CN102637901A - Electrolyte for lithium ion battery and preparation method thereof - Google Patents
Electrolyte for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN102637901A CN102637901A CN2012101230800A CN201210123080A CN102637901A CN 102637901 A CN102637901 A CN 102637901A CN 2012101230800 A CN2012101230800 A CN 2012101230800A CN 201210123080 A CN201210123080 A CN 201210123080A CN 102637901 A CN102637901 A CN 102637901A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- solvent
- lithium
- main
- additive
- 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
- 239000003792 electrolyte Substances 0.000 claims description 190
- 239000002904 solvent Substances 0.000 claims description 131
- 229910001416 lithium ion Inorganic materials 0.000 claims description 120
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 119
- 239000000203 mixture Substances 0.000 claims description 96
- 239000000654 additive Substances 0.000 claims description 65
- 230000000996 additive effect Effects 0.000 claims description 65
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- 239000011261 inert gas Substances 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 36
- -1 lithium fluorosilicate Chemical compound 0.000 claims description 30
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 24
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 17
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 13
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 9
- AUAPIRIJQKYWQJ-UHFFFAOYSA-N CNC.C1(CCCCC1)[C]C1CCCCC1 Chemical compound CNC.C1(CCCCC1)[C]C1CCCCC1 AUAPIRIJQKYWQJ-UHFFFAOYSA-N 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- CVUINYZTKUMRKI-UHFFFAOYSA-N but-1-ene;sulfurous acid Chemical class CCC=C.OS(O)=O CVUINYZTKUMRKI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 16
- 239000007774 positive electrode material Substances 0.000 description 15
- 229910013063 LiBF 4 Inorganic materials 0.000 description 14
- 229910013870 LiPF 6 Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910013872 LiPF Inorganic materials 0.000 description 12
- 101150058243 Lipf gene Proteins 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- 229910013684 LiClO 4 Inorganic materials 0.000 description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 101100248451 Arabidopsis thaliana RICE2 gene Proteins 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BZWQNMUGNDAMBX-UHFFFAOYSA-N butyl butane-1-sulfonate Chemical compound CCCCOS(=O)(=O)CCCC BZWQNMUGNDAMBX-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 150000002576 ketones Chemical class 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte for a lithium ion battery and a preparation method thereof. The electrolyte consists of a main electrolyte, an electrolyte additive, a main solvent and a solvent additive. The preparation method comprises the following steps of: A. under the condition of vacuum or inert gas protection, respectively mixing the main solvent and the solvent additive with a drying agent (lithium oxide) which is dried to be at constant weight in advance, and mixing and filtering to remove the lithium oxide and lithium hydroxide sediment; B. uniformly mixing the dried main solvent and the dried solvent additive from the step A; and C. adding a main electrolyte mixture and an electrolyte additive into the solvent mixed in the step B, and agitating and dissolving under the vacuum and inert gas protection to prepare a solution with the mass mol concentration of the main electrolyte of 0.5-1.5 M. The electrolyte has the advantages of abundant resources, low price and no toxin, effectively improves the work temperature range of the battery and effectively prolongs the circulating service life of the battery, so that various types of the lithium ion batteries are manufactured; and the electrolyte is particularly suitable for manufacturing a lithium ion power battery with high power capacity and high multiplying power charging and discharging capacity.
Description
Technical field
The present invention relates to technical field of chemical power; Be specifically related to a kind of lithium-ion battery electrolytes again; The preparation method who also relates to a kind of lithium-ion battery electrolytes simultaneously can be used for making the lithium ion battery of various models, also is applicable to that manufacturing is used for the lithium-ion-power cell of high power charging-discharging.
Background technology
At present, the existing used electrolyte of industrial manufacturing lithium ion battery is mainly LiPF
6, LiBF
4Deng being that electrolytical, electrolyte concentration is at 0.1～2.0M (mol/L; Hereinafter to be referred as M) EC-EMC, EC-EMC-EMC, EC-EMC-DEC, (wherein EC is an ethylene carbonate to EC-DMC-DEC-PC; EMC is a methyl ethyl carbonate, and DEC is a diethyl carbonate, and DMC is a dimethyl carbonate; PC is propene carbonate, and is as follows) etc. organic substance be the solution of solvent.Electrolyte is very big to the lithium ion battery performance impact; This is because bath composition and concentration and its conductivity and electrode reaction are closely related, and the conductivity of electrolyte and the invertibity of electrode reaction directly affect discharge capacity of lithium ion battery, the direct and electrolyte effect of the stability of electrolyte; Can influence the security performance (Guo Yingjun etc. of lithium ion battery; Lithium-ion battery electrolytes progress [J]. new material industry, 2007,8:60-64).Lithium-ion battery electrolytes is most important to specific capacity, operating temperature range, charge and discharge cycles efficient and the security performance of lithium ion battery.And EC, DEC, DMC, EMC equal solvent be mainly used in lithium rechargeable battery, and PC and DME (1,2-dimethoxy-ethane/glycol dimethyl ether) are mainly used in disposable lithium-battery.Because PC is used for secondary cell; Very poor with the graphite cathode compatibility of lithium ion battery, PC decomposes at graphite electrode surface in the charge and discharge process, can cause coming off of graphite linings; (the Liao Hongying etc. thereby the charge/discharge capacity of reduction battery and cycle performance significantly descend; Lithium-ion battery electrolytes [J]. industry forum, 2003,9:34-37.).Crown ether and cryptate can form the clad type chelate with lithium ion, can improve the solubility of lithium salts in organic solvent, realize anion with cationic effective separate with lithium ion and solvent separate the conductance of raising electrolyte; Some fluoro chain ether such as C
4F
9OCH
3Etc. the recommended secondary lithium battery electrolyte that is used for, can improve organic electrolyte thermal stability (He Zhengzhen etc., the progress of lithium-ion battery electrolytes and functional additive thereof [J]. contemporary chemical industry, 2011,40 (9): 928-930.); The trialkyl aryl-silane joins in the lithium ion battery electrolyte commonly used by 3～8% mass ratio; Can improve the security performance of electrolyte; Battery do not smolder when overcharging, not on fire, do not explode that (the bear beautiful jade is strong etc.; Lithium ion battery is clicked right anti-overcharging additive progress [J]. chemical industry progress, 2011,30 (6): 1198-1204).Research shows: trace (0.5%) HMDS (HMDS) can suppress lithium-ion battery electrolytes LiPF in storage process
6Hydrolysis and pyrolysis; Reduce water and hydrofluoric content in the electrolyte; Improve the storage stability and the thermal stability (Hu Lixin etc. of lithium-ion battery electrolytes; HMDS is as lithium-ion battery electrolytes Study of Stabilizers [J]. chemistry and bioengineering, 2011,28 (2): 24-26.).
