CN1529384A - Lithium ion cell gel liquor formula and method for preparing gel electrolytic liquor using same - Google Patents
Lithium ion cell gel liquor formula and method for preparing gel electrolytic liquor using same Download PDFInfo
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- CN1529384A CN1529384A CNA03158361XA CN03158361A CN1529384A CN 1529384 A CN1529384 A CN 1529384A CN A03158361X A CNA03158361X A CN A03158361XA CN 03158361 A CN03158361 A CN 03158361A CN 1529384 A CN1529384 A CN 1529384A
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- China
- Prior art keywords
- lithium ion
- ion battery
- gel electrolyte
- gel
- prescription
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- -1 silicane compound Chemical class 0.000 claims abstract description 29
- 150000002148 esters Chemical class 0.000 claims abstract description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 239000011245 gel electrolyte Substances 0.000 claims description 37
- 239000003792 electrolyte Substances 0.000 claims description 22
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims description 2
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- PFCDCPSYOAAJFZ-UHFFFAOYSA-N diethyl carbonate;dimethyl carbonate Chemical compound COC(=O)OC.CCOC(=O)OCC PFCDCPSYOAAJFZ-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- YHNYOPGEKPRPNL-UHFFFAOYSA-N ethene;sulfurous acid Chemical compound C=C.OS(O)=O YHNYOPGEKPRPNL-UHFFFAOYSA-N 0.000 claims description 2
- QNFHZGRFPZTWLQ-UHFFFAOYSA-N ethyl formate;methyl acetate Chemical compound CCOC=O.COC(C)=O QNFHZGRFPZTWLQ-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BZCWFJMZVXHYQA-UHFFFAOYSA-N 3-dimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C(C)=C BZCWFJMZVXHYQA-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910017704 MH-Ni Inorganic materials 0.000 description 1
- 229910017739 MH—Ni Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- QWYSJTTWCUXHQO-UHFFFAOYSA-N [F].OC(=O)C=C Chemical compound [F].OC(=O)C=C QWYSJTTWCUXHQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
Classifications
-
- Y02E60/122—
Landscapes
- Secondary Cells (AREA)
Abstract
Materials and related weights contained in the formula are as following: silicane compound possessing unsaturation double bond 0-20%, esters monomer possessing unsaturation double bond 0-20%, performed polymer of homopolymerization or copolymer of silicane compound and esters monomer 0-20%, crosslinking agent 0-20%, thermal booster 0.01-5%, nonaqueous solvent containing lithium salt 60-96%. Density of lithium salt is 0.3M-1.5M. Moreover, monomer of silicane compound and esters monomer is not equal to zero at same time. According to above formula through procedure of thermal polymerization, mixed liquor forms gel state lithium ion polymer dielectric in structure of polymer interpenetrating networks. Ionic conductivity at room temperature reaches to 7.0xl0 to the power -3 S/cm, and good safety, performances of discharging in high power and low temperature is provided.
Description
Technical field
The present invention relates to the electrolyte of lithium ion battery, refer more particularly to a kind of prescription of gel electrolyte and with this formulation gel method of electrolyte.
Background technology
The lithium ion battery that begins one's study from the fifties in last century, because it has higher volumetric specific energy, gravimetric specific energy and favorable environment protection, just progressively replace lead-acid battery, Ni-Cd and MH-Ni battery, and be widely used in the portable electric appts such as mobile phone, notebook computer, have good application prospects.Can be divided into liquid lithium ionic cell and polymer Li-ion battery according to employed electrolytical difference in the lithium ion battery.Liquid lithium ionic cell has good high charge-discharge speed and cryogenic property, but its shortcoming is: liquid electrolyte might be leaked, and can endanger the fail safe of battery; And, limited the arbitrariness of its shape because the liquid lithium ionic cell external packing is aluminum hull or box hat.
1993, the U.S. Bellcore company reported first full solid state polymer lithium ion battery, adopt polymer dielectric film to replace liquid electrolyte solution, and pack with aluminum-plastic composite membrane, make battery can make arbitrary shape, add plasticizer by adopting, the compound back extraction of pole piece and barrier film heat produces a large amount of holes, by a large amount of micro-porous adsorption electrolyte.But meeting generation burr, Working Procedure Controlling difficulty, methanol extraction can cause problems such as environmental pollution after said method existed complex process, grid to cut off.
