CN103107363A - Non-water electrolysis solution of lithium ion battery and corresponding lithium ion battery thereof - Google Patents
Non-water electrolysis solution of lithium ion battery and corresponding lithium ion battery thereof Download PDFInfo
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- CN103107363A CN103107363A CN2013100383771A CN201310038377A CN103107363A CN 103107363 A CN103107363 A CN 103107363A CN 2013100383771 A CN2013100383771 A CN 2013100383771A CN 201310038377 A CN201310038377 A CN 201310038377A CN 103107363 A CN103107363 A CN 103107363A
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- Prior art keywords
- lithium ion
- ion battery
- electrolytic solution
- carbonate
- nonaqueous electrolytic
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 48
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 26
- 239000008151 electrolyte solution Substances 0.000 claims description 23
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013375 LiC Inorganic materials 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- QBDVHBCBEPBBPL-UHFFFAOYSA-N P(O)(O)O.C(C)(=O)OC=C Chemical compound P(O)(O)O.C(C)(=O)OC=C QBDVHBCBEPBBPL-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- AZEQMGPWGQJEBN-UHFFFAOYSA-N phosphorous acid;prop-1-ene Chemical group CC=C.OP(O)O AZEQMGPWGQJEBN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 37
- 239000002904 solvent Substances 0.000 abstract description 6
- -1 phosphite ester compound Chemical class 0.000 abstract 2
- 229940125904 compound 1 Drugs 0.000 description 38
- 238000002360 preparation method Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 22
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 229910015645 LiMn Inorganic materials 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention aims to provide a non-water electrolysis solution for a high-performance lithium ion battery. The non-water electrolysis solution comprises a lithium salt, an organic solvent and a phosphite ester compound containing unsaturated bond, wherein the unsaturated phosphite ester compound is contributed to forming a stable compact passivating film (SEI film) on the surface of an electrode, and a solvent molecule is prevented from further decomposing. According to the scheme of the invention, the obtained electrolysis solution can improve a high temperature storage performance and a cycle performance of the battery.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to field of lithium ion secondary.
Background technology
In recent years, portable type electronic product, such as camera, Digital Video, mobile phone, notebook computer etc. is widely used in daily life.Reduce size, weight reduction, increasing the service life is development trend and the requirement of electronic product industry.Therefore, it is the active demand of industry development that the power supply product that exploitation matches with portable type electronic product, especially exploitation can provide the lightweight secondary cell of high-energy-density.
With lead-acid battery, nickel-cadmium cell, Ni-MH battery is compared, and the characteristics such as lithium ion battery is large because of its energy density, operating voltage is high, the life-span is long, environmental protection are widely used in the portable battery product.
Lithium ion battery mainly is comprised of positive and negative electrode, electrolyte and barrier film.Positive pole is mainly the transition metal oxide that contains lithium, and negative pole is mainly Carbon Materials.Because the average discharge volt of lithium ion battery is about 3.6-3.7V, need to be in the charging/discharging voltages of 0-4.2V stable electrolyte component.For this reason, lithium ion battery electrolyte used must be non-aqueous solution electrolysis liquid, for example: usually use the mixture that comprises cyclic carbonate ester solvent (as ethylene carbonate) and linear carbonates solvent (as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate) as solvent, lithium hexafluoro phosphate is as the electrolyte of solute.
