CN107017432A - Nonaqueous electrolytic solution and lithium ion battery - Google Patents
Nonaqueous electrolytic solution and lithium ion battery Download PDFInfo
- Publication number
- CN107017432A CN107017432A CN201610058323.5A CN201610058323A CN107017432A CN 107017432 A CN107017432 A CN 107017432A CN 201610058323 A CN201610058323 A CN 201610058323A CN 107017432 A CN107017432 A CN 107017432A
- Authority
- CN
- China
- Prior art keywords
- electrolytic solution
- nonaqueous electrolytic
- phosphoric acid
- cyclic anhydride
- acid cyclic
- 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.)
- Granted
Links
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 105
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 71
- -1 Phosphoric acid cyclic anhydride compound Chemical class 0.000 claims abstract description 67
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 3
- IEJCIJGHMBBDMU-UHFFFAOYSA-N oct-4-enedinitrile Chemical class N#CCCC=CCCC#N IEJCIJGHMBBDMU-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 18
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 35
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 35
- 238000002360 preparation method Methods 0.000 description 35
- 229910001290 LiPF6 Inorganic materials 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C(CCC*NC1[C@@](*)CC1)OC)C1[C@@](C*(C)(*)C2CCC2)C2[*+]1*2 Chemical compound CC(C(CCC*NC1[C@@](*)CC1)OC)C1[C@@](C*(C)(*)C2CCC2)C2[*+]1*2 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 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 2
- 239000002253 acid Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013098 LiBF2 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 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
- H01M10/056—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/09—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton containing at least two cyano groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of nonaqueous electrolytic solution and lithium ion battery.The nonaqueous electrolytic solution includes：Non-aqueous organic solvent；Lithium salts；And additive.The additive includes：Phosphoric acid cyclic anhydride compound；And the dinitrile compound containing unsaturated bond.The nonaqueous electrolytic solution of the present invention can improve the stability of positive electrode active materials under high voltages, suppress nonaqueous electrolytic solution in positive electrode surface oxidation Decomposition, improve the chemical property of lithium ion battery under high voltage condition.The lithium ion battery of the present invention can be used for high voltage condition for a long time.
Description
Technical field
The present invention relates to field of batteries, more particularly to a kind of nonaqueous electrolytic solution and lithium ion battery.
Background technology
Lithium ion battery has that energy density is high, operating voltage is high, self-discharge rate is low, has extended cycle life,
It is pollution-free to wait unique advantage, it is widely used in the electronic products such as camera, mobile phone as power supply.
In recent years, with the fast development of smart electronicses product, the endurance to lithium ion battery is proposed
Higher requirement.In order to improve the energy density of lithium ion battery, exploitation high-voltage lithium ion batteries are
One of effective ways.At present, operating voltage turns into numerous scientific researches in more than 4.35V lithium ion battery
The focus of unit and business research.But under high voltages, the oxidation activity rise of positive electrode active materials,
Stability declines, and causes nonaqueous electrolytic solution easily to occur electrochemical oxidation reactions, Jin Erfen in positive electrode surface
Solution produces gas.Meanwhile, transition metal (such as nickel, cobalt, manganese) meeting in positive electrode active materials
Generation reduction reaction and dissolution, so as to cause lithium ion battery chemical property further to deteriorate.Therefore,
It is the emphasis developed in high-voltage lithium ion batteries in the oxidation Decomposition of positive electrode surface to overcome nonaqueous electrolytic solution
Problem.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of nonaqueous electrolytic solution and
Lithium ion battery, the nonaqueous electrolytic solution can be used for high voltage condition for a long time, and ensure that lithium ion battery has
There is excellent chemical property.
In order to achieve the above object, in one aspect of the invention, the invention provides a kind of nonaqueous electrolytic solution,
It includes：Non-aqueous organic solvent；Lithium salts；And additive.The additive includes：Phosphoric acid cyclic anhydride
Compound；And the dinitrile compound containing unsaturated bond.
In another aspect of this invention, the invention provides a kind of lithium ion battery, it includes：Non- water power
Solve liquid；Positive plate；Negative plate；And barrier film, isolation positive plate and negative plate.The non-aqueous solution electrolysis
Liquid is the nonaqueous electrolytic solution according to one aspect of the present invention.
