CN102738511B - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
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- CN102738511B CN102738511B CN201210005068.XA CN201210005068A CN102738511B CN 102738511 B CN102738511 B CN 102738511B CN 201210005068 A CN201210005068 A CN 201210005068A CN 102738511 B CN102738511 B CN 102738511B
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- lithium
- ion battery
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- carbonate
- lithium ion
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 239000000654 additive Substances 0.000 claims abstract description 38
- 230000000996 additive effect Effects 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical group C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 aromatic radical Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021435 silicon-carbon complex Inorganic materials 0.000 claims description 4
- 239000011867 silicon-carbon complex material Substances 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 2
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 21
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 206010042674 Swelling Diseases 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 4
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000010261 cell growth Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XTCNPVFUGSHDJG-UHFFFAOYSA-N 3-(cyclopropylmethylidene)pentanenitrile Chemical group CCC(CC#N)=CC1CC1 XTCNPVFUGSHDJG-UHFFFAOYSA-N 0.000 description 2
- OIQDAVBXDLGCID-UHFFFAOYSA-N 3-methylbut-3-enenitrile Chemical group CC(=C)CC#N OIQDAVBXDLGCID-UHFFFAOYSA-N 0.000 description 2
- 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
- PXAIKTVRZLRWPU-UHFFFAOYSA-N 5-(cyclohexylmethylidene)dodecanenitrile Chemical group C(CCCCCC)C(CCCC#N)=CC1CCCCC1 PXAIKTVRZLRWPU-UHFFFAOYSA-N 0.000 description 2
- 229910012623 LiNi0.5Co0.2 Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YGYJZSFWORXUDH-UHFFFAOYSA-N hexadec-3-enenitrile Chemical group CCCCCCCCCCCCC=CCC#N YGYJZSFWORXUDH-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- YHNYOPGEKPRPNL-UHFFFAOYSA-N ethene;sulfurous acid Chemical compound C=C.OS(O)=O YHNYOPGEKPRPNL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
Classifications
-
- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to technical field of lithium ion, particularly relate to a kind of lithium-ion battery electrolytes that can improve high-temperature storage performance of lithium ion battery, including nonaqueous solvent and the lithium salts being dissolved in nonaqueous solvent, it is characterized in that: described electrolyte also includes additive, described additive is the compound represented by following formula (I)。In formula (I), R1、R2、R3Selected from hydrogen atom, alkyl containing 1～12 carbon atom, the cycloalkyl containing 3～8 carbon atoms and the aromatic radical containing 6～12 carbon atoms, n is the integer of 0～7。This compound can be passivated positive pole, negative terminal surface effectively, it is suppressed that the electrolyte component oxidation Decomposition at positive electrode surface, the reduction decomposition in negative terminal surface, thus reducing the aerogenesis of battery, improves the high-temperature storage performance of lithium ion battery。Additionally, the invention also discloses a kind of lithium ion battery comprising this electrolyte。
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of lithium-ion battery electrolytes that can improve high-temperature storage performance of lithium ion battery and use the secondary cell of this electrolyte。
Background technology
Lithium ion battery has energy density height, running voltage is high, have extended cycle life, memory-less effect, the advantage such as environmentally friendly, now having become the main power source of mobile consumer electronics, lithium ion battery application technology in electric automobile, intelligent grid etc. also reaches its maturity。
Along with the development of lithium power technology, it is desirable to lithium ion battery can have higher energy density。In order to improve the energy density of lithium ion battery, currently mainly there are two kinds of trend: one is the positive electrode that some nickel element content are high, and the lithium nickel cobalt manganese oxide such as lithium nickel cobalt aluminum oxide, high nickel content is exploited for lithium ion battery；Two is the charge cutoff voltage improving lithium ion battery, makes positive pole deviate from higher proportion of lithium ion, thus obtaining higher capacity, reaches to improve the demand of energy density。