In addition; 200710143920.9 number Chinese invention patent application discloses a kind of " constituent of electrolyte of low temp lithium ion battery "; Consisting of of this electrolyte: EC (ethylene carbonate), PC (propene carbonate), DME (1; 2-dimethoxy-ethane/glycol dimethyl ether), EMC (methyl ethyl carbonate), DEC (diethyl carbonate), 1,3-PS (1, the 3-propane sultone), LiPF
6This patent is disclosed to be a kind of low temperature functional electrolyte, can improve battery electrical property at low temperatures.200810087478.7 disclose a kind of " lithium-ion battery electrolytes ", the disclosed electrolyte of this patent comprises primary solvent: at least a and lithium salts in gamma-valerolactone, acetate methyl isobutyryl ester, acetate 2-methoxyl group ethyl ester, acetate 2-ethoxy ethyl ester and the diethy-aceto oxalate.200710123621.9 number Chinese invention patent application discloses " a kind of lithium-ion battery electrolytes ".The disclosed technology of this patent application is: a kind of lithium-ion battery electrolytes contains electrolyte and organic solvent; Organic solvent is EC, PC, DMC, EMC, DEC, biphenyl goods cyclohexyl benzene; And additive vinylene carbonate, polypropylene carbonate alkene ester, gamma-butyrolacton, 1, a kind of goods in 3-N-morpholinopropanesulfonic acid lactone, the butyl sultone is multiple.The click right side of this disclosure of the Invention conducts electricity very well, internal resistance is little, can long-time heavy-current discharge, have stable high-temperature performance.201110243969.8 number one Chinese patent application discloses " a kind of lithium-ion battery electrolytes "; Its electrolyte is selected the mixture of di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two fluoroform sulfimide lithiums for use; Nonaqueous solvents is 1; 4-butane sultones, benzyltrimethyl ketone, N, a kind of in dinethylformamide, methyl ethyl carbonate, methyl-sulfoxide, oxolane, acetone, ethyl acetate, the propylene sulfite.It is said: this is invented technological disclosed electrolyte and has stability, high low temperature serviceability, high conductivity, excellent, the energy density advantages of higher of high rate performance preferably.But the disclosed technology of this patent application is not used the data of the correlated performance of the battery that this technology electrolyte makes.
The correlative study of comprehensive above-mentioned existing lithium-ion battery electrolytes and disclosed related patent U.S. Patent No. technology are visible; Prior art is that electrolyte, common organic solvent are solution and some functional additive etc. with the lithium salts; The lithium ion battery of the lithium-ion battery electrolytes manufacturing of manufacturing obviously exists following not enough: 1) high temperature or low-temperature working poor performance, even higher (more than 55 ℃) or lower (below 30 ℃) battery can't work fully or service behaviour very poor; 2) power-type lithium ion battery high current charge-discharge weak effect influences the operate as normal of lithium ion battery group, has seriously limited the range of application of lithium-ion-power cell; 3) the battery storage capacity decay is serious, directly influences the capacity of lithium ion battery and recycles the life-span; 4) anti-over-charging poor performance influences lithium ion battery efficiency for charge-discharge, battery capacity and recycles the life-span; 5) poor safety performance, normally discharge and recharge and battery classification partial volume process in and all have actual potential safety hazard in the course of work; 6) many electrolyte solvents such as furans, pyridine and acetone etc. have bigger toxicity, in the process of the production of lithium ion battery and use and old and useless battery, more or less can cause pollution to a certain degree.Though above-mentioned deficiency not exclusively is due to the lithium-ion battery electrolytes, all deficiencies all with electrolyte conductivity can, with the compatibility of electrode, the fail safe of electrode charge and discharge performance and cycle life, battery is all had direct influence.Therefore, it is all within reason how lithium ion battery is stressed the high request of electrolyte, and it is not enough to solve prior art, and electrolyte also is one of crucial factor.
Summary of the invention
In order to solve the above-mentioned deficiency that prior art exists; The objective of the invention is to be to provide a kind of lithium-ion battery electrolytes; The lithium ion battery of the present invention's preparation; Ability operate as normal under-40～65 ℃ of temperature range working environments, lithium ion battery efficiency for charge-discharge, heavy-current discharge effect, discharge capacity obviously improve, charge and discharge cycles significant prolongation in useful life, and the lithium ion battery comprehensive electrochemical significantly improves.
Another object of the present invention is the preparation method who has been to provide a kind of lithium-ion battery electrolytes, and technology is simple, additive amount is few, price is low, and is remarkable to improving lithium ion battery comprehensive electrochemical effect.Not changing under the existing electrolyte production equipment condition, can realize the manufacturing of all kinds lithium ion battery, be specially adapted to make the lithium-ion-power cell of high power capacity, high power charging-discharging.