Relative to prior art, beneficial effects of the present invention are：
The nonaqueous electrolytic solution of the present invention can improve the stability of positive electrode active materials under high voltages, suppress
Nonaqueous electrolytic solution improves the electrochemistry of lithium ion battery under high voltage condition in positive electrode surface oxidation Decomposition
Energy.
The lithium ion battery of the present invention can be used for high voltage condition for a long time.
Embodiment
The following detailed description of the nonaqueous electrolytic solution and lithium ion battery according to the present invention.
Illustrate nonaqueous electrolytic solution according to a first aspect of the present invention first, it includes：Non-aqueous organic solvent；
Lithium salts；And additive.The additive includes：Phosphoric acid cyclic anhydride compound；And contain unsaturated bond
Dinitrile compound.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, phosphoric acid cyclic anhydride compound can be in positive pole
Surface of active material reaction generation Low ESR passivating film, improves positive electrode active materials structures under high voltages
Stability, suppresses crystal structure and caves in, improve the stabilization of oxygen atom in positive electrode active materials under high voltages
Property；Dinitrile compound containing unsaturated bond can be in the transition metal in positive electrode surface and positive electrode active materials
Multiple tooth complex reaction occurs for element, and occurs the fine and close positive-pole protective layer of polymerisation generation, plays stabilization
The effect of transition metal, so as to effectively suppress nonaqueous electrolytic solution in positive electrode surface under high voltages
Reaction, suppresses transition metal dissolution.The dinitrile compound of unsaturated bond is prior to phosphoric acid cyclic anhydride chemical combination
Thing does not need specific reaction potential in positive electrode surface formation diaphragm, and it is made by multiple tooth complexing
It is in network structure with the protective layer with the transition metal formation in positive electrode active materials, to phosphoric acid cyclic anhydride
The formation of the passivating film of compound has inducing action, it is uniformly dispersed on network structure, final institute
The composite protection film even structure of formation is fine and close, electrolyte resistance burn into heat endurance.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the phosphoric acid cyclic anhydride compound is optional
From one or more of compounds with formula (I) structure,
In formula (I), R1、R2、R3It is each independently selected from alkyl, carbon atom that carbon number is 1~7
Number is 6~15 and the group containing at least one phenyl ring.The alkyl is to lose any one on alkane molecule
The group that individual hydrogen atom is formed.The alkane may be selected from linear paraffin, branched paraffin, cycloalkane
Any one.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, R1、R2、R3Can be independently of one another
Alkyl, phenyl selected from carbon number for 1~3.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, R1、R2、R3Can be identical.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the phosphoric acid cyclic anhydride compound is optional
From tripropyl phosphoric acid cyclic anhydride, trimethyl phosphoric acid cyclic anhydride, triethyl group phosphoric acid cyclic anhydride and triphenyl phosphoric acid cyclic anhydride
In one or more.Following formula (1)~(4) of correspondence, wherein, R1、R2、R3It is identical, point
Wei not n-propyl, methyl, ethyl, phenyl.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the dintrile containing unsaturated bond
Compound may be selected from one or more of compounds with formula (II) structure,
In formula (II), A1Selected from the alkylene that carbon number is 1~10, A2It is selected from carbon number
1~10 alkylene, A3It is 1~10 alkyl, A selected from H or carbon number4Selected from H or carbon atom
Number is 1~10 alkyl.The alkyl is loses any one hydrogen atom institute shape on hydrocarbon molecules
Into group.The alkylene is by losing the base that any two hydrogen atom is formed on hydrocarbon molecules
Group.The hydrocarbon compound can include any one in alkane, cycloalkane, alkene, alkynes, aromatic hydrocarbon
Kind.The alkane may be selected from any one in linear paraffin, branched paraffin, cycloalkane.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, A1May be selected from carbon number is
1~5 alkylidene.A2It may be selected from the alkylidene that carbon number is 1~5.A3It may be selected from H, carbon former
The aryl that the alkyl or carbon number that subnumber is 1~5 are 6~10.A4May be selected from H, carbon number is
1~5 alkyl or carbon number is 6~10 aryl.The alkylidene is to lose to appoint on alkane molecule
The group that two hydrogen atoms of meaning are formed.The alkyl is that any one hydrogen original is lost on alkane molecule
The group that son is formed.The aryl is that any one hydrogen original is lost on the aromatic rings of fragrant hydrocarbon molecule
The group that son is formed.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the dintrile containing unsaturated bond