But under fully charged state, the negative pole of lithium ion battery has highly reduced property, and is just having high oxidative。In actual use, the lasting of electronic product uses heating and battery to use the factors such as ambient temperature rising to be all likely to make battery place at high operating temperatures。At high temperature, the positive pole of battery, negative pole reactivity further enhance, cause that lithium-ion battery electrolytes and negative pole, positive pole react, produce gas, cause cell expansion。Especially, the positive electrode of high nickel content under identical charge cutoff voltage or identical positive electrode be charged to higher blanking voltage and all can improve the oxidability of positive pole, the problem of oxidation of electrolyte is even more serious, and the phenomenon of cell expansion becomes apparent from。This not only results in the damage of battery itself, also result in the damage of the equipment using battery simultaneously, owing to cell expansion deformation causes inside battery to be short-circuited or battery packages bag bursts and causes that flammable electrolyte is revealed time serious, there is the risk causing the security incidents such as fire。It is thus desirable to effective method solves the battery flatulence problem that the decomposition of electrolyte causes。
Thus can reflecting, necessary offer one can suppress electrolyte and positive pole, negative pole to react at high operating temperatures, thus improving the electrolyte of high-temperature storage performance of lithium ion battery and comprising the lithium ion battery of this electrolyte。
Summary of the invention
An object of the present invention is in that: for the deficiencies in the prior art, and provides one that electrolyte and positive pole, negative pole can be suppressed at high operating temperatures to react, thus improving the electrolyte of high-temperature storage performance of lithium ion battery。
In order to reach above-mentioned technical purpose, the present invention adopts the following technical scheme that
A kind of lithium-ion battery electrolytes, including nonaqueous solvent and the lithium salts being dissolved in nonaqueous solvent, described electrolyte also includes additive, and described additive is the compound represented by following formula (I):
Formulas I
Wherein R1、R2、R3Selected from hydrogen atom, alkyl containing 1～12 carbon atom, the cycloalkyl containing 3～8 carbon atoms and the aromatic radical containing 6～12 carbon atoms, n is the integer of 0～7。
The compound that formula (I) represents, containing itrile group and ethylene linkage in molecular structure, itrile group can form stronger complexing with transition metal atoms, and transition metal atoms is also had certain complexing by ethylene linkage；Double bond is likely to and is reduced in negative terminal surface simultaneously, oxidized at positive electrode surface, thus there is electrochemical polymerization effect, generates polymer inactivation film, and the itrile group in molecular formula makes ethylene linkage be activated, and filming function further enhances。Therefore this compound can be passivated positive pole, negative terminal surface effectively, it is suppressed that the electrolyte component oxidation Decomposition at positive electrode surface, the reduction decomposition in negative terminal surface, thus reducing the aerogenesis of battery, improves the high-temperature storage performance of lithium ion battery。
For this compound, R in formula (I)1、R2、R3It is each independently selected from hydrogen atom, alkyl containing 1～12 carbon atom, the cycloalkyl containing 3～8 carbon atoms and the aromatic radical containing 6～12 carbon atoms。If the carbon number of these groups is too much, then being easily caused additive viscosity increases, and electrolytic conductivity reduces, so that battery performance worsens；Simultaneously as the synergism of the space steric effect of each functional group, double bond and itrile group and surface reaction activity reduce, cause that the improvement effect of the high temperature storage of battery is reduced by it。