The present invention is achieved through following technical proposals:
A kind of lithium-ion battery electrolytes is made up of main electrolyte, additive agent electrolyte, organic solvent (or claiming main solvent) and solvent additive; Wherein, main electrolyte mol ratio is respectively 0.5～1: 0.1～0.3: 0.01～0.05: 0.01～0.05 lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), lithium fluorosilicate (Li
2SiF
6) and lithium perchlorate (LiClO
4) four mixture; Additive agent electrolyte is that mol ratio is three perfluor ethyls, the three lithium fluophosphate (LiPF of main electrolyte molal quantity 0.1～0.5%
3(C
2F
5)
3), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), lithium carbonate (Li
2CO
3) and lithium acetate (LiAc) in the mixture that mixes of mass ratioes such as three kinds or four kinds; Main solvent is that equal-volume is than the ethylene carbonate (EC), diethyl carbonate (DEC), the dimethyl carbonate (DMC), 1 that mix; 2-dimethoxy-ethane/glycol dimethyl ether (DME), methyl ethyl carbonate (EMC), 1, three kinds or four kinds mixture in 3-propane sultone (1.3-PS), sulfurous acid glycol ester (ES/DTO), dicyclohexyl carbon dimethylamine (DCC), sulfurous acid butene esters (BS), the vinylethylene carbonate (VEC); Solvent additive is an equal-volume than the HMDS (HMDS), the diethyl (cyano methyl) that mix, account for main solvent volume ratio 0.1～0.5% any three kinds mixture in acid esters (DECP), sulfuric acid propylene ester (TS), the methane-disulfonic acid methylene ester (CDE) of seeing.
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; At vacuum (1～10kpa; Following vacuum is this vacuum ranges) or the condition of inert gas shielding under, be respectively the drier lithia (Li of prior vacuumize to the constant weight of solvent 1～5% with mass ratio with main solvent, solvent additive (general designation " solvent ")
2O) mix, stirred 4～12 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step; The dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.1～0.5% than the main solvent that mixes; Vacuum (1～10kpa) or the condition of inert gas shielding under mix, promptly obtain electrolyte solvent.
The 3rd step, with vacuum (be dried under 1～10kpa) condition constant weight, mol ratio is 0.5～1: 0.1～0.3: 0.01～0.05: 0.01～0.05 lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), lithium fluorosilicate (Li
2SiF
6) and lithium perchlorate (LiClO
4) main electrolyte mixture and be dried to constant weight etc. mole mix, total mole number accounts for the additive agent electrolyte of main electrolyte mixture total mole number 0.1～0.5%; Joining second goes on foot in the solvent that mixes; Vacuum or inert gas shielding were stirred 4～8 hours down; Be made into main electrolyte molality (annotate: additive agent electrolyte concentration is not counted in, below identical) and be the solution of 0.5～1.5M (M=mol/L, below identical).
Described main solvent is ethylene carbonate (EC), diethyl carbonate (DEC), the dimethyl carbonate (DMC), 1 that volume ratio is mixed; 2-dimethoxy-ethane/glycol dimethyl ether (DME), methyl ethyl carbonate (EMC), 1, the mixture of any three kinds or four kinds in 3-propane sultone (1.3-PS), sulfurous acid glycol ester (ES/DTO), dicyclohexyl carbon dimethylamine (DCC), sulfurous acid butene esters (BS), the vinylethylene carbonate (VEC).
Described solvent additive is an equal-volume than the HMDS (HMDS), the diethyl (cyano methyl) that the mix any three kinds mixture in acid esters (DECP), sulfuric acid propylene ester (TS), the methane-disulfonic acid methylene ester (CDE) of seeing.
Described main electrolyte is that mol ratio is respectively 0.5～1: 0.1～0.3: 0.01～0.05: 0.01～0.05 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixture.
Described electrolysis additive be mol ratio be main electrolyte molal quantity 0.1～0.5%, etc. the LiPF that mixes of mass ratio
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3, and LiAc in three kinds or four kinds mixture.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
Adopt technical scheme of the present invention, can obtain following obvious effects:
The lithium ion battery of producing with the lithium-ion battery electrolytes of the present invention's technology preparation; Owing to used the compound additive combination that can improve the existing positive active material of using always (cobalt acid lithium, lithium nickelate, LiMn2O4 or cobalt nickel LiMn2O4 ternary material and LiFePO4 etc.), negative electrode active material (lithium ion battery negative pole active materials material " active graphite ") and electrolyte property simultaneously; Make the lithium ion battery of manufacturing can obtain following effect: first; The utilance of positive active material and negative electrode active material improves greatly; Thereby can effectively improve the efficiency for charge-discharge of battery, and then improve the discharge capacity of lithium ion battery; The second, the effective utilization that has improved positive active material, reduced positive active material and negative electrode active material crystal habit in use change, come off etc., high current charge-discharge effect, electrode and the discharge capacity of the cell of electrode are significantly improved; The 3rd, effectively raise the operating temperature range of lithium ion battery, battery can more efficiently be worked in-45～65 ℃ of temperature ranges, and the discharge capacity first under-45～65 ℃ of conditions reaches more than 70% of design capacity theoretical value; The 4th, prolonged life-span that recycles of battery effectively, compared with prior art, the lithium ion battery of manufacturing of the present invention recycles the life-span and prolongs and reach 132～253 charge and discharge cycles; The 5th, have good anti-over-charging electrical property, overcharge the capacity that overcharges in the experimentation and surpass security incidents generations such as the significantly not interior voltage rise height of design capacity 50% battery, burning, blast.