Compound can have symmetrical structure.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the dintrile containing unsaturated bond
Compound may be selected from 1,4- dicyano -2- butylene, 1,6- dicyano -3- hexenes and 1,4- dicyanos -2,3- two
One or more in methyl-2-butene.Following formula (5)~(7) of correspondence.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the phosphoric acid cyclic anhydride compound is non-
Weight/mass percentage composition in water electrolysis liquid can be 0.1%~3%.When phosphoric acid cyclic anhydride compound is in nonaqueous electrolytic solution
In weight/mass percentage composition it is too low when, its surface of positive electrode active material generate Low ESR passivating film it is anti-
Should be not enough fully unobvious to the improvement result of the chemical property of lithium ion battery；When phosphoric acid cyclic anhydride
When weight/mass percentage composition of the compound in nonaqueous electrolytic solution is too high, it is generated in surface of positive electrode active material
Low ESR passivating film thickeies, impedance increase, is unfavorable for the cycle performance of lithium ion battery on the contrary.Preferably,
The upper limit of weight/mass percentage composition scope of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution may be selected from
2%th, 1%, lower limit may be selected from 0.1%, 0.2%, 0.5%.It is further preferred that the phosphoric acid cyclic anhydride
Weight/mass percentage composition of the compound in nonaqueous electrolytic solution can be 0.5%~2%.It is further preferred that described
Weight/mass percentage composition of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution can be 0.5%~1%.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the dintrile containing unsaturated bond
Weight/mass percentage composition of the compound in nonaqueous electrolytic solution can be 0.1%~4%.As two containing unsaturated bond
When weight/mass percentage composition of the nitrile compound in nonaqueous electrolytic solution is too low, itself and transition in positive electrode active materials
The chelation structure of metallic element formation is not fine and close enough, and unsaturated bond polymerization crosslinking degree is relatively low, it is impossible to effectively
Form fine and close protective layer, it is impossible to which the oxidation effectively between suppression nonaqueous electrolytic solution and positive electrode active materials is also
Original reaction, so that the chemical property of lithium ion battery can not be improved；When two nitrilations containing unsaturated bond
When weight/mass percentage composition of the compound in nonaqueous electrolytic solution is too high, itself and the transition in positive electrode active materials are golden
The complexing for belonging to element formation is too strong, and polymerization crosslinking degree is high, and the protective layer of formation is very thick, is unfavorable for
Lithium ion passes through, and causes positive pole impedance to dramatically increase, and the cycle performance of lithium ion battery can be caused to be deteriorated.
Preferably, weight/mass percentage composition model of the dinitrile compound containing unsaturated bond in nonaqueous electrolytic solution
The upper limit enclosed may be selected from 3%, 2%, and lower limit may be selected from 0.1%, 0.2%, 0.5%.It is further preferred that
Weight/mass percentage composition of the dinitrile compound containing unsaturated bond in nonaqueous electrolytic solution can be
0.2%~3%.It is further preferred that quality hundred of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution
It can be 0.5%~2% to divide content.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the non-aqueous organic solvent may be selected from
Ethylene carbonate (being abbreviated as EC), propene carbonate (being abbreviated as PC), dimethyl carbonate (are write a Chinese character in simplified form
For DMC), diethyl carbonate (being abbreviated as DEC), methyl ethyl carbonate (being abbreviated as EMC), γ-
Butyrolactone (being abbreviated as BL), methyl formate (being abbreviated as MF), Ethyl formate (being abbreviated as MA),
Ethyl propionate (being abbreviated as EP), propyl propionate (being abbreviated as PP) and tetrahydrofuran (being abbreviated as THF)
In one or more.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the lithium salts may be selected from organolithium
Salt, inorganic lithium salt or its combination.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, fluorine member can be contained in the lithium salts
One or more in element, boron element, P elements.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, the lithium salts may be selected from hexafluorophosphoric acid
Lithium LiPF6, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double (fluorine sulphurs
Acyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(it is abbreviated as
LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) (being abbreviated as LiDFOB), hexafluoroarsenate lithium
LiAsF6, lithium perchlorate LiClO4, trifluoromethanesulfonic acid lithium LiCF3SO3In one or more.
In nonaqueous electrolytic solution described according to a first aspect of the present invention, in the nonaqueous electrolytic solution, lithium
The concentration of salt can be 0.5M~1.5M.Preferably, the concentration of lithium salts can be 0.8M~1.2M.