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the quality of described additive accounts for 0.1wt% to the 15wt% of electrolyte gross mass。0.1wt%～15wt% that the content of additive is electrolyte gross weight is comparatively suitable。If too low, to high temperature storage improvement DeGrain, its passivation to both positive and negative polarity of Ruo Taigaozeyin, causing that internal battery impedance increases, battery capacity reduces。The quality of additive accounts for the 0.1wt%～15wt% of electrolyte gross mass, it is possible to make battery obtain good high-temperature behavior, has higher capacity simultaneously and plays。
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the quality of described additive accounts for 1wt% to the 10wt% of electrolyte gross mass。
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the quality of described additive accounts for 2wt% to the 5wt% of electrolyte gross mass。
As a kind of improvement of lithium-ion battery electrolytes of the present invention, in described additive, n is the integer of 1～7。For this compound, when itrile group and ethylene linkage are joined directly together, when namely the n in Formulas I is 0, itrile group and ethylene linkage can form stronger conjugated structure, and additive is more easy to electrochemical polymerization on positive and negative electrode surface, causes that interfacial film is thicker, interface impedance is relatively big, thus causing the greater loss of anode specific capacity；Carbon number between itrile group and ethylene linkage, when namely the n in Formulas I is not 0, high temperature storage is not only improved significantly by the introducing of this compound, and the infringement of anode specific capacity is also smaller。Therefore comprehensive battery capacity plays and high-temperature storage performance, it is preferred that compound is ethylene linkage and itrile group not conjugation, and when namely formula n is not 0, the compound represented by Formulas I is the most suitable；Considering that n increases, namely molecule carbon chain length increases, and causes that electrolyte viscosity increases, and electrical conductivity reduces, and therefore the value of n is comparatively suitable with 1～7。
As a kind of improvement of lithium-ion battery electrolytes of the present invention, described additive is 3-butene nitrile。
A kind of improvement as lithium-ion battery electrolytes of the present invention, described solvent is ethylene carbonate, Allyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, vinylene carbonate, fluorinated ethylene carbonate, methyl formate, ethyl acetate, methyl butyrate, acrylic acid methyl ester., ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, anhydride, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, dimethyl sulfoxide, methyl sulfide, at least one in gamma-butyrolacton and oxolane。
A kind of lithium ion battery of offer is provided, including plus plate current-collecting body and the positive active material, negative current collector and the negative electrode active material being coated on negative current collector, isolating membrane and the electrolyte that are coated on plus plate current-collecting body, described electrolyte is the lithium-ion battery electrolytes described in above-mentioned paragraph。
Hinge structure, the additive containing thiazolinyl and itrile group is with the addition of due in the electrolyte that the lithium ion battery of the present invention uses, battery has better stability when completely filling, because electrolyte therein is not easily decomposed by the positive pole of state-of-charge and negative pole, thus reducing the generation of gas, therefore the lithium ion battery of the present invention has the advantage that cell thickness expansion is little when high temperature storage, has better performance。
As a kind of improvement of lithium ion battery of the present invention, described positive active material includes at least one in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide。
Improve described negative electrode active material as lithium ion battery of the present invention a kind of and include at least one in soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon complex or lithium titanate。
The battery that the electrolyte of the present invention is assembled into for these positive active materials and negative electrode active material can both play the effect improving high-temperature storage performance。
Detailed description of the invention
Comparative example 1
The preparation of electrolyte:
Ethylene carbonate (EC), Allyl carbonate (PC), diethyl carbonate (DEC) are mixed with the mass ratio of 40: 40: 20, obtains nonaqueous solvent, and by lithium hexafluoro phosphate (LiPF6) be dissolved in above-mentioned nonaqueous solvent as lithium salts, obtain basic electrolyte。
The preparation of lithium ion battery:
By active substance LiNi0.5Co0.2Mn0.3O2(LNCM), conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) in mass ratio 96: 2: 2 in N-Methyl pyrrolidone dicyandiamide solution, be sufficiently stirred for mix homogeneously after, be coated on Al paper tinsel dry, cold pressing, obtain anode pole piece。
After active substance graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickening agent carboxymethyl cellulose sodium (CMC) are sufficiently stirred for mix homogeneously according to mass ratio 95: 2: 2: 1 in deionized water solvent system, be coated on Cu paper tinsel dry, cold pressing, obtain cathode pole piece。
Using polyethylene (PE) porous polymer film as isolating membrane。
Anode pole piece, isolating membrane, cathode pole piece are folded in order, makes isolating membrane be in the middle of kathode to play the effect of isolation, and wind and obtain naked battery core。Naked battery core is placed in outer package, injects the basic electrolyte prepared and encapsulate。
Embodiment 1
The preparation of electrolyte:
Ethylene carbonate (EC), Allyl carbonate (PC), diethyl carbonate (DEC) are mixed with the mass ratio of 40: 40: 20, obtains nonaqueous solvent, and by lithium hexafluoro phosphate (LiPF6) be dissolved in above-mentioned nonaqueous solvent as lithium salts, obtain basic electrolyte。Then in basic electrolyte, add 2-butylene nitrile again as additive, make the quality of 2-butylene nitrile account for the 3wt% of electrolyte gross mass。
The preparation of lithium ion battery:
By positive active material LiNi0.5Co0.2Mn0.3O2(LNCM), conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) in mass ratio 96: 2: 2 in N-Methyl pyrrolidone dicyandiamide solution, be sufficiently stirred for mix homogeneously after, be coated on Al paper tinsel dry, cold pressing, obtain anode pole piece。
After negative electrode active material Delanium, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickening agent carboxymethyl cellulose sodium (CMC) are sufficiently stirred for mix homogeneously according to mass ratio 95: 2: 2: 1 in deionized water solvent system, be coated on Cu paper tinsel dry, cold pressing, obtain cathode pole piece。
Using polyethylene (PE) porous polymer film as isolating membrane。
Anode pole piece, isolating membrane, cathode pole piece are folded in order, makes isolating membrane be in the middle of kathode to play the effect of isolation, and wind and obtain naked battery core。Naked battery core is placed in outer package, injects the basic electrolyte prepared and encapsulate。
Embodiment 2
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylene carbonate (EC), the mass ratio of three respectively 40: 40: 20, additive is 4-dodecyl-3-butene nitrile, and the quality of 4-dodecyl-3-butene nitrile accounts for the 0.1wt% of electrolyte gross mass。
Positive active material is cobalt acid lithium (LiCoO2)；Negative electrode active material is the mixture of native graphite and hard carbon, the mass ratio of the two respectively 85: 15。
All the other, with embodiment 1, repeat no more here。
Embodiment 3
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of Ethyl methyl carbonate (EMC), gamma-butyrolacton and vinylene carbonate (VC), the mass ratio of three respectively 80: 10: 10, additive is 3-methyl-3-butene nitrile, and the quality of 3-methyl-3-butene nitrile accounts for the 0.5wt% of electrolyte gross mass。
Positive active material is cobalt acid lithium (LiCoO2) and lithium nickelate (LiNiO2) mixture, the mass ratio of the two respectively 90: 10；Negative electrode active material is Delanium and the mixture of soft carbon, the mass ratio of the two respectively 70: 30。
All the other, with embodiment 1, repeat no more here。
Embodiment 4
As different from Example 1, the nonaqueous solvent of electrolyte is methyl propyl carbonate (PMC), fluorinated ethylene carbonate (FEC) and N, the mixture of dinethylformamide (DMF), the mass ratio of three respectively 90: 5: 5, additive is 3-cycloalkyl-4-phenyl-3-butene nitrile, and the quality of 3-cycloalkyl-4-phenyl-3-butene nitrile accounts for the 1wt% of electrolyte gross mass。