Summary of the invention
At above-mentioned present situation, the present invention will provide a kind of prescription of gel electrolyte of lithium ion battery and with this formulation gel method of electrolyte.Described lithium-ion battery electrolytes is liquid before thermal polymerization, by forming gel after the thermal polymerization; Since no working fluid, thereby can be prepared into arbitrary shape with aluminum-plastic composite membrane, and have higher safety performance and higher ionic conducting property.
The concrete technical scheme that the utility model adopts is: described gel electrolyte of lithium ion battery prescription is characterized in: this prescription comprises following material: homopolymerization or performed polymer, crosslinking agent, the thermal initiator of copolymer and the nonaqueous solvents that includes lithium salts with the silane compound of unsaturated double-bond, the esters monomer with unsaturated double-bond, above-mentioned silane compound and esters monomer; The content of above-mentioned each composition is (representing with percentage by weight):
Silane compound: 0～20%
Esters monomer: 0～20%
Performed polymer: 0～20%
Crosslinking agent: 1～20%
Thermal initiator: 0.01～5%
The nonaqueous solvents that includes lithium salts: 60～96%, wherein the concentration of lithium salts is 0.3M～1.5M; And the silane compound in the above-mentioned composition and the content of esters monomer can not be zero simultaneously.
Silane compound of the present invention is represented by formula (1):
R-Si(R
1R
2R
3) (1)
Wherein, R is any in the following structure: CH
2=CH-, CH
2=CH-CH
2-, CH
2=CH-COOCH
2-, CH
2=CH-COOCH
2CH
2CH
2-, CH
2=C (CH
3)-COOCH
2-, CH
2=C (CH
3)-COOCH
2CH
2CH
2-; R
1, R
2, R
3Represent CH
3-, C
2H
5-, CH
3O-, C
2H
5O-,
Or
That is: R
1Can represent CH
3-, C
2H
5-, CH
3O-, C
2H
5O-,
Or
In any, R
2Can represent CH
3-, C
2H
5-, CH
3O-, C
2H
5O-,
Or
In any, R
3Can represent CH
3-, C
2H
5-, CH
3O-, C
2H
5O-,
Or
In any.As: CH
2=C (CH
3) COOCH
2Si (OCH
3)
3, CH
2=C (CH
3) COOCH
2CH
2CH
2Si (OCH
3)
3, CH
2=C (CH
3) COOCH
2CH
2CH
2Si (OCH
3)
2(CH
3) etc.And the weight ratio preferred 1～5% that silane compound is shared.
Esters monomer of the present invention is selected from least a in the following material: (Alpha-Methyl) alkyl acrylate, alkyl acrylate, (Alpha-Methyl) acrylic acid fluoroalkane ester, acrylic acid fluoroalkane ester.As: CH
2=C (CH
3) COOCH
3, CH
2=C (CH
3) COOCH
2CF
3, CH
2=CCOOCH
2CH
2CH
3Deng.And the weight ratio preferred 1～5% that esters monomer is shared.
The homopolymerization of a kind of silane compound with unsaturated double-bond of the present invention and a kind of ester class with unsaturated double-bond or the performed polymer of copolymer, be to make performed polymer with different molecular weight by the polymerisation in bulk mode, perhaps at organic solvent (as toluene, isopropyl alcohol etc.) under the situation of Cun Zaiing, make performed polymer by the polymerisation in solution mode; The number-average molecular weight of above-mentioned performed polymer is＜50,000, preferred＜20,000.And the weight ratio preferred 0～6% that performed polymer is shared.
Crosslinking agent of the present invention is a polyethylene glycol dimethacrylate, can be represented by (2) formula:
CH
2=C (R) COO (CH
2CH
2O)
n-COC (R)=CH
2(2) wherein, n=0～12, R represents H or CH
3As: CH
2=C (CH
3) COOCH
2CH
2OCOC (CH
3)=CH
2, CH
2=C (CH
3) COO (CH
2CH
2O)
4COC (CH
3)=CH
2, CH
2=CHCOO (CH
2CH
2O)
12COCH=CH
2Deng.And the weight ratio preferred 1～6% that crosslinking agent is shared.