Lithium ion battery is in the initial charge process, and lithium ion takes off embedding out from the lithium metal oxide of cathode active material, and the migration of anode carbon electrode, then be embedded in material with carbon element under the driving of voltage.In this process, electrolyte and carbon anode surface react, and produce Li
2CO
3, Li
2O, the materials such as LiOH, thus at carbon anode surface formation one deck passivating film, this passivating film is referred to as solid electrolyte interface (SEI) film.Due to no matter be the charging or the discharge, lithium ion must pass through this layer SEI film, so the performance of SEI film has determined many performances (as cycle performance, high-temperature behavior, high rate performance) of battery.The SEI film can stop the further decomposition of electrolyte solvent after initial charge forms, and forms ion channel in charge and discharge cycles subsequently.Yet along with the carrying out that discharges and recharges, the expansion that electrode repeats and contraction SEI film may break or dissolving gradually, the anode that thereupon exposes continues to react with electrolyte, produce simultaneously gas, thereby increase the interior pressure of battery, and significantly reduce the cycle life of battery.Especially battery stores under hot conditions and carry out charge and discharge cycles under hot conditions, and the SEI film is easier to be destroyed, thereby causes battery bulging and cycle performance obviously to descend.The kind of the carbonic ester that uses according to electrolyte and the type of anode active material, the gas of generation mainly comprises CO, CO
2, CH
4, C
2H
6Deng.
Because the quality of SEI film is most important to high-temperature storage performance and the cycle performance of lithium ion battery, therefore improve the quality of SEI film to realizing that high performance lithium ion battery is very necessary by regulation and control.In order to address this problem, people attempt adding a small amount of additive and improve the SEI film in electrolyte, to improving the performance of lithium ion battery.Researcher has been developed a series of film for additive such as vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluorinated ethylene carbonate (FEC) etc. through great efforts, they can form more stable SEI on the graphite cathode surface, thereby significantly improved the cycle performance of lithium ion battery, simultaneously also improved to a certain extent the high-temperature storage performance, so these additives have obtained in commercial lithium-ion batteries generally using.But the formed SEI of above-mentioned film for additive is still stable not under the high-temperature storage condition, still the decomposition of electrolyte can occur and cause inflatable at higher temperature, thereby bring serious potential safety hazard, therefore be necessary to develop the high-temperature storage performance that new additive further improves lithium ion battery.
Summary of the invention
The object of the invention is to, a kind of high performance lithium ion battery nonaqueous electrolytic solution is provided.
For achieving the above object, the invention provides a kind of lithium ion battery nonaqueous electrolytic solution, comprising:
Lithium salts;
Organic solvent; And
The bi-ester of phosphite that contains unsaturated bond, this compound is as shown in structural formula 1:
(structural formula 1)
R wherein
1, R
2, R
3Independently be selected from respectively the alkyl that carbon number is 1-4, and R
1, R
2, R
3In at least one is unsaturated alkyl.
Preferably, the described bi-ester of phosphite structure that contains unsaturated bond is as shown in structural formula 2:
(structural formula 2)
R wherein
4Be selected from saturated hydrocarbyl or undersaturated alkyl that carbon number is 1-4.
Preferably, the described bi-ester of phosphite structure that contains unsaturated bond is as shown in structural formula 3:
(structural formula 3)
R wherein
5Be selected from saturated hydrocarbyl or undersaturated alkyl that carbon number is 1-4.
Preferably, the described bi-ester of phosphite that contains unsaturated bond is selected from one of following material or its mixture: tricresyl phosphite vinyl acetate, tricresyl phosphite propylene.
Another with the exemplary compound in the described compound of structure 1 shown in table 1, but be not restricted to this.
Table 1
According to lithium ion battery nonaqueous electrolytic solution of the present invention, contain unsaturated bi-ester of phosphite.This unsaturated bi-ester of phosphite helps to have stoped the further decomposition of solvent molecule at the stable fine and close passivating film (SEI film) of battery electrode surface formation.Can improve high-temperature storage performance and the cycle performance of battery according to the electrolyte of the solution of the present invention.
According to lithium ion battery nonaqueous electrolytic solution provided by the present invention, be preferably 0.01%-2% by the content of the described unsaturated bi-ester of phosphite of structural formula 1 in electrolyte by the electrolyte total weight.It is easier in the effective SEI film of battery electrode surface formation when the content of unsaturated phosphite ester in electrolyte is not less than 0.01%.More preferably, unsaturated phosphite ester can further improve the stability of SEI film when the content of electrolyte is not less than 0.1%, thereby further improves high-temperature storage performance and the cycle performance of battery.On the other hand, not higher than 2% the time, can suppress the increase of the internal resistance of cell when the content of unsaturated bi-ester of phosphite in electrolyte.More preferably, the content of unsaturated bi-ester of phosphite in electrolyte can further not suppress the increase of the internal resistance of cell higher than 1% the time, thereby further improves high-temperature storage and the cycle performance of battery.
