) is 10/90 to 70/30.
25. according to the non-aqueous electrolytic solution of claim 12, the volume ratio of the linear carbonate (2-1) of the total amount of wherein said ethylene carbonate and propylene carbonate (1) and described symmetry and the total amount of asymmetrical linear carbonate (2-2) is 10/90 to 70/30.
26. according to the non-aqueous electrolytic solution of claim 16, the volume ratio of the linear carbonate (2-1) of the total amount of wherein said ethylene carbonate and propylene carbonate (1) and described symmetry and the total amount of asymmetrical linear carbonate (2-2) is 10/90 to 70/30.
27. according to the non-aqueous electrolytic solution of one of claim 1-2,4-7, wherein said nonaqueous solvents also comprises and is selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
28. according to the non-aqueous electrolytic solution of claim 3, wherein said nonaqueous solvents also comprises and is selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
29. also comprising, non-aqueous electrolytic solution according to Claim 8, wherein said nonaqueous solvents be selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
30. according to the non-aqueous electrolytic solution of claim 9, wherein said nonaqueous solvents also comprises and is selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
31. according to the non-aqueous electrolytic solution of claim 12, wherein said nonaqueous solvents also comprises and is selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
32. according to the non-aqueous electrolytic solution of claim 16, wherein said nonaqueous solvents also comprises and is selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
33. according to the non-aqueous electrolytic solution of claim 21, wherein said nonaqueous solvents also comprises and is selected from following aromatic compounds: biphenyl, alkyl biphenyl, terphenyl, the partial hydrogenation product of terphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, diphenyl ether and dibenzofuran.
34. according to the non-aqueous electrolytic solution of one of claim 1-2,4-7, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
35. according to the non-aqueous electrolytic solution of claim 3, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
36. non-aqueous electrolytic solution according to Claim 8, wherein said electrolyte solution also comprise concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
37. according to the non-aqueous electrolytic solution of claim 9, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
38. according to the non-aqueous electrolytic solution of claim 12, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
39. according to the non-aqueous electrolytic solution of claim 16, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
40. according to the non-aqueous electrolytic solution of claim 21, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
41. according to the non-aqueous electrolytic solution of claim 27, wherein said electrolyte solution also comprises concentration to be 0.001～0.2 mole/L and to be selected from following lithium salts: LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2And LiCF
3SO
3
42. a lithium secondary battery is characterized in that it comprises the negative pole and the positive pole that can embed and deviate from lithium, and according to the non-aqueous electrolytic solution of one of claim 1～41.
43. lithium secondary battery according to claim 42, wherein as positive active material, described positive pole comprises the lithium-compound transition metal oxide that is selected from lithium-cobalt/cobalt oxide, lithium-nickel oxide and lithium-Mn oxide, perhaps comprises by replacing the composite oxides that the part transition metal obtains in the composite oxides with another metal.
44. a lithium secondary battery, it comprises the negative pole and the positive pole that can embed and deviate from lithium, and non-aqueous electrolytic solution, wherein
Described negative pole comprises carbonaceous material as active material; Described non-aqueous electrolytic solution mainly comprises the nonaqueous solvents of lithium salts and dissolving lithium salts, and as lithium salts, this non-aqueous electrolytic solution comprises the LiPF that concentration is 0.2～2 mole/L
6And with respect to LiPF
6Mol ratio be 0.005～0.4 LiBF
4And/or the lithium salts shown in the following formula (1); Described nonaqueous solvents mainly comprises:
(1) ethylene carbonate and/or propylene carbonate,
(2) linear carbonate, and
(3) vinylene carbonate:
In the formula, the R representative has the straight or branched alkylidene of 1～20 carbon atom, and condition is that this alkylidene chain has no more than 12 carbon atoms except that side chain.
45. according to the lithium secondary battery of claim 44, wherein the straight or branched alkylidene with 1～20 carbon atom of R representative is replaced by fluorine atom.