The thermal initiator that is used for preparing the gelatin polymer polymerization reaction of the present invention is selected from least a of following material: azodiisobutyronitrile (CH
3(CH
3) (CN) C-N=N-C (CN) (CH
3) CH
3), dibenzoyl peroxide ((C
6H
5COO)
2), peroxy dicarbonate two (4-tert-butyl group cyclohexyl) ((C
6H
11OCO
2)
2), laurylperoxide acyl ((CH
3(CH
2)
10COO)
2), di-isopropyl peroxydicarbonate (((CH
3)
2CHOCOO)
2) etc.And the weight ratio preferred 0.04～2% that thermal initiator is shared.
The nonaqueous solvents that includes lithium salts of the present invention, lithium salts wherein are selected from least a in the following material: LiPF
6, LiBF
4, LiClO
4, CF
3SO
3Li, (CF
3SO
2)
2Nli, LiAsF
6Nonaqueous solvents wherein is selected from least a in the following material: vinyl carbonate; Third rare carbonic ester; The butylene carbonic ester; 1,2-dimethyl vinyl carbonate; Ethyl butyl carbonate; Carbonic acid first butyl ester; Dibutyl carbonate; Diethyl carbonate; Dimethyl carbonate; Chloro-ethylene carbonate; The trifluoromethyl ethylene carbonate; The carbonic acid di-n-propyl ester; Carbonic acid two-isopropyl ester; Methyl ethyl carbonate; Ethyl propyl carbonic acid ester; The ethylene isopropyl ester; Carbonic acid first propyl ester; Carbonic acid first isopropyl ester; Dimethoxy-ethane; Diethoxyethane; Oxolane; The 2-methyltetrahydrofuran; The diglycol ethylene dimethyl ether; The triethylene glycol dimethyl ether contracts; Tetraethyleneglycol dimethyl ether contracts; 1, the 3-dioxolane; Dimethyl sulfoxide (DMSO); Sulfolane; The 4-methyl isophthalic acid, 3-DOL; Gamma-butyrolacton; Methyl formate; Ethyl formate; Methyl acetate; Ethyl acetate; Methyl propionate; Ethyl propionate; Methyl butyrate; Ethyl butyrate; Inferior vinyl carbonate; The propane sultone; The ethene sulfite.And described lithium salts is preferred: LiPF
6And LiBF
4In a kind of or two kinds.The concentration of lithium salts is preferred: 0.8M～1.3M.It is preferred to include the shared weight ratio of the nonaqueous solvents of lithium salts: 80～95%.
As follows with the process prescription that gel electrolyte of lithium ion battery prescription of the present invention prepares gel electrolyte:
Together as the precursor of gel polymer electrolyte, this ratio is to elect according to the electrochemistry fail safe of lithium ion battery and the performance optimization of battery with silane compound recited above, esters monomer, performed polymer, crosslinking agent, liquid lithium ion electrolyte and thermal initiator mixed in accordance with regulations.Then mixed liquor is stirred and mix fully.Before thermal polymerization, mixed liquor has good flowability under the room temperature in long time, can soak into and infiltrate through in barrier film and the positive and negative pole material, is suitable for the vacuum liquid-injection equipment of cell preparation.
With after the mixed liquor sealing, carry out thermal polymerization and form gel then.Thermal polymerization process can be an one-step polymerization, and polymerization temperature is 40～100C.Also can be that the substep thermal polymerization forms gel, and adopt high temperature initiation, low temperature polymerization, wherein, initiation temperature be 70～100 ℃, and polymerization temperature is 25～50 ℃.