The present invention is applicable to the lithium rechargeable battery of making various models, also can be used for making cylindrical, the lithium-ion-power cell of all kinds, various models.
Compared with prior art, the present invention has following advantage and useful effect:
The first, a kind of lithium-ion battery electrolytes of the present invention's preparation; Because the used primary raw material of electrolyte of the present invention's preparation all is more common raw material; Abundant, cheap, the nontoxic or low toxicity of originating; Therefore low production cost is specially adapted to the application of the bigger lithium-ion-power cell production field of electrolyte consumption, and can increase more production cost; Can not cause problem of environmental pollution;
The second, a kind of lithium-ion electrolyte of the present invention's preparation; Owing to used abundant relatively multiple additive agent electrolyte, the solvent additive in relative low price, source; And the main relatively electrolyte of the consumption of additive and main solvent are less; On the basis of significantly improving the lithium ion battery comprehensive electrochemical, can't significantly increase extra production cost;
Three, a kind of lithium-ion battery electrolytes of the present invention's preparation; Owing to used multiple, the multi-functional compound additive combination that can improve positive active material, negative electrode active material and electrolyte property simultaneously; Make the utilance of positive active material and negative electrode active material improve greatly; Thereby can effectively improve the efficiency for charge-discharge of battery, and then improve the discharge capacity of battery, the same model capacity of lithium ion battery has increased more than the 100mAh than prior art;
Four, a kind of lithium-ion battery electrolytes of the present invention's preparation; Owing to used the micromolecule lithium salts additive that can improve positive active material, negative electrode active material and electrolyte property simultaneously; Improving effective utilization of positive active material; Reduced the change of positive active material and negative electrode active material crystal habit in use, electrolytic conductivity improves, when the high current charge-discharge effect of electrode is significantly improved; Make the solidifying point of electrolyte reduce, the elevation of boiling point, make lithium ion battery in wider temperature range, can work more effectively;
Five, a kind of lithium ion battery special electrolysis liquid of the present invention's preparation; Owing to used the composite electrolyte additive and the double solvents additive that can improve positive active material, negative electrode active material and electrolyte property simultaneously; Make electrolyte solution and can improving in the compatibility between lithium ion cell positive, the negative pole; Make to form solid/electrolyte interface film (SEI) between electrolyte and the both positive and negative polarity solid effectively, make the embedding/eliminating efficiency of lithium ion improve, promptly the efficiency for charge-discharge of lithium ion battery is able to obvious improvement; Improved effective utilization of positive active material simultaneously; Reduced the change of positive active material and negative electrode active material crystal habit in use, the high current charge-discharge effect of electrode and battery is obviously improved, efficiency for charge-discharge has increased more than 10% than prior art;
Six, the lithium-ion battery electrolytes of the present invention's preparation; Owing to used the compound additive combination that can improve positive active material, negative electrode active material and electrolyte property simultaneously, multiple additive agent electrolyte, electrolysis additive; Effectively raise the operating temperature range of battery, battery can be worked in-45～65 ℃ of temperature ranges effectively;
Seven, a kind of lithium-ion battery electrolytes of the present invention's preparation; Owing to used the compound additive combination that can improve positive active material, negative electrode active material and electrolyte property simultaneously; Prolonged the life-span that recycles of battery effectively; Compare with the battery that the electrolyte that prior art is produced is assembled; Because the electricity that the electrolysis fluid power of present technique improves the electrode active material utilance, improve SEI film between electrolyte and the electrode, improve electrolyte is led efficient, makes the lithium ion battery of making improve greatly than the charge-discharge performance under the high magnification, the 2C multiplying power recycles the life-span all above the control cell performance.
Eight, a kind of lithium-ion battery electrolytes of the present invention's preparation; Owing to used the compound additive combination that can improve positive active material, negative electrode active material and electrolyte property simultaneously; Prolonged the life-span that recycles of battery effectively; Compare with the battery that the electrolyte that prior art is produced is assembled, the 2C multiplying power recycles the life-span comparison has increased by 132～253 charge and discharge cycles than battery.
Description of drawings
Fig. 1 is a kind of discharge capacity curve of lithium ion battery in the time of-45 ℃ of electrolyte assembling;
Fig. 2 is a kind of discharge capacity curve of lithium ion battery in the time of-30 ℃ of electrolyte assembling;
Fig. 3 is a kind of discharge capacity curve of lithium ion battery in the time of-15 ℃ of electrolyte assembling;
Fig. 4 is a kind of discharging efficiency curve of lithium ion battery in the time of 0 ℃ of electrolyte assembling;
Fig. 5 is a kind of discharge capacity curve of lithium ion battery in the time of 15 ℃ of electrolyte assembling;
Fig. 6 is a kind of discharge capacity curve of lithium ion battery in the time of 25 ℃ of electrolyte assembling;
Fig. 7 is a kind of discharge capacity curve of lithium ion battery in the time of 35 ℃ of electrolyte assembling;
Fig. 8 is a kind of discharge capacity curve of lithium ion battery in the time of 45 ℃ of electrolyte assembling;
Fig. 9 is a kind of discharge capacity curve of lithium ion battery in the time of 55 ℃ of electrolyte assembling;
Figure 10 is a kind of discharge capacity curve of lithium ion battery in the time of 65 ℃ of electrolyte assembling;
Wherein: A～2000mAh18650 type lithium ion battery of the present invention, B～same model contrast lithium ion battery; Discharge and recharge all is under 2C multiplying power, constant current charge-discharge test condition, to accomplish.
Embodiment
Below in conjunction with embodiment and Figure of description, the present invention is done further detailed description.
