CN112321761A - Preparation method of adhesive for lithium ion battery - Google Patents
Preparation method of adhesive for lithium ion battery Download PDFInfo
- Publication number
- CN112321761A CN112321761A CN202011217699.9A CN202011217699A CN112321761A CN 112321761 A CN112321761 A CN 112321761A CN 202011217699 A CN202011217699 A CN 202011217699A CN 112321761 A CN112321761 A CN 112321761A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- lithium
- parts
- phase
- ion battery
- 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.)
- Pending
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 52
- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 44
- 239000000839 emulsion Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical class FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012071 phase Substances 0.000 claims description 100
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 36
- 238000004321 preservation Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000008346 aqueous phase Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- -1 acrylamide isopropyl lithium Chemical compound 0.000 claims description 15
- 239000012874 anionic emulsifier Substances 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 15
- 239000002738 chelating agent Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000006174 pH buffer Substances 0.000 claims description 14
- 239000012875 nonionic emulsifier Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 5
- AZEPWULHRMVZQR-UHFFFAOYSA-M lithium;dodecanoate Chemical compound [Li+].CCCCCCCCCCCC([O-])=O AZEPWULHRMVZQR-UHFFFAOYSA-M 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- PLXOUIVCSUBZIX-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)COC(=O)C=C PLXOUIVCSUBZIX-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical group [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-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
- WPWBEPFBNICXAF-UHFFFAOYSA-L [Li+].S(=O)(=O)(O)C(C(=O)[O-])CC(=O)[O-].[Li+] Chemical compound [Li+].S(=O)(=O)(O)C(C(=O)[O-])CC(=O)[O-].[Li+] WPWBEPFBNICXAF-UHFFFAOYSA-L 0.000 claims description 3
- SLGKFAQSCDYULE-UHFFFAOYSA-N lithium;4-methylbenzenesulfonic acid Chemical compound [Li].CC1=CC=C(S(O)(=O)=O)C=C1 SLGKFAQSCDYULE-UHFFFAOYSA-N 0.000 claims description 3
- YFVGRULMIQXYNE-UHFFFAOYSA-M lithium;dodecyl sulfate Chemical compound [Li+].CCCCCCCCCCCCOS([O-])(=O)=O YFVGRULMIQXYNE-UHFFFAOYSA-M 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000003995 emulsifying agent Substances 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007792 addition Methods 0.000 description 38
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000867 polyelectrolyte Polymers 0.000 description 6
- 238000007872 degassing Methods 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 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 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 4
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- BQTOJCOSKKLTAB-UHFFFAOYSA-L [Na+].O1P(OC1CO)(=O)OP(=O)([O-])[O-].[Na+] Chemical compound [Na+].O1P(OC1CO)(=O)OP(=O)([O-])[O-].[Na+] BQTOJCOSKKLTAB-UHFFFAOYSA-L 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- HIEFKCXDWLRVHA-UHFFFAOYSA-L O(P1(OC(C)OP(O1)(=O)[O-])=O)O.[Na+].[Na+].OOP1(OC(C)OP(O1)(=O)[O-])=O Chemical compound O(P1(OC(C)OP(O1)(=O)[O-])=O)O.[Na+].[Na+].OOP1(OC(C)OP(O1)(=O)[O-])=O HIEFKCXDWLRVHA-UHFFFAOYSA-L 0.000 description 1
- JQMIZWRAHVPDTG-UHFFFAOYSA-N OC(CCC(O)=O)=O.O[S-](=O)=O.[Li+] Chemical compound OC(CCC(O)=O)=O.O[S-](=O)=O.[Li+] JQMIZWRAHVPDTG-UHFFFAOYSA-N 0.000 description 1
- YMWAKBHYGURHGI-UHFFFAOYSA-N S(=O)(=O)(O)O.C(CCCCCCCCCCC)[Li] Chemical group S(=O)(=O)(O)O.C(CCCCCCCCCCC)[Li] YMWAKBHYGURHGI-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- KQCITBQWXRFAOB-UHFFFAOYSA-N lithium;toluene Chemical group [Li].CC1=CC=CC=C1 KQCITBQWXRFAOB-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007964 self emulsifier Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of an adhesive for a lithium ion battery, belonging to the technical field of emulsion polymerization in high polymer materials. It comprises the following steps: 1) preparing water-phase pre-emulsion; 2) preparing an initiator dropwise adding phase; 3) preparation of oil phase dropwise addition phase: adding 30-50 parts of styrene, 1-3 parts of unsaturated fluoroacrylate and 0.3-0.7 part of molecular weight regulator into a batching tank, and stirring for 1-2 hours to prepare an oil phase dropwise adding phase; 4) preparing an initial product; 5) terminating the reaction; 6) and preparing the adhesive for the lithium ion battery. The invention adopts the reactive emulsifier, introduces the raw materials of fluorine-containing monomer, halogen-containing electrolyte and the like into the molecule, and prepares the lithium ion battery adhesive with high strength, high bonding strength, high temperature resistance, flame retardance and excellent electrolytic property; the problems that the electrode material of the lithium ion battery is easy to fall off and the solvent is easy to volatilize and expand are solved.