The gel electrolyte that the present invention is cross-linked to form by thermal polymerization, owing to be under the situation that liquid lithium ion electrolyte exists, with silane compound with unsaturated double-bond and the ester derivative with unsaturated double-bond is monomer, the polyethylene glycol dimethacrylate compound is a crosslinking agent, formation has the gel-state lithium ion polymer electrolyte of polymer interpenetration network structure, its swelling and not dissolving in organic solvent, and the polymer with silane compound of unsaturated double-bond makes resulting gel rubber system have good rigidity, polymer with ester derivative of unsaturated double-bond makes resulting gel rubber system have good adhesion and toughness, therefore this lithium ion battery gel electrolyte has very high liquid electrolyte containing ability, and very high ionic conductivity, thereby guarantee that it has good high-multiplying power discharge and cryogenic property; And, its security performance is obviously improved owing to can effectively prevent the seepage of electrolyte.The cross-linked structure of gel also makes it have enough intensity simultaneously, guarantees that gel fully contacts with positive and negative pole material, effectively reduces the internal resistance of cell, improves the cycle life of battery.
Execution mode
Utilize the performance of prescription of the present invention and the resulting gel electrolyte of preparation method below by specific embodiment explanation.
Embodiment 1
Methacryloxypropyl trimethoxy silane: 3.5wt%
Performed polymer (Mn=10,000): 3wt%
Poly-six ethylene glycol dimethacrylates: 3wt%
Peroxy dicarbonate two (4-tert-butyl group cyclohexyl): 0.1wt%
Liquid electrolyte solution, 1M LiPF6, DMC: EMC: EC=1: 1: 1 (weight ratio): 90.4%
By above-mentioned percentage by weight preparation mixed liquor, mixed liquor has good flowability, after stirring fully, carries out the segmentation thermal polymerization, and polymerization temperature is 60 ℃, and time 48h, mobile mixed electrolytic solution have formed stabilizing gel attitude electrolyte.All these operations all are to carry out in the argon atmospher of doing.
Estimate the chemical property and the physical property of the gel electrolyte that forms:
(1) gel electrolyte that takes a morsel presses makes a simple and easy battery between two stainless steel electrodes.Measure the frequency response of AC impedance.Reach 8.8 * 10 according to ionic conductivity to the gel electrolyte that the analysis showed that embodiment 1 of frequency response
-3S/cm.
(2) small amount of gel is positioned between two sheet glass presses, examine under a microscope and have or not electrolyte to flow out.As a result, find that the gel that embodiment 1 forms does not have the electrolyte outflow.
Embodiment 2
3-methacryloxypropyl dimethoxy silane: 2wt%
Acrylic acid fluorine propyl ester: 2wt%
Performed polymer (Mn=30,000): 3wt%
Ethylene glycol dimethacrylate: 3wt%
Dibenzoyl peroxide: 0.1wt%
Liquid electrolyte solution, 1MLiPF6, DMC: EC=1: 1 (weight ratio): 88.9%
By above-mentioned percentage by weight preparation mixed liquor, mixed liquor is pale yellow transparent and have good flowability, after stirring fully, carries out the segmentation thermal polymerization then, and first section polymerization temperature is 100 ℃, time 10min; Second section polymerization temperature is 35 ℃, and time 96h, mobile mixed electrolytic solution have formed stabilizing gel attitude electrolyte.All these operations all are to carry out in the argon atmospher of doing.
Estimate the chemical property and the physical property of the gel electrolyte that forms:
(1) gel electrolyte that takes a morsel presses makes a simple and easy battery between two stainless steel electrodes.Measure the frequency response of AC impedance.Reach 9.2mS/cm according to ionic conductivity to the gel electrolyte that the analysis showed that embodiment 2 of frequency response.
(2) small amount of gel is positioned between two sheet glass presses, examine under a microscope and have or not electrolyte to overflow.As a result, find that gel that embodiment 2 forms does not have electrolyte and overflows.