46. be used for the non-aqueous electrolytic solution of lithium secondary battery, described lithium secondary battery comprises: contain carbonaceous material as the negative pole that can embed and deviate from the active material of lithium; Contain the positive pole that can embed and deviate from the active material of lithium; Reach the non-aqueous electrolytic solution of the nonaqueous solvents that mainly comprises lithium salts and dissolving lithium salts, in the described non-aqueous electrolytic solution
As lithium salts, described non-aqueous electrolytic solution comprises the LiPF that concentration is 0.2～2 mole/L
6, and with respect to LiPF
6Mol ratio be 0.005～0.4 LiBF
4And/or the lithium salts shown in the following formula (1); And described nonaqueous solvents mainly comprises:
(1) ethylene carbonate and/or propylene carbonate,
(2) linear carbonate, and
(3) vinylene carbonate:
In the formula, the R representative has the straight or branched alkylidene of 1～20 carbon atom, and condition is that this alkylidene chain has no more than 12 carbon atoms except that side chain.
47. according to the non-aqueous electrolytic solution that is used for lithium secondary battery of claim 46, wherein the straight or branched alkylidene with 1～20 carbon atom of R representative is replaced by fluorine atom.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003051684 | 2003-02-27 | ||
| JP51684/2003 | 2003-02-27 | ||
| JP134694/2003 | 2003-05-13 | ||
| JP174756/2003 | 2003-06-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1698232A CN1698232A (en) | 2005-11-16 |
| CN100347903C true CN100347903C (en) | 2007-11-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200480000437XA Expired - Lifetime CN100347903C (en) | 2003-02-27 | 2004-02-25 | Nonaqueous electrolytic solution and lithium secondary battery |
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| CN (1) | CN100347903C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101342509B1 (en) | 2007-02-26 | 2013-12-17 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| EP1978587B1 (en) * | 2007-03-27 | 2011-06-22 | Hitachi Vehicle Energy, Ltd. | Lithium secondary battery |
| US20100266905A1 (en) * | 2007-09-19 | 2010-10-21 | Lg Chem, Ltd. | Non-aqueous electrolyte lithium secondary battery |
| CN101969136B (en) * | 2010-07-27 | 2013-06-12 | 天津力神电池股份有限公司 | Lithium ion battery capable of guaranteeing overcharge safety performance |
| JP5776663B2 (en) * | 2012-10-16 | 2015-09-09 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
| WO2014088009A1 (en) * | 2012-12-06 | 2014-06-12 | 宇部興産株式会社 | Nonaqueous electrolyte solution and electrical storage device employing same |
| CN112886054A (en) * | 2019-11-29 | 2021-06-01 | 深圳新宙邦科技股份有限公司 | Lithium-rich manganese-based lithium ion battery |
| CN111477960B (en) * | 2020-05-29 | 2021-11-30 | 珠海市赛纬电子材料股份有限公司 | Electrolyte and lithium ion battery using same |
| CN113937356B (en) * | 2020-06-29 | 2023-01-17 | 深圳新宙邦科技股份有限公司 | Electrolyte and battery |
| CN114122514A (en) * | 2020-08-31 | 2022-03-01 | 诺莱特电池材料(苏州)有限公司 | Electrolyte and battery |
| CN112599853A (en) * | 2020-11-30 | 2021-04-02 | 远景动力技术(江苏)有限公司 | Electrolyte and lithium ion battery |
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| JP2000277146A (en) * | 1999-03-24 | 2000-10-06 | At Battery:Kk | Rectangular nonaqueous electrolyte secondary battery |
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| JP2001148258A (en) * | 1999-11-19 | 2001-05-29 | Sumitomo Chem Co Ltd | Non-aqueous electrolytic solution and lithium secondary battery |
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| JPH087922A (en) * | 1994-06-22 | 1996-01-12 | Asahi Chem Ind Co Ltd | Organic electrolytic secondary cell |
| US6114070A (en) * | 1997-06-19 | 2000-09-05 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
| JP2000277146A (en) * | 1999-03-24 | 2000-10-06 | At Battery:Kk | Rectangular nonaqueous electrolyte secondary battery |
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| JP2001148258A (en) * | 1999-11-19 | 2001-05-29 | Sumitomo Chem Co Ltd | Non-aqueous electrolytic solution and lithium secondary battery |
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