According to lithium ion battery nonaqueous electrolytic solution provided by the invention, can be further add the cycle performance that one or more additives in vinylene carbonate (VC), fluorinated ethylene carbonate (FEC), vinyl ethylene carbonate (VEC) improve battery in the electrolyte.
Preferably, lithium ion battery of the present invention comprises cyclic carbonate and linear carbonate with the solvent of nonaqueous electrolytic solution, cyclic carbonate wherein comprises one or more in ethylene carbonate (EC), propene carbonate (PC), butylene (BC), and linear carbonate wherein comprises one or more in dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC).
Lithium ion battery of the present invention comprises LiPF with the solute of nonaqueous electrolytic solution
6, LiBF
4, LiSbF
6, LiAsF
6, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3, LiN (SO
2F)
2In at least a.LiPF preferably wherein
6Or the mixture of itself and other lithium salts.
Lithium ion battery of the present invention is applied to have in the lithium ion battery of negative pole and positive pole with nonaqueous electrolytic solution, and described negative pole is made by material with carbon element, metal alloy, otide containing lighium thing and material etc.Wherein, the preferred graphite of material with carbon element or be coated on graphite surface with graphite-phase than amorphous carbon and material with carbon element.Described positive electrode preferably adopts lithium-containing transition metal oxide, for example is selected from one or more in following material: LiCoO
2, LiNiO
2, LiMn
2O
4, LiCo
1-yM
yO
2, LiNi
1-yM
yO
2, LiMn
2-yM
yO
4, LiNi
xCo
yMn
zM
1-x-y-zO
2, wherein M is selected from one or more in Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
The present invention also provides a kind of lithium ion battery, comprising: lithium ion battery nonaqueous electrolytic solution provided by the invention in foregoing; Can embed the positive pole with removal lithium embedded; Can embed the negative pole with removal lithium embedded; And be placed in barrier film between positive pole and negative pole.
The present invention also provides above-described unsaturated bi-ester of phosphite improving the application of lithium ion battery with the aspect of performance of nonaqueous electrolytic solution and lithium ion battery in addition.
Embodiment
By describing technology contents of the present invention, structural feature in detail, being realized purpose and effect, described in detail below in conjunction with execution mode.
Embodiment 1
1) preparation of electrolyte
Ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) in mass ratio for EC:DEC:EMC=1:1:1 mixes, are then added lithium hexafluoro phosphate (LiPF
6) to molar concentration be 1mol/L, add again the compound 1, the compound 2 that refer in the compound 1(embodiment by the gross mass 0.5% of electrolyte ... refer to the compound of the reference numeral enumerated in table 1, below each example in like manner) shown in unsaturated bi-ester of phosphite.
2) preparation of positive plate
The quality of pressing 93:4:3 is than blended anode active material lithium nickel cobalt manganese oxide LiNi
0.5Co
0.2Mn
0.3O
2, conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF) then are dispersed in them in METHYLPYRROLIDONE (NMP), obtain anode sizing agent.Slurry is uniformly coated on the two sides of aluminium foil, through oven dry, calendering and vacuumize, and burn-ons with supersonic welder and obtain positive plate after the aluminum lead-out wire, the thickness of pole plate is at 120-150 μ m.
3) preparation of negative plate
Press the mass ratio mixing negative active core-shell material modified natural graphite of 94:1:2.5:2.5, conductive carbon black Super-P, binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC) then are dispersed in them in deionized water, obtain cathode size.Slurry is coated on the two sides of Copper Foil, through oven dry, calendering and vacuumize, and burn-ons with supersonic welder and obtain negative plate after nickel making outlet, the thickness of pole plate is at 120-150 μ m.