Embodiment 3
3-methacryloxypropyl dimethoxy silane: 1wt%
The inclined to one side trifluoro ethyl ester of methacrylic acid: 1.5wt%
Performed polymer (Mn=5,000): 5wt%
Poly-ten ethylene glycol dimethacrylates: 2wt%
Di-isopropyl peroxydicarbonate: 0.1wt%
Liquid electrolyte solution, 1MLiPF6, EMC: EC=1: 1 (weight ratio): 90.4%
By above-mentioned percentage by weight preparation mixed liquor, mixed liquor has good flowability, after stirring fully, carries out the segmentation thermal polymerization then, and first section polymerization temperature is 70 ℃, time 30min; Second section polymerization temperature is 40 ℃, time 72h, and mobile electrolyte mixed liquor has formed stabilizing gel attitude electrolyte.All these operations all are to carry out in the argon atmospher of doing.
Estimate the chemical property and the physical property of the gel electrolyte that forms:
(1) gel electrolyte that takes a morsel presses makes a simple and easy battery between two stainless steel electrodes.Measure the frequency response of AC impedance.Reach 8.2mS/cm according to ionic conductivity to the gel electrolyte that the analysis showed that embodiment 3 of frequency response.
(2) small amount of gel is positioned between two sheet glass presses, examine under a microscope and have or not electrolyte to overflow.As a result, find that gel that embodiment 3 forms does not have electrolyte and overflows.
Claims (21)
1, gel electrolyte of lithium ion battery prescription is characterized in that: this prescription comprises following material: homopolymerization or performed polymer, crosslinking agent, the thermal initiator of copolymer and the nonaqueous solvents that includes lithium salts with the silane compound of unsaturated double-bond, the esters monomer with unsaturated double-bond, above-mentioned silane compound and esters monomer; The content of above-mentioned each composition is (representing with percentage by weight):
Silane compound: 0～20%
Esters monomer: 0～20%
Performed polymer: 0～20%
Crosslinking agent: 1～20%
Thermal initiator: 0.01～5%
The nonaqueous solvents that includes lithium salts: 60～96%, wherein the concentration of lithium salts is 0.3M～1.5M;
And the silane compound in the above-mentioned composition and the content of esters monomer can not be zero simultaneously.
2, gel electrolyte of lithium ion battery prescription as claimed in claim 1, it is characterized in that: described silane compound is expressed from the next:
R-Si(R
1R
2R
3)
Wherein, R is any in the following structure, CH
2=CH-, CH
2=CH-CH
2-, CH
2=CH-COOCH
2-, CH
2=CH-COOCH
2CH
2CH
2-, CH
2=C (CH
3)-COOCH
2-, CH
2=C (CH
3)-COOCH
2CH
2CH
2-; R
1, R
2, R
3Represent CH
3-, C
2H
5-, CH
3O-, C
2H
5O-,
Or
3, gel electrolyte of lithium ion battery prescription as claimed in claim 1 or 2 is characterized in that: the content of described silane compound (representing with percentage by weight) is: 1～5%.
4, gel electrolyte of lithium ion battery prescription as claimed in claim 1 is characterized in that: described esters monomer: be selected from least a in the following material: (Alpha-Methyl) alkyl acrylate, alkyl acrylate, (Alpha-Methyl) acrylic acid fluoroalkane ester, acrylic acid fluoroalkane ester.
5, as claim 1 or 4 described gel electrolyte of lithium ion battery prescriptions, it is characterized in that: the content of described esters monomer (representing with percentage by weight) is: 1～5%.
6, gel electrolyte of lithium ion battery prescription as claimed in claim 1 is characterized in that: the content of described performed polymer (representing with percentage by weight) is: 0～6%.
7, gel electrolyte of lithium ion battery prescription as claimed in claim 1 is characterized in that: described performed polymer is to make the performed polymer with different molecular weight by the polymerisation in bulk mode.
8, gel electrolyte of lithium ion battery prescription as claimed in claim 1 is characterized in that: described performed polymer is under the situation that organic solvent exists, the performed polymer that makes by the polymerisation in solution mode.
9, as claim 1 or 7 or 8 described gel electrolyte of lithium ion battery prescriptions, it is characterized in that: the number-average molecular weight of described performed polymer is＜50000.
10, gel electrolyte of lithium ion battery prescription as claimed in claim 9, it is characterized in that: the number-average molecular weight of described performed polymer is＜20000.