Embodiment 1:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; The main solvent EC that will mix for volume ratio, DEC, VEC (vinylethylene carbonate) three's mixture, equal-volume are respectively the drier lithia (Li of prior vacuumize to the constant weight of solvent 5% with mass ratio than the mixture of three kinds of the solvent additive HMDS (HMDS) that mixes, DECP (diethyl (cyano methyl) see acid esters), TS (sulfuric acid propylene ester)
2O) mix, stirred 4 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.1% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.5: 0.1: 0.01: 0.01 main electrolyte LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixture, and be dried to constant weight etc. mole mix, total mole number accounts for the additive agent electrolyte LiPF of main electrolyte mixture total mole number 0.1%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3Three kinds of mixtures join in second electrolyte solvent that mix of step, and vacuum or inert gas shielding were stirred 4 hours down, and being made into main electrolyte molality (annotate: additive agent electrolyte concentration is not counted in, below identical) is the solution of 0.5M.
Described a kind of nickel-base alkaline electrokinetic cell special electrolysis liquid is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; Discharge and recharge under-45 ℃ of condition 2C rate charge-discharge conditions in temperature; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 1 for details.
Embodiment 2:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; Than the mixture of three kinds of the main solvent EC, DEC, the BS (sulfurous acid butene esters) that mix, the equal-volume mixture than the solvent additive HMDS (HMDS) that mixes, TS (sulfuric acid propylene ester), CDE (methane-disulfonic acid methylene ester) three, is respectively the drier lithia (Li of prior vacuumize to the constant weight of solvent 5% with equal-volume with mass ratio
2O) mix, stirred 4 hours, remove by filter lithia and lithium hydroxide deposition.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.1% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.6: 0.1: 0.02: the electrolytical LiPF of 0.02 master
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixture, and be dried to constant weight etc. mole mix, total mole number account for main electrolyte mixture total mole number 0.15%, etc. the LiCF of mixed in molar ratio
3SO
3, Li
2CO
3, and LiAc (lithium acetate) additive agent electrolyte, join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 4 hours down, the solution that to be made into main electrolyte molality be 0.65M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; Discharge and recharge under-30 ℃ of condition 2C rate charge-discharge conditions in temperature; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 2 for details.
Embodiment 3:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; With equal-volume than the DMC that mixes, 1.3-PS, BS (sulfurous acid butene esters) three's mixture main solvent, equal-volume admixture solvent additive than the DECP that mixes (diethyl (cyano methyl) see acid esters), TS (sulfuric acid propylene ester), CDE (methane-disulfonic acid methylene ester), with mass ratio be the drier lithia (Li of prior vacuumize to the constant weight of solvent 4%
2O) mix, stirred 10 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.2% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.7: 0.2: 0.03: 0.03 main electrolyte LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixture, and be dried to constant weight etc. mole mix, total mole number accounts for the LiCF of main electrolyte mixture total mole number 0.2%
3SO
3, Li
2CO
3, and the mixture additive agent electrolyte of LiAc (lithium acetate), join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 5 hours down, the solution that to be made into main electrolyte molality be 0.8M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; Discharge and recharge under-15 ℃ of condition 2C rate charge-discharge conditions in temperature; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 3 for details.
Embodiment 4:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; With equal-volume than the EC that mixes, EMC, DCC (dicyclohexyl carbon dimethylamine) mixture main solvent, equal-volume than the admixture solvent additive that mixes DECP (diethyl (cyano methyl) see acid esters), TS (sulfuric acid propylene ester), CDE (methane-disulfonic acid methylene ester), with mass ratio be the drier lithia (Li of prior vacuumize to the constant weight of solvent 4%
2O) mix, stirred 10 hours, the dry water that removes in desolvating removes by filter lithia and lithium hydroxide deposition, guarantees that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.2% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.75: 0.2: 0.03: 0.03 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.25%
3(C
2F
5)
3, Li
2CO
3And LiAc (lithium acetate) three's mixture additive agent electrolyte, joining in second solvent that mix of step, vacuum or inert gas shielding were stirred 5 hours down, the solution that to be made into main electrolyte molality be 0.9M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling are to discharge and recharge under 0 ℃ of condition 2C rate charge-discharge condition in temperature, test charge-discharge performance, high temperature performance etc.; And with the down test of contrast test battery the same terms, the result sees accompanying drawing 4 for details.
Embodiment 5:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; With equal-volume than the EMC that mixes, ES/DTO (sulfurous acid glycol ester), DCC (dicyclohexyl carbon dimethylamine) three's mixture main solvent, equal-volume admixture solvent additive than the HMDS (HMDS) that mixes, DECP (diethyl (cyano methyl) see acid esters), CDE (methane-disulfonic acid methylene ester) three, with mass ratio be the drier lithia (Li of prior vacuumize to the constant weight of solvent 3%
2O) mix, stirred 8 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.3% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.8: 0.25: 0.035: 0.035 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.3%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3Three's mixture additive agent electrolyte joins in second solvent that mix of step, and vacuum or inert gas shielding were stirred 6 hours down, the solution that to be made into main electrolyte molality be 1.0M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; In temperature is to discharge and recharge under 15 ℃ of condition 2C rate charge-discharge conditions; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 5 for details.
Embodiment 6:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; With equal-volume than the mixture main solvent of the EC that mixes, EMC, 1.3-PS, BS (sulfurous acid butene esters) four, equal-volume than any three kinds admixture solvent additive among the HMDS (HMDS) that mixes, TS (sulfuric acid propylene ester), the CDE (methane-disulfonic acid methylene ester), with mass ratio be the drier lithia (Li of prior vacuumize to the constant weight of solvent 3%
2O) mix, stirred 8 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.35% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.85: 0.25: 0.04: 0.04 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.35%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3, and the mixture additive agent electrolyte of LiAc (lithium acetate) four, join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 6 hours down, the solution that to be made into main electrolyte molality be 1.1M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; In temperature is to discharge and recharge under 25 ℃ of condition 2C rate charge-discharge conditions; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 6 for details.