4) preparation of battery core
Place thickness and be the polyethene microporous membrane of 20 μ m between positive plate and negative plate as barrier film, then the sandwich structure that positive plate, negative plate and barrier film is formed is reeled, put into square aluminum metal-back after again coiling body being flattened, the lead-out wire of both positive and negative polarity is welded on respectively on the relevant position of cover plate, and with laser-beam welding machine, cover plate and metal-back are welded as a whole, obtain treating the battery core of fluid injection.
5) fluid injection of battery core and changing into
Be controlled at dew point in the glove box below-40 ℃, the electrolyte of above-mentioned preparation is injected battery core by liquid injection hole, the amount of electrolyte will guarantee to be full of the space in battery core.Then change into according to the following steps: 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min, after shelving 1hr, shaping is sealed, then further with the electric current constant current charge of 0.2C to 4.2V, after normal temperature shelf 24hr, with the electric current constant-current discharge of 0.2C to 3.0V.
6) normal-temperature circulating performance test
At room temperature with the electric current constant current charge of 1C to 4.2V then constant voltage charge to electric current drop to 0.1C, then with the electric current constant-current discharge of 1C to 3.0V, so 300 weeks of circulation, discharge capacity and the discharge capacity in the 300th week in the 1st week of record are calculated as follows the capability retention that normal temperature circulates:
The discharge capacity * 100% in the discharge capacity in capability retention=the 300th week/the 1st week
7) high temperature cyclic performance test
Battery is placed in the baking oven of 45 ℃ of constant temperature, with the electric current constant current charge of 1C to 4.2V then constant voltage charge to electric current drop to 0.1C, then with the electric current constant-current discharge of 1C to 3.0V, so circulated for 300 weeks, record discharge capacity and the discharge capacity in the 300th week in the 1st week, be calculated as follows the capability retention of high temperature circulation:
The discharge capacity * 100% in the discharge capacity in capability retention=the 300th week/the 1st week
8) high-temperature storage performance test
At room temperature with the electric current constant current charge of 1C to 4.2V then constant voltage charge to electric current drop to 0.1C, measure the thickness of battery, the baking oven that then battery is placed in 85 ℃ of constant temperature stores 4h, takes out relief battery cool to room temperature, measure the thickness of battery, be calculated as follows the thickness swelling of battery:
Cell thickness * 100% before thickness swelling=(cell thickness before the cell thickness after storage-storage)/storage
Embodiment 2
In the preparation of electrolyte, 0.5% compound 1 is changed into 0.5% compound 2, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 2.
Embodiment 3
In the preparation of electrolyte, 0.5% compound 1 is changed into 0.5% compound 5, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 2.
Embodiment 4
In the preparation of electrolyte, 0.5% compound 1 is changed into 0.5% compound 7, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 2.
Comparative example 1
Do not add in the preparation of electrolyte compound 1, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 2.
Table 2
Data by table 2 can be found out, compare with the electrolyte that does not contain additive, and normal-temperature circulating performance, high temperature cyclic performance and the high-temperature storage performance of having added the prepared battery of electrolyte of unsaturated bi-ester of phosphite all are significantly improved.
Embodiment 5
In the preparation of electrolyte, 0.5% compound 1 is changed into 0.01% compound 1, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 3.
Embodiment 6
In the preparation of electrolyte, 0.5% compound 1 is changed into 0.1% compound 1, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 3.
Embodiment 7
In the preparation of electrolyte, 0.5% compound 1 is changed into 1% compound 1, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 3.
Embodiment 8
In the preparation of electrolyte, 0.5% compound 1 is changed into 2% compound 1, other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 3.
Table 3
Can find out from the data of table 3, when the addition of compound 1 in electrolyte brings up to 0.1% from 0.01%, the normal-temperature circulating performance of battery, high temperature circulation and high-temperature storage performance improve gradually, but when addition surpasses 1%, normal-temperature circulating performance and the high temperature cyclic performance of battery descend to some extent, but still obviously are better than not adding the battery of compound 1.