Positive active material is LiMn2O4 (LiMnO2) and lithium nickelate (LiNiO2) mixture, the mass ratio of the two respectively 20: 80；Negative electrode active material is silicon。
All the other, with embodiment 1, repeat no more here。
Embodiment 5
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of ethylene carbonate (EC), ethyl acetate and N-Methyl pyrrolidone (NMP), the mass ratio of three respectively 95: 2: 3, additive is 3-phenyl-4-ring octyl group-allyl acetonitrile, and the quality of 3-phenyl-4-ring octyl group-allyl acetonitrile accounts for the 5wt% of electrolyte gross mass。
Positive active material is lithium nickel cobalt aluminum oxide (LiNi0.5Co0.2Al0.3O2) (LNCA) and lithium nickelate (LiNiO2) mixture, the mass ratio of the two respectively 20: 80；Negative electrode active material is Si oxide and the mixture of silicon-carbon complex, the mass ratio of the two respectively 60: 40。
All the other, with embodiment 1, repeat no more here。
Embodiment 6
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylene carbonate (EC), the mass ratio of three respectively 40: 40: 20, additive is 3-butene nitrile, and the quality of 3-butene nitrile accounts for the 3wt% of electrolyte gross mass。
Positive active material is LiMn2O4 (LiMnO2) and cobalt acid lithium (LiCoO2) mixture, the quality of the two respectively ratio is for 45: 55；Negative electrode active material is the mixture of Delanium, native graphite and hard carbon, and the mass ratio of three respectively 50: 45: 5。
All the other, with embodiment 1, repeat no more here。
Embodiment 7
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of ethylene carbonate (EC), ethylene sulfurous acid number and acetonitrile, the mass ratio of three respectively 85: 10: 5, additive be 10-to benzene hexyl-9-decene nitrile, and the quality of benzene hexyl-9-decene nitrile is accounted for the 8wt% of electrolyte gross mass by 10-。
Positive active material is Li, Ni, Mn oxide (LiNi0.5Mn0.5O2), LiMn2O4 (LiMnO2) and cobalt acid lithium (LiCoO2) mixture, the quality of three respectively ratio is for 10: 20: 70；Negative electrode active material is lithium titanate。
All the other, with embodiment 1, repeat no more here。
Embodiment 8
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of Allyl carbonate (PC), dimethyl sulfoxide (DMSO) and methyl butyrate, the mass ratio of three respectively 75: 10: 15, additive is 5-heptyl-6-cyclohexyl-5-hexene nitrile, and the quality of 5-heptyl-6-cyclohexyl-5-hexene nitrile accounts for the 10wt% of electrolyte gross mass。
Positive active material is LiMn2O4 (LiMnO2) and cobalt acid lithium (LiCoO2) mixture, the quality of the two respectively ratio is for 45: 55；Negative electrode active material is silicon-carbon complex。
All the other, with embodiment 1, repeat no more here。
Embodiment 9
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Allyl carbonate (PC), the mass ratio of three respectively 50: 30: 20, additive is 3-ethyl-4-cyclopropyl-3-butene nitrile, and the quality of 3-ethyl-4-cyclopropyl-3-butene nitrile accounts for the 15wt% of electrolyte gross mass。
Positive active material is lithium nickelate (LiNiO2) and cobalt acid lithium (LiCoO2) mixture, the quality of the two respectively ratio is for 45: 55；Negative electrode active material is the mixture of Delanium, native graphite and soft carbon, and the mass ratio of three respectively 50: 45: 5。
All the other, with embodiment 1, repeat no more here。
Embodiment 10
As different from Example 1, the nonaqueous solvent of electrolyte is the mixture of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Allyl carbonate (PC), the mass ratio of three respectively 70: 10: 20, additive is 3-butene nitrile, and the quality of 3-butene nitrile accounts for the 2wt% of electrolyte gross mass。
Positive active material is lithium nickel cobalt aluminum oxide (LiNi0.5Co0.2Al0.3O2) (LNCA) and lithium nickelate (LiNiO2) mixture, the quality of the two respectively ratio is for 40: 60；Negative electrode active material is the mixture of Delanium, native graphite and hard carbon, and the mass ratio of three respectively 50: 45: 5。
All the other, with embodiment 1, repeat no more here。
Battery capacity is tested
The battery of comparative example 1 and embodiment 1 to 10 is respectively taken 5, and at normal temperatures with 0.5C multiplying power constant current charge to voltage 4.25V, charging to electric current further under 4.2V constant voltage is 0.04C, is discharged to voltage for 2.9V with 0.5C multiplying power constant current further。Take the discharge capacity of final step 0.5C constant current as battery capacity, by this capacity quality divided by positive pole effective active matter, obtain the specific discharge capacity of each battery positive electrode active material。The average data of the specific discharge capacity of each Battery pack is as shown in table 1。