Secondly lithium ion battery described according to a second aspect of the present invention is illustrated, it includes：Nonaqueous electrolytic solution；
Positive plate；Negative plate；And barrier film, isolation positive plate and negative plate.The nonaqueous electrolytic solution is root
According to the nonaqueous electrolytic solution described in first aspect present invention.
In lithium ion battery described according to a second aspect of the present invention, the charging of the lithium ion battery is whole
Only voltage can be not less than 4.35V.It is further preferred that the end of charge voltage of the lithium ion battery is
4.35V~5V.The lithium ion battery of the present invention can be used for more than 4.35V high voltage condition for a long time.
In lithium ion battery described according to a second aspect of the present invention, the positive plate may include positive pole collection
Fluid and the positive pole diaphragm being coated on plus plate current-collecting body.The positive pole diaphragm may include positive-active material
Material, binding agent and conductive agent.The positive electrode active materials may be selected from cobalt acid lithium LiCoO2, nickle cobalt lithium manganate,
One or more in LiMn2O4.
In lithium ion battery described according to a second aspect of the present invention, the negative plate may include negative pole collection
Fluid and the cathode membrane being coated on negative current collector.The cathode membrane may include negative electrode active material
Material, binding agent and conductive agent.The negative active core-shell material may be selected from graphite and/or silicon.
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate
The application rather than limitation scope of the present application.
Comparative example 1
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate (EC), carbonic acid third
Alkene ester (PC) and diethyl carbonate (DEC) EC in mass ratio:PC:DEC=1:1:1 ratio mixing is equal
It is even, obtain non-aqueous organic solvent.LiPF is added into non-aqueous organic solvent6, obtain LiPF6Concentration is
1mol/L solution, as nonaqueous electrolytic solution.
(2) preparation of positive plate：Weigh 1.42kg Solvents N-methyls -2-Pyrrolidone (being abbreviated as NMP),
1.2kg binding agents polyvinylidene fluoride (is abbreviated as PVDF, the weight/mass percentage composition of polyvinylidene fluoride is
10%), 0.16kg conductive agents electrically conductive graphite and 7.2kg positive electrode active materials cobalt acid lithiums (LiCoO2),
It is sufficiently mixed and is uniformly mixing to obtain anode sizing agent.It is 16 μm that anode sizing agent is uniformly coated into thickness
On plus plate current-collecting body aluminium foil, 120 DEG C toast 1h obtain positive pole diaphragm, afterwards through overcompaction, cut
To positive plate.
(3) preparation of negative plate：Weigh 1.2kg thickeners sodium carboxymethylcellulose (be abbreviated as CMC,
The weight/mass percentage composition of sodium carboxymethylcellulose for 1.5%), 0.07kg binding agent SBR emulsion (fourths
The weight/mass percentage composition of benzene rubber for 50%), 2.4kg negative active core-shell material powdered graphites, be sufficiently mixed
It is uniformly mixing to obtain cathode size.Cathode size is uniformly coated to the negative pole currect collecting that thickness is 12 μm
On body copper foil, toast 1h at 120 DEG C and obtain cathode membrane, obtain negative plate through overcompaction, cutting afterwards.
(4) preparation of lithium ion battery：Barrier film is used as by 12 μm of polypropylene film of thickness.Will
Positive plate, barrier film, negative plate are folded in order, barrier film is in the middle of both positive and negative polarity and are played isolation
Effect, then winds the naked battery core of squarely.Naked battery core is loaded into aluminum foil sack, removed in 80 DEG C of bakings
After water, inject nonaqueous electrolytic solution, by processes such as Vacuum Package, standing, chemical conversion, shapings, that is, complete
The preparation of lithium ion battery.