Embodiment 9
In the preparation of electrolyte, 0.5% compound 1 is changed into the combination of 1% vinylene carbonate (VC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 4.
Embodiment 10
In the preparation of electrolyte, 0.5% compound 1 is changed into the combination of 1% fluorinated ethylene carbonate (FEC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 4.
Embodiment 11
In the preparation of electrolyte, 0.5% compound 1 is changed into the combination of 1% vinyl ethylene carbonate (VEC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 4.
Comparative example 2
In the preparation of electrolyte, 0.5% compound 1 is changed into 1% vinylene carbonate (VC), other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 4.
Comparative example 3
In the preparation of electrolyte, 0.5% compound 1 is changed into 1% fluorinated ethylene carbonate (FEC), other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 4.
Comparative example 4
In the preparation of electrolyte, 0.5% compound 1 is changed into 1% vinyl ethylene carbonate (VEC), other is identical with embodiment 1, and the data of normal temperature circulation, high temperature circulation and high-temperature storage that test obtains see Table 4.
Table 4
Can find out from the data of table 4, on the basis of using VC, FEC or VEC, further add compound 1 and can make battery obtain better high-temperature storage performance, normal-temperature circulating performance and high temperature cyclic performance also are improved simultaneously.
Embodiment 12
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiNi into
1/3Co
1/3Mn
1/3O
2And in the preparation of electrolyte, 0.5% compound 1 is changed into outside the combination of 1% vinylene carbonate (VC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Embodiment 13
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiNi into
0.8Co
0.15Al
0.05O
2And in the preparation of electrolyte, 0.5% compound 1 is changed into outside the combination of 1% vinylene carbonate (VC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Embodiment 14
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiCoO into
2And in the preparation of electrolyte, 0.5% compound 1 is changed into outside the combination of 1% vinylene carbonate (VC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Embodiment 15
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiMn into
2O
4And in the preparation of electrolyte, 0.5% compound 1 is changed into outside the combination of 1% vinylene carbonate (VC) and 0.5% compound 1, other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Comparative example 5
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiNi into
1/3Co
1/3Mn
1/3O
2And in the preparation of electrolyte, 0.5% compound 1 is changed into outside 1% vinylene carbonate (VC), other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Comparative example 6
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiNi into
0.8Co
0.15Al
0.05O
2And in the preparation of electrolyte, 0.5% compound 1 is changed into outside 1% vinylene carbonate (VC), other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Comparative example 7
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiCoO into
2And in the preparation of electrolyte, 0.5% compound 1 is changed into outside 1% vinylene carbonate (VC), other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Comparative example 8
Except with positive electrode LiNi
0.5Co
0.2Mn
0.3O
2Change LiMn into
2O
4And in the preparation of electrolyte, 0.5% compound 1 is changed into outside 1% vinylene carbonate (VC), other is identical with embodiment 1, and the data of testing the normal temperature circulation, high temperature circulation and the high-temperature storage that obtain see Table 5.
Table 5
Can find out from the data of table 5, with LiNi
1/3Co
1/3Mn
1/3O
2, LiNi
0.8Co
0.15Al
0.05O
2, LiCoO
2, LiMn
2O
4In lithium ion battery for positive electrode, add the high-temperature storage performance that compound 1 also can improve battery, also can improve normal-temperature circulating performance and the high temperature cyclic performance of battery simultaneously.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (11)
1. lithium ion battery nonaqueous electrolytic solution comprises:
Lithium salts;
Organic solvent; And
The bi-ester of phosphite that contains unsaturated bond, this compound is as shown in structural formula 1:
(structural formula 1)
R wherein
1, R
2, R
3Independently be selected from respectively the alkyl that carbon number is 1-4, and R
1, R
2, R
3In at least one is unsaturated alkyl.