High temperature storage is tested
The battery of comparative example 1, embodiment 1 to 10 is respectively taken 5, and at normal temperatures with 0.5C multiplying power constant current charge to voltage for 4.25V, charging to electric current further under 4.2V constant voltage is 0.04C so that it is be in 4.2V fully charged state。Test the full charge pond thickness before storage and be designated as D0。Again the battery of fully charged state is placed in 85 DEG C of baking ovens, after four hours, battery is taken out, test the thickness after its storage immediately and be designated as D1。The thickness swelling before and after battery storage is calculated according to following formula
ε=(D1-D0)/D0× 100%
The average thickness expansion rate of each Battery pack of gained is as shown in table 1。
By the data in contrast 1, embodiment 1 and 6 in table 1 it can be seen that the 3-butene nitrile of the 2-butylene nitrile or 3% mass ratio that introduce 3% mass ratio in basic electrolyte all can be effectively improved the high-temperature storage performance of battery core。The thickness swelling of 56.1% after storing compared to 85 DEG C of basic electrolyte battery, introduces after the 2-butylene nitrile of 3% mass ratio, 3-butene nitrile the thickness swelling of battery respectively 12.9%, 13.8%, and tool improves significantly。But the positive electrode specific capacity compared to basic electrolyte 149.4mAh/g plays, after introducing the 2-butylene nitrile of 3% mass ratio, 3-butene nitrile, the positive electrode specific capacity of battery plays respectively 140.3mAh/g and 147.1mAh/g, have dropped 6.1% and 1.9% respectively。It can be seen, the high-temperature storage performance of battery is all improved significantly by 2-butylene nitrile and 3-butene nitrile, but the itrile group of 2-butylene nitrile and ethylene linkage are joined directly together, and its conjugated structure can bring bigger positive electrode specific capacity to lose；It is separated by between itrile group and the ethylene linkage of 3-butene nitrile a carbon atom, the loss of positive electrode specific capacity is just much smaller。Therefore, the carbon number between itrile group and the ethylene linkage of this compound preferred structure is not 0。
From table 1, the data in comparative example 1 and embodiment 2 to 10 are it can be seen that after introducing the additive of the present invention in basic electrolyte, the specific capacity of battery core positive pole can decrease。When the introduction volume of additive is less than 1%, the loss amount of positive electrode specific capacity is less than 0.5%；When additive introduction volume is 5%, the loss of positive electrode specific capacity is 1.3%；When the introduction volume of additive reaches 15%, the loss of positive electrode specific capacity reaches 11.9%。However as increasing of additive introduction volume, battery core thickness swelling after 85 DEG C of storages is gradually lowered。Thickness swelling after the storage of 85 DEG C of comparative example 1 battery reaches 56%, and after introducing 1% additive, thickness swelling is reduced to 17.1%；When additive introduction volume is 15%, thickness swelling is only 6.9%。The consideration of integrated capacity and thickness swelling, 0.1～15% is the introduction volume that such additive optimizes。
The positive discharge specific capacity of the lithium ion battery of table 1 comparative example 1 and embodiment 1 to 10 and 85 DEG C of storage thickness swellings
The announcement of book and instruction according to the above description, above-mentioned embodiment can also be modified and revise by those skilled in the art in the invention。Therefore, the invention is not limited in detailed description of the invention disclosed and described above, should also be as some modifications and changes of the present invention falling in the scope of the claims of the present invention。Although additionally, employ some specific terms in this specification, but these terms are intended merely to convenient explanation, and the present invention does not constitute any restriction。
Claims (9)