Comparative example 2
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride is added into non-aqueous organic solvent, LiPF is added after being well mixed6, obtain
Tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as non-
Water electrolysis liquid.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Comparative example 3
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Isosorbide-5-Nitrae-dicyano -2- butylene is added into non-aqueous organic solvent, LiPF is added after being well mixed6, obtain
It is 1%, LiPF to 1,4- dicyano -2- butylene weight/mass percentage composition6Concentration is 1mol/L solution, i.e.,
For nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Comparative example 4
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 4%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Comparative example 5
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 5%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 1
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 0.2%, Isosorbide-5-Nitrae-dicyano -2- fourths to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Alkene weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 2
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 0.5%, Isosorbide-5-Nitrae-dicyano -2- fourths to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Alkene weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 3
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 4
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 2%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 5
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and double (propionitrile) ethers of ethylene glycol are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 3%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 6
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 0.2%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 7
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 0.5%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 8
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 1%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 9
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 2%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 10
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 3%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Embodiment 11
(1) preparation of nonaqueous electrolytic solution：In drying shed, by ethylene carbonate, propene carbonate and
Diethyl carbonate EC in mass ratio:PC:DEC=1:1:1 ratio is well mixed, and obtains non-aqueous organic molten
Agent.Tripropyl phosphoric acid cyclic anhydride and Isosorbide-5-Nitrae-dicyano -2- butylene are added into non-aqueous organic solvent, is well mixed
After add LiPF6, it is 1%, Isosorbide-5-Nitrae-dicyano -2- butylene to obtain tripropyl phosphoric acid cyclic anhydride weight/mass percentage composition
Weight/mass percentage composition is 4%, LiPF6Concentration is 1mol/L solution, as nonaqueous electrolytic solution.
The preparation of remaining step and condition with lithium ion battery in comparative example 1.
Table 1 provides the composition of comparative example 1-5 and embodiment 1-11 nonaqueous electrolytic solution.
The nonaqueous electrolytic solution of table 1 is constituted
Next the test process of lithium ion battery is illustrated.
(1) the high-temperature storage performance test of lithium ion battery
The high-temperature storage performance of the lithium ion battery to being prepared in comparative example 1-5 and embodiment 1-11 is entered respectively
Row test, method is as follows：At 25 DEG C, first lithium ion battery is charged to 0.5C constant current
End of charge voltage is 4.4V, then using 4.4V constant-voltage charges to electric current as 0.05C, tests lithium-ion electric
The thickness in pond is simultaneously designated as h0；Lithium ion battery is put into 60 DEG C of insulating box afterwards, 30 days are incubated, and
The thickness of lithium ion battery was tested every 5 days and h is designated asn, n is the number of days that high-temperature lithium ion battery is stored.
High-temperature lithium ion battery store n days after thickness swelling (%)=(hn-h0)/h0× 100%.
(2) the cycle performance test of lithium ion battery
The cycle performance of the lithium ion battery to being prepared in comparative example 1-5 and embodiment 1-11 is surveyed respectively
Examination, method is as follows：At 25 DEG C, after lithium ion battery is stood into 30 minutes, with 0.5C multiplying power constant currents
End of charge voltage is charged to for 4.4V, then using 4.4V constant-voltage charges to electric current as 0.05C, and is stood
5 minutes, then with 0.5C multiplying powers constant-current discharge to 3.0V, this is a charge and discharge cycles process, this
Discharge capacity is the discharge capacity first of lithium ion battery, and 200 charge and discharge cycles processes are carried out afterwards.
The discharge capacity of capability retention (%)=n-th circulation after the circulation of lithium ion battery n times/first
Discharge capacity × 100%.
The high-temperature storage performance test result of the lithium ion battery of table 2
The cycle performance test result of the lithium ion battery of table 3
It can be seen that from comparative example 1-3 test results and tripropyl phosphoric acid individually added in nonaqueous electrolytic solution
Cyclic anhydride or Isosorbide-5-Nitrae-dicyano -2- butylene, can slightly improve high-temperature storage performance and the circulation of lithium ion battery
Performance, but DeGrain, still occur swollen after high-temperature lithium ion battery storage and after long-term circulation
Gas problem.Embodiment 1-11 adds 1,4- dicyano -2- butylene and tripropyl simultaneously in nonaqueous electrolytic solution
Phosphoric acid cyclic anhydride, the high-temperature storage performance and cycle performance of lithium ion battery are all significantly improved.It is right
Ratio 4 adds high level tripropyl phosphoric acid cyclic anhydride in nonaqueous electrolytic solution, and comparative example 5 adds higher contain
Isosorbide-5-Nitrae-dicyano -2- butylene is measured, by the dinitrile compound and phosphoric acid cyclic anhydride of unsaturated bond are in positive electrode surface institute
Form composite protection film to thicken, impedance increase causes high-temperature storage performance and cycle performance to reduce on the contrary.
It is can be seen that from embodiment 1-5 test result when tripropyl phosphoric acid cyclic anhydride is in nonaqueous electrolytic solution
Weight/mass percentage composition when reaching 3%, the low-resistance resist passivation generated due to it in surface of positive electrode active material
Film thickeies, and impedance increase, the Capacity fading of lithium ion battery is accelerated, but still is better than comparative example 1-3.