2. lithium ion battery nonaqueous electrolytic solution according to claim 1, is characterized in that, the described bi-ester of phosphite structure that contains unsaturated bond is as shown in structural formula 2:
(structural formula 2)
R wherein
4Be selected from saturated hydrocarbyl or undersaturated alkyl that carbon number is 1-4.
3. lithium ion battery nonaqueous electrolytic solution according to claim 1, is characterized in that, the described bi-ester of phosphite structure that contains unsaturated bond is as shown in structural formula 3:
(structural formula 3)
R wherein
5Be selected from saturated hydrocarbyl or undersaturated alkyl that carbon number is 1-4.
4. lithium ion battery nonaqueous electrolytic solution according to claim 1, is characterized in that, the described bi-ester of phosphite that contains unsaturated bond is selected from one of following material or its mixture: tricresyl phosphite vinyl acetate, tricresyl phosphite propylene.
5. the described lithium ion battery nonaqueous electrolytic solution of according to claim 1 to 4 any one, is characterized in that, the described content that contains the bi-ester of phosphite of unsaturated bond counts 0.01% ~ 2% by the total weight of electrolyte.
6. the described lithium ion battery nonaqueous electrolytic solution of according to claim 1 to 4 any one, it is characterized in that, described lithium ion battery also contains one or more in following material with nonaqueous electrolytic solution: vinylene carbonate, fluorinated ethylene carbonate, vinyl ethylene carbonate.
7. the described lithium ion battery nonaqueous electrolytic solution of according to claim 1 to 4 any one, is characterized in that, described organic solvent is the mixture of cyclic carbonate and linear carbonate.
8. lithium ion battery nonaqueous electrolytic solution according to claim 7, is characterized in that, described cyclic carbonate comprises: one or more in ethylene carbonate, propene carbonate, butylene.
9. lithium ion battery nonaqueous electrolytic solution according to claim 7, is characterized in that, described linear carbonate comprises: one or more in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate.
10. the described lithium ion battery nonaqueous electrolytic solution of according to claim 1 to 4 any one, is characterized in that, described lithium salts is selected from: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3, LiN (SO
2F)
2In at least a.
11. a lithium ion battery comprises:
The described lithium ion battery nonaqueous electrolytic solution of claim 1 to 10 any one;
Can embed the positive pole with removal lithium embedded;
Can embed the negative pole with removal lithium embedded; And
Be placed in the barrier film between positive pole and negative pole.
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| PCT/CN2013/072310 WO2014117421A1 (en) | 2013-01-31 | 2013-03-07 | Non-aqueous electrolyte for lithium ion batteries and corresponding lithium ion battery thereof |
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| CN103880881A (en) * | 2014-04-16 | 2014-06-25 | 苏州科技学院相城研究院 | Method for preparing allyl phosphonic acid dimethyl ester |
| CN105336987A (en) * | 2015-11-17 | 2016-02-17 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN106340672A (en) * | 2015-07-08 | 2017-01-18 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN107516745A (en) * | 2017-08-16 | 2017-12-26 | 中节能万润股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell |
| TWI635640B (en) * | 2013-07-31 | 2018-09-11 | 艾迪科股份有限公司 | Lithium secondary cell and electrolyte for lithium secondary cell |
| CN108649265A (en) * | 2018-05-10 | 2018-10-12 | 桑德集团有限公司 | Electrolysis additive, lithium battery electrolytes and lithium battery |
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| CN111384438A (en) * | 2018-12-29 | 2020-07-07 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
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| CN111384438A (en) * | 2018-12-29 | 2020-07-07 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN111384391A (en) * | 2018-12-29 | 2020-07-07 | 深圳新宙邦科技股份有限公司 | High-nickel lithium ion battery |
| CN111384391B (en) * | 2018-12-29 | 2022-03-11 | 深圳新宙邦科技股份有限公司 | High-nickel lithium ion battery |
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| CN103107363B (en) | 2015-06-10 |
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