1. a lithium-ion battery electrolytes, including nonaqueous solvent and the lithium salts being dissolved in nonaqueous solvent, it is characterised in that: described electrolyte also includes additive, and described additive is the compound represented by following formula (I):
Formulas I
Wherein R1、R2、R3Selected from hydrogen atom, alkyl containing 1 ~ 12 carbon atom, the cycloalkyl containing 3 ~ 8 carbon atoms and the aromatic radical containing 6 ~ 12 carbon atoms, n is the integer of 1 ~ 7。
2. lithium-ion battery electrolytes according to claim 1, it is characterised in that: the quality of described additive accounts for 0.1wt% to the 15wt% of electrolyte gross mass。
3. lithium-ion battery electrolytes according to claim 2, it is characterised in that: the quality of described additive accounts for 1wt% to the 10wt% of electrolyte gross mass。
4. lithium-ion battery electrolytes according to claim 2, it is characterised in that: the quality of described additive accounts for 2wt% to the 5wt% of electrolyte gross mass。
5. lithium-ion battery electrolytes according to claim 3, it is characterised in that: described additive is 3-butene nitrile。
6. lithium-ion battery electrolytes according to claim 1, it is characterized in that: described solvent is ethylene carbonate, Allyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, vinylene carbonate, fluorinated ethylene carbonate, methyl formate, ethyl acetate, methyl butyrate, acrylic acid methyl ester., ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, anhydride, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, dimethyl sulfoxide, methyl sulfide, at least one in gamma-butyrolacton and oxolane。
7. a lithium ion battery, including plus plate current-collecting body and the positive active material, negative current collector and the negative electrode active material being coated on negative current collector, isolating membrane and the electrolyte that are coated on plus plate current-collecting body, it is characterised in that: described electrolyte is the lithium-ion battery electrolytes described in any one of claim 1 to 6。
8. lithium ion battery according to claim 7, it is characterised in that: described positive active material includes at least one in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide。
9. lithium ion battery according to claim 7, it is characterised in that: described negative electrode active material includes at least one in soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon complex or lithium titanate。
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| CN103078141A (en) * | 2013-01-25 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN104332649B (en) * | 2014-09-09 | 2016-12-07 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of electrolyte and its preparation method and application |
| CN105990602A (en) * | 2015-02-24 | 2016-10-05 | 江苏省新动力电池及其材料工程技术研究中心有限公司 | Method for manufacturing high-capacity high-power power type lithium ion battery |
| CN105514435B (en) * | 2016-01-28 | 2018-06-29 | 江苏金坛长荡湖新能源科技有限公司 | A kind of lithium ion battery anode slurry and preparation method thereof |
| CN109904447B (en) * | 2019-03-29 | 2022-02-25 | 蜂巢能源科技有限公司 | Lithium-ion batteries and electric vehicles |
| CN111129664A (en) * | 2019-12-20 | 2020-05-08 | 杉杉新材料（衢州）有限公司 | Lithium ion battery electrolyte and lithium ion battery thereof |
| CN111952670A (en) * | 2020-07-12 | 2020-11-17 | 复旦大学 | A lithium-ion battery with a wide operating temperature range |
| CN113767500B (en) * | 2020-08-13 | 2023-01-20 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device |
| CN113067033B (en) * | 2021-03-22 | 2023-02-28 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN114556662A (en) * | 2021-03-30 | 2022-05-27 | 宁德新能源科技有限公司 | A kind of electrolyte and electrochemical device containing the electrolyte |
| CN113140797B (en) * | 2021-04-25 | 2022-09-20 | 湖州师范学院 | Non-aqueous electrolyte with polynitrile compound and lithium ion battery |
| CN113871712B (en) * | 2021-09-24 | 2024-01-26 | 远景动力技术(江苏)有限公司 | Lithium ion battery electrolyte, preparation method thereof and lithium ion battery |
| CN113764738B (en) * | 2021-10-12 | 2024-05-14 | 远景动力技术(江苏)有限公司 | Electrolyte for improving high-temperature storage characteristics of battery and lithium ion battery |
| CN115332638B (en) * | 2022-10-14 | 2023-03-24 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device and electronic device |
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