Thus, addition of the tripropyl phosphoric acid cyclic anhydride in nonaqueous electrolytic solution is preferably 0.2%~2%, further excellent
Elect 0.5%~1% as.
It is can be seen that from embodiment 6-11 test result when Isosorbide-5-Nitrae-dicyano -2- butylene is in nonaqueous electrolytic solution
In weight/mass percentage composition when reaching 4%, due to itself and the transition metal shape in positive electrode active materials
Into complexing it is too strong, and polymerization crosslinking degree is high, and the very thick lithium ion that is unfavorable for of protective layer of formation passes through,
Positive pole impedance is caused to dramatically increase, lithium ion battery Capacity fading accelerates, but still is better than comparative example
1-3.Thus, Isosorbide-5-Nitrae-mass fraction of the dicyano -2- butylene in nonaqueous electrolytic solution is preferably 0.2%~3%,
More preferably 0.5%~2%.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application,
Although the application with preferred embodiment disclose as above, but and be not used to limit the application, it is any to be familiar with sheet
Technical professional, in the range of technical scheme is not departed from, utilizes the technology of the disclosure above
Content makes a little variation or modification is equal to equivalence enforcement case, belongs to technical scheme scope
It is interior.
Claims (10)
1. a kind of nonaqueous electrolytic solution, including：
Non-aqueous organic solvent；
Lithium salts；And
Additive；
Characterized in that,
The additive includes：
Phosphoric acid cyclic anhydride compound；And
Dinitrile compound containing unsaturated bond.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that the phosphoric acid cyclic anhydride chemical combination
Thing is selected from one or more of compounds with formula (I) structure,
In formula (I), R1、R2、R3It is each independently selected from alkyl, carbon that carbon number is 1~7
Atomicity is 6~15 and the group containing at least one phenyl ring；Preferably, R1、R2、R3It is each independent
Ground is selected from alkyl, phenyl of the carbon number for 1~3.
3. nonaqueous electrolytic solution according to claim 2, it is characterised in that R1、R2、R3It is identical.
4. the nonaqueous electrolytic solution according to Claims 2 or 3, it is characterised in that the phosphoric acid cyclic anhydride
Compound is selected from tripropyl phosphoric acid cyclic anhydride, trimethyl phosphoric acid cyclic anhydride, triethyl group phosphoric acid cyclic anhydride and triphenyl
One or more in phosphoric acid cyclic anhydride.
5. nonaqueous electrolytic solution according to claim 1, it is characterised in that described to contain unsaturated bond
Dinitrile compound be selected from one or more of compounds with formula (II) structure,
In formula (II), A1Selected from the alkylene that carbon number is 1~10, A2It is selected from carbon number
1~10 alkylene, A3It is 1~10 alkyl, A selected from H or carbon number4Selected from H or carbon atom
Number is 1~10 alkyl.
6. nonaqueous electrolytic solution according to claim 5, it is characterised in that
A1Selected from the alkylidene that carbon number is 1~5；
A2Selected from the alkylidene that carbon number is 1~5；
A3The aryl that the alkyl or carbon number for being 1~5 selected from H, carbon number are 6~10；
A4The aryl that the alkyl or carbon number for being 1~5 selected from H, carbon number are 6~10.
7. nonaqueous electrolytic solution according to claim 5, it is characterised in that described to contain unsaturated bond
Dinitrile compound there is symmetrical structure.
8. the nonaqueous electrolytic solution according to claim 5 or 7, it is characterised in that described to contain insatiable hunger
1,4- dicyano -2- butylene, 1,6- dicyano -3- hexenes and 1,4- dicyan are selected from the dinitrile compound of key
One or more in base -2,3- dimethyl -2- butylene.
9. nonaqueous electrolytic solution according to claim 1, it is characterised in that
Weight/mass percentage composition of the phosphoric acid cyclic anhydride compound in nonaqueous electrolytic solution is 0.1%~3%, preferably
For 0.5%~2%；
Weight/mass percentage composition of the dinitrile compound containing unsaturated bond in nonaqueous electrolytic solution be
0.1%~4%, preferably 0.5%~2%.
10. a kind of lithium ion battery, including：
Nonaqueous electrolytic solution；
Positive plate；
Negative plate；And
Barrier film, isolation positive plate and negative plate；
Characterized in that,
The nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to any one of claim 1-9.
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