11, gel electrolyte of lithium ion battery prescription as claimed in claim 1, it is characterized in that: described crosslinking agent is the polyethylene glycol dimethacrylate compound, is expressed from the next:
CH
2＝C(R)COO(CH
2CH
2O)
n-COC(R)＝CH
2
Wherein, n=0～12, R represents H or CH
3
12, as claim 1 or 11 described gel electrolyte of lithium ion battery prescriptions, it is characterized in that: the content of described crosslinking agent (representing with percentage by weight) is: 1～6%.
13, gel electrolyte of lithium ion battery prescription as claimed in claim 1 is characterized in that: described thermal initiator is selected from least a in the following material: azodiisobutyronitrile, dibenzoyl peroxide, peroxy dicarbonate two (4-tert-butyl group cyclohexyl), laurylperoxide acyl, di-isopropyl peroxydicarbonate.
14, as claim 1 or 13 described gel electrolyte of lithium ion battery prescriptions, it is characterized in that: the content of described thermal initiator (representing with percentage by weight) is: 0.04～2%.
15, gel electrolyte of lithium ion battery prescription as claimed in claim 1 is characterized in that: the described nonaqueous solvents that includes lithium salts: lithium salts wherein is selected from least a in the following material: LiPF
6, LiBF
4, LiClO
4, CF
3SO
3Li, (CF
3SO
2)
2Nli, LiAsF
6Nonaqueous solvents wherein is selected from least a in the following material: vinyl carbonate; Third rare carbonic ester; The butylene carbonic ester; 1,2-dimethyl vinyl carbonate; Ethyl butyl carbonate; Carbonic acid first butyl ester; Dibutyl carbonate; Diethyl carbonate; Dimethyl carbonate; Chloro-ethylene carbonate; The trifluoromethyl ethylene carbonate; The carbonic acid di-n-propyl ester; Carbonic acid two-isopropyl ester; Methyl ethyl carbonate; Ethyl propyl carbonic acid ester; The ethylene isopropyl ester; Carbonic acid first propyl ester; Carbonic acid first isopropyl ester; Dimethoxy-ethane; Diethoxyethane; Oxolane; The 2-methyltetrahydrofuran; The diglycol ethylene dimethyl ether; The triethylene glycol dimethyl ether contracts; Tetraethyleneglycol dimethyl ether contracts; 1, the 3-dioxolane; Dimethyl sulfoxide (DMSO); Sulfolane; The 4-methyl isophthalic acid, 3-DOL; Gamma-butyrolacton; Methyl formate; Ethyl formate; Methyl acetate; Ethyl acetate; Methyl propionate; Ethyl propionate; Methyl butyrate; Ethyl butyrate; Inferior vinyl carbonate; The propane sultone; The ethene sulfite.
16, gel electrolyte of lithium ion battery prescription as claimed in claim 15 is characterized in that: described lithium salts is selected from least a in the following material: LiPF
6, LiBF
4
17, as claim 1 or 15 or 16 described gel electrolyte of lithium ion battery prescriptions, it is characterized in that: the concentration of lithium salts is in the described nonaqueous solvents that includes lithium salts: 0.8M～1.3M.
18, as claim 1 or 15 described gel electrolyte of lithium ion battery prescriptions, it is characterized in that: the described content (representing with percentage by weight) that includes the nonaqueous solvents of lithium salts is: 80～95%.
19, prepare the gel method of electrolyte with the described gel electrolyte of lithium ion battery prescription of arbitrary claim in the above-mentioned claim 1～18, it is characterized in that: at first each composition is mixed, be mixed with mixed liquor, and stir; Then above-mentioned mixed liquor is carried out thermal polymerization, finally form gel.
20, preparation gel method of electrolyte as claimed in claim 19, it is characterized in that: described thermal polymerization is an one-step polymerization, polymerization temperature is 40～100 ℃.
21, preparation gel method of electrolyte as claimed in claim 19, it is characterized in that: described thermal polymerization is a step-by-step polymerization, and adopts high temperature initiation, low temperature polymerization, and wherein, initiation temperature is 70～100 ℃, and polymerization temperature is 25～50 ℃.
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