Embodiment 7:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; With equal-volume than the mixture main solvent of the 1.3-PS that mixes, ES/DTO (sulfurous acid glycol ester), DCC (dicyclohexyl carbon dimethylamine), BS (sulfurous acid butene esters) four, equal-volume than any three kinds admixture solvent additive among the HMDS (HMDS) that mixes, TS (sulfuric acid propylene ester), the CDE (methane-disulfonic acid methylene ester), with mass ratio be the drier lithia (Li of prior vacuumize to the constant weight of solvent 2%
2O) mix, stirred 6 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.4% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.9: 0.26: 0.04: 0.04 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.4%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3, and the mixture additive agent electrolyte of LiAc (lithium acetate) four, join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 6 hours down, the solution that to be made into main electrolyte molality be 1.25M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; In temperature is to discharge and recharge under 35 ℃ of condition 2C rate charge-discharge conditions; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 7 for details.
Embodiment 8:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; The mixture main solvent that equal-volume is more all than the EC that mixes, DME, BS (sulfurous acid butene esters), VEC (vinylethylene carbonate) three, equal-volumes are respectively the drier lithia (Li of prior vacuumize to the constant weight of solvent 2% with mass ratio than the HMDS (HMDS) that mixes, DECP (diethyl (cyano methyl) see acid esters), TS (sulfuric acid propylene ester) three's admixture solvent additive
2O) mix, stirred 4 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.4% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 0.95: 0.28: 0.046: 0.046 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.45%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3, and the mixture additive agent electrolyte of LiAc (lithium acetate) four, join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 4 hours down, the solution that to be made into main electrolyte molality be 1.3M.
Described a kind of nickel-base alkaline electrokinetic cell special electrolysis liquid is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; In temperature is to discharge and recharge under 45 ℃ of condition 2C rate charge-discharge conditions; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 8 for details.
Embodiment 9:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; With equal-volume than the mixture main solvent of the EC that mixes, 1.3-PS, ES/DTO (sulfurous acid glycol ester), DCC (dicyclohexyl carbon dimethylamine) four, equal-volume than the HMDS (HMDS) that mixes, DECP (diethyl (cyano methyl) see acid esters), CDE (methane-disulfonic acid methylene ester) three's admixture solvent additive, be respectively the drier lithia (Li of prior vacuumize to the constant weight of solvent 1% with mass ratio
2O) mix, stirred 4 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.5% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 1: 0.3: 0.045: 0.045 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight, etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.45%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3, and the mixture additive agent electrolyte of LiAc (lithium acetate), join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 8 hours down, the solution that to be made into main electrolyte molality be 1.4M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; In temperature is to discharge and recharge under 55 ℃ of condition 2C rate charge-discharge conditions; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 9 for details.
Embodiment 10:
A kind of preparation method of lithium-ion battery electrolytes the steps include:
The first step; Under the condition of vacuum or inert gas shielding; Than the mixture main solvent of four kinds of the 1.3-PS, ES/DTO (sulfurous acid glycol ester), DCC (dicyclohexyl carbon dimethylamine), the BS (sulfurous acid butene esters) that mix, the equal-volume admixture solvent additive than three kinds of the HMDS (HMDS), TS (sulfuric acid propylene ester), the CDE (methane-disulfonic acid methylene ester) that mix, is respectively the drier lithia (Li of prior vacuumize to the constant weight of solvent 1% with equal-volume with mass ratio
2O) mix, stirred 12 hours, remove by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent.
Second step, the dry good equal-volume of the first step is mixed with dry solvent additive good, that account for main solvent volume ratio 0.5% than the main solvent that mixes, under the condition of vacuum or inert gas shielding, mix, promptly obtain electrolyte solvent.
The 3rd step, be dried under the vacuum condition constant weight, mol ratio was respectively 1: 0.3: 0.05: 0.05 LiPF
6, LiBF
4, Li
2SiF
6And LiClO
4Four mixing owner electrolyte, and be dried to constant weight etc. mole mix, total mole number accounts for the LiPF of main electrolyte mixture total mole number 0.5%
3(C
2F
5)
3, LiCF
3SO
3, Li
2CO
3, and the mixture additive agent electrolyte of four kinds of LiAc (lithium acetate), join in the solvent that second step mixed, vacuum or inert gas shielding were stirred 8 hours down, the solution that to be made into main electrolyte molality be 1.5M.
Described a kind of lithium-ion battery electrolytes is exactly to be prepared from according to the method described above.
A kind of lithium-ion battery electrolytes with preparation; 18650 type 2000mAh lithium ion batteries of assembling; In temperature is to discharge and recharge under 65 ℃ of condition 2C rate charge-discharge conditions; Test charge-discharge performance, high temperature performance etc., and test down with contrast test battery the same terms, the result sees accompanying drawing 10 for details.