Description
Technical Field
The invention belongs to the technical field of emulsion polymerization in high polymer materials, and relates to a preparation method of an adhesive for a lithium ion battery.
Background
With the progress of the times and the development of technologies, various intelligent devices, electronic products, mobile and communication devices have been developed rapidly, and the daily life of people is affected by the gradual increase of various aspects, and the intelligent devices, the electronic products, the mobile and communication devices become an indispensable part of the life of people gradually. In recent years, the development concepts of green energy conservation, safety, environmental protection and sustainability are gradually deepened, and people show great enthusiasm for green and environment-friendly new energy electronic products. With the popularization and application of electronic products such as smart phones, notebook computers, intelligent robots, electric vehicles and the like, the development of energy supply and storage technologies of lithium ion batteries is directly promoted.
The lithium ion battery is used as a secondary battery, has the characteristic of recycling, has no phenomenon of pollutant discharge in the using process, has the characteristics of green energy conservation, safety, environmental protection and sustainable use, and is widely used as an energy supply and storage module of electronic products.
With the continuous improvement of the living standard and the living quality of people, electronic products and lithium ion batteries play more and more important roles in the life of people, and the safety, the energy density, the power density, the cycle service life and the production cost of the lithium ion batteries are also more and more emphasized by people.
At present, the performance of a lithium ion battery is mainly limited by factors such as electrode materials, battery adhesives, electrolytes, solvents, preparation processes and the like, so that after the lithium ion battery is recycled for a certain time, the electrode materials gradually fall off from the adhesives and base materials, electrode material particles in the electrolytes and the solvents are increased, collision among particles in the lithium ion battery is aggravated, the heat dissipation efficiency of the battery is reduced, solvent molecules are gasified and volatilized, and the lithium ion battery is expanded and swelled. In addition, the falling of the electrode material can cause the real capacity of the lithium ion battery to be reduced, the energy density to be reduced, and the internal short circuit of the battery can be caused, so that the lithium ion battery has the potential safety hazard of combustion and explosion, and the safe use of electronic products is influenced.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a binder for a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an adhesive for a lithium ion battery comprises the following steps of counting the components in parts by weight,
1) preparation of aqueous phase pre-emulsion: adding 40-50 parts of deionized water, 1-3 parts of reactive anionic emulsifier, 1-3 parts of reactive nonionic emulsifier, 1-5 parts of unsaturated carboxylic acid monomer, 0.2-0.5 part of electrolyte, 0.1-0.3 part of neutralizer, 0.02-0.05 part of pH buffer and 0.01-0.05 part of chelating agent into a batching tank, and stirring for 1-2 hours to prepare an aqueous phase pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 30-40 parts of deionized water and 0.5-1.1 parts of an initiator into a batching tank, and stirring for 0.5-1 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: adding 30-50 parts of styrene, 1-3 parts of unsaturated fluoroacrylate and 0.3-0.7 part of molecular weight regulator into a batching tank, and stirring for 1-2 hours to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: adding 20-30 parts of deionized water and 5-10 parts of butadiene into a polymerization reaction kettle, taking 20-30% of the aqueous phase pre-emulsion prepared in the step 1, taking 10-20% of the initiator dropwise addition phase prepared in the step 2 and taking 10-20% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 70-90 ℃, and carrying out heat preservation reaction for 0.5-1.5 hours;
after the heat preservation is finished, beginning to dropwise add 90-95 parts of butadiene, the rest of the water phase pre-emulsion prepared in the step 1, the rest of the initiator dropwise-added phase prepared in the