Claims (2)
1. a lithium-ion battery electrolytes is made up of main electrolyte, additive agent electrolyte, main solvent and solvent additive;
Described main electrolyte is the mixture of the mol ratio lithium hexafluoro phosphate, LiBF4, lithium fluorosilicate and the lithium perchlorate that are respectively 0.5 ~ 1:0.1 ~ 0.3:0.01 ~ 0.05:0.01 ~ 0.05;
Described additive agent electrolyte be mol ratio be in three perfluor ethyls, three lithium fluophosphates, trifluoromethyl sulfonic acid lithium, lithium carbonate and the lithium acetate of main electrolyte molal quantity 0.1～0.5% three kinds or four kinds etc. the mixture that mixes of mass ratio;
Described main solvent is that equal-volume is than the ethylene carbonate, diethyl carbonate, dimethyl carbonate, glycol dimethyl ether, the methyl ethyl carbonate, 1 that mix, three kinds or four kinds mixture in 3-propane sultone, sulfurous acid glycol ester, dicyclohexyl carbon dimethylamine, sulfurous acid butene esters, the vinylethylene carbonate;
Described solvent additive is that equal-volume is than any three kinds mixture in the HMDS that mixes, account for main solvent volume ratio 0.1～0.5%, diethyl (cyano methyl) phosphonate ester, sulfuric acid propylene ester, the methane-disulfonic acid methylene ester;
Above-mentioned electrolyte master electrolyte concentration is 0.5～1.5M, and additive agent electrolyte concentration is not counted in.
2. the preparation method of the described a kind of lithium-ion battery electrolytes of claim 1 the steps include:
The first step; Under the condition of vacuum 1～10kpa or inert gas shielding; With main solvent, solvent additive is that the drier lithia that the prior vacuum 1～10kpa of solvent 1～5% is dried to constant weight mixes with mass ratio respectively; Stirred 4～12 hours, and removed by filter lithia and lithium hydroxide deposition, guarantee that water content is lower than 10ppm in the solvent;
Second step, the dry good main solvent of the first step is mixed with dry good solvent additive, under the condition of vacuum 1～10kpa or inert gas shielding, mix, promptly obtain electrolyte solvent;
The 3rd step; With being dried to the main electrolyte mixture of constant weight and the additive agent electrolyte that is dried to constant weight under vacuum 1～10kpa condition; Joining second goes on foot in the solvent that mixes; Vacuum or inert gas shielding were stirred 4～8 hours down, the solution that to be made into main electrolyte molality be 0.5～1.5M;
The described solvent of the first step is represented main solvent or solvent additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210123080.0A CN102637901B (en) | 2012-04-24 | 2012-04-24 | Electrolyte for lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210123080.0A CN102637901B (en) | 2012-04-24 | 2012-04-24 | Electrolyte for lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102637901A true CN102637901A (en) | 2012-08-15 |
| CN102637901B CN102637901B (en) | 2014-07-16 |
Family
ID=46622205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210123080.0A Active CN102637901B (en) | 2012-04-24 | 2012-04-24 | Electrolyte for lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102637901B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219508A (en) * | 2013-04-12 | 2013-07-24 | 北京理工大学 | Electrolyte modification method to improve cycle stability and low temperature performance of 5V LiNi0.5Mn1.5O4 cathode material |
| CN103794816A (en) * | 2012-10-30 | 2014-05-14 | 丰田自动车株式会社 | Non-aqueous electrolyte secondary battery |
| CN104112869A (en) * | 2013-04-19 | 2014-10-22 | 南通力合新能源有限公司 | Nonaqueous electrolyte additive capable of improving high-temperature impedance performance of manganese-contained lithium ion battery |
| CN106848234A (en) * | 2017-02-20 | 2017-06-13 | 海宁聚兴新能源科技有限公司 | A kind of cell negative electrode material |
| CN108155415A (en) * | 2017-11-29 | 2018-06-12 | 清远佳致新材料研究院有限公司 | A kind of lithium-ion battery electrolytes and lithium ion battery |
| CN108306018A (en) * | 2017-12-28 | 2018-07-20 | 骆驼集团武汉光谷研发中心有限公司 | A kind of lithium iron phosphate dynamic battery improving low temperature charging performance |
| US10355312B2 (en) | 2014-03-27 | 2019-07-16 | Daikin Industries, Ltd. | Electrolyte and electrochemical device |
| CN110994023A (en) * | 2019-11-29 | 2020-04-10 | 湖北宇电能源科技股份有限公司 | Lithium ion battery safety electrolyte, preparation method and application thereof, and lithium ion battery |
| CN111640986A (en) * | 2020-05-28 | 2020-09-08 | 珠海冠宇电池股份有限公司 | High-safety electrolyte suitable for high-energy-density lithium ion battery |
| CN112038696A (en) * | 2020-08-07 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | High-voltage electrolyte and lithium ion battery comprising same |
| CN112133958A (en) * | 2020-09-25 | 2020-12-25 | 天科新能源有限责任公司 | Method for inhibiting moisture generation in lithium ion battery |
| WO2023177162A1 (en) * | 2022-03-16 | 2023-09-21 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070105022A1 (en) * | 2005-11-10 | 2007-05-10 | Byd Company Limited | Type of non-aqueous electrolyte |
| CN101442144A (en) * | 2009-01-14 | 2009-05-27 | 北京化学试剂研究所 | Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte |
| CN101783422A (en) * | 2009-01-16 | 2010-07-21 | 比亚迪股份有限公司 | Additive and electrolyte containing the same and lithium-ion battery |
| CN102064344A (en) * | 2010-12-21 | 2011-05-18 | 东莞市杉杉电池材料有限公司 | Novel electrolyte for power battery |
-
2012
- 2012-04-24 CN CN201210123080.0A patent/CN102637901B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070105022A1 (en) * | 2005-11-10 | 2007-05-10 | Byd Company Limited | Type of non-aqueous electrolyte |
| CN101442144A (en) * | 2009-01-14 | 2009-05-27 | 北京化学试剂研究所 | Method for stabilizing color and luster, moisture and fluohydric acid content of non-aqueous electrolyte |
| CN101783422A (en) * | 2009-01-16 | 2010-07-21 | 比亚迪股份有限公司 | Additive and electrolyte containing the same and lithium-ion battery |
| CN102064344A (en) * | 2010-12-21 | 2011-05-18 | 东莞市杉杉电池材料有限公司 | Novel electrolyte for power battery |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794816A (en) * | 2012-10-30 | 2014-05-14 | 丰田自动车株式会社 | Non-aqueous electrolyte secondary battery |
| CN103219508A (en) * | 2013-04-12 | 2013-07-24 | 北京理工大学 | Electrolyte modification method to improve cycle stability and low temperature performance of 5V LiNi0.5Mn1.5O4 cathode material |
| CN104112869A (en) * | 2013-04-19 | 2014-10-22 | 南通力合新能源有限公司 | Nonaqueous electrolyte additive capable of improving high-temperature impedance performance of manganese-contained lithium ion battery |
| US10355312B2 (en) | 2014-03-27 | 2019-07-16 | Daikin Industries, Ltd. | Electrolyte and electrochemical device |
| CN106848234A (en) * | 2017-02-20 | 2017-06-13 | 海宁聚兴新能源科技有限公司 | A kind of cell negative electrode material |
| CN108155415A (en) * | 2017-11-29 | 2018-06-12 | 清远佳致新材料研究院有限公司 | A kind of lithium-ion battery electrolytes and lithium ion battery |
| CN108306018A (en) * | 2017-12-28 | 2018-07-20 | 骆驼集团武汉光谷研发中心有限公司 | A kind of lithium iron phosphate dynamic battery improving low temperature charging performance |
| CN110994023A (en) * | 2019-11-29 | 2020-04-10 | 湖北宇电能源科技股份有限公司 | Lithium ion battery safety electrolyte, preparation method and application thereof, and lithium ion battery |
| CN110994023B (en) * | 2019-11-29 | 2023-05-16 | 湖北宇电能源科技股份有限公司 | Lithium ion battery safety electrolyte, preparation method and application thereof, and lithium ion battery |
| CN111640986A (en) * | 2020-05-28 | 2020-09-08 | 珠海冠宇电池股份有限公司 | High-safety electrolyte suitable for high-energy-density lithium ion battery |
| CN111640986B (en) * | 2020-05-28 | 2021-05-25 | 珠海冠宇电池股份有限公司 | High-safety electrolyte suitable for high-energy-density lithium ion battery |
| CN112038696A (en) * | 2020-08-07 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | High-voltage electrolyte and lithium ion battery comprising same |
| CN112133958A (en) * | 2020-09-25 | 2020-12-25 | 天科新能源有限责任公司 | Method for inhibiting moisture generation in lithium ion battery |
| WO2023177162A1 (en) * | 2022-03-16 | 2023-09-21 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102637901B (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102637901B (en) | Electrolyte for lithium ion battery and preparation method thereof | |
| CN102522590B (en) | Non-aqueous organic electrolyte, lithium ion secondary battery containing non-aqueous organic electrolyte, preparation method of lithium ion secondary battery and terminal communication equipment | |
| CN105720304B (en) | A non-aqueous electrolyte and a lithium ion battery | |
| CN102224630B (en) | Non-aqueous electrolytic solution, and lithium battery comprising same | |
| CN105070940B (en) | A kind of electrolyte containing imine lithium and the battery using the electrolyte | |
| CN103618111A (en) | Ion liquid electrolytic solution and secondary lithium battery containing electrolytic solution | |
| CN102412417A (en) | Non-aqueous electrolyte for improving high-temperature electrochemical performance of lithium ion battery and application thereof | |
| CN101867064A (en) | Low temperature type lithium ion battery electrolyte with high temperature property and lithium ion battery | |
| CN104934638A (en) | High-voltage electrolyte for lithium ion battery | |
| CN109786840B (en) | High-safety organic electrolyte, secondary battery, preparation method and application | |
| CN103641751A (en) | Alkali metal salts of binary or ternary fluorine-containing sulfimide and ionic liquid and applications thereof | |
| CN108987808A (en) | A kind of high-voltage lithium ion batteries nonaqueous electrolytic solution and lithium ion battery | |
| CN104282942A (en) | High-performance electrolyte and application of high-performance electrolyte in secondary battery | |
| CN103840209A (en) | Nonaqueous organic electrolyte additive, preparation method of nonaqueous organic electrolyte additive, nonaqueous organic electrolyte and lithium ion secondary battery | |
| CN102903956A (en) | Lithium titanate battery and electrolyte for lithium titanate battery | |
| CN106299472A (en) | A kind of high security lithium ion battery electrolyte and application thereof | |
| CN102760881A (en) | Surface-coated natural graphite, preparation method thereof and lithium ion battery | |
| CN103531843A (en) | Electrolytic solution for high-temperature high-magnification type lithium ion battery | |
| US20200136183A1 (en) | Electrolyte and lithium ion battery | |
| CN101453036A (en) | Non-aqueous electrolytic solution for lithium ion secondary battery and manufacturing method thereof | |
| CN105206873A (en) | Phosphazene perfluoroalkanesulfonylimide lithium electrolyte and battery using electrolyte | |
| CN105762410B (en) | A kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution | |
| CN103682436A (en) | Electrolyte for high-ageing-resistance manganese-containing lithium ion battery and application of electrolyte | |
| CN108987802A (en) | A kind of high-voltage lithium ion batteries nonaqueous electrolytic solution | |
| CN103326064A (en) | A safe lithium ion battery electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510000 No. 38, Yunfeng Road, Xinhua Industrial Zone, Xinhua Town, Huadu District, Guangzhou, Guangdong Patentee after: Guangzhou Yuntong Lithium Battery Co.,Ltd. Address before: 510800, Yunfeng Road, Xinhua Industrial Zone, Huadu District, Guangdong, Guangzhou 38, China Patentee before: GUANGZHOU WINTONIC BATTERY & MAGNET Co.,Ltd. |
|
| CP03 | Change of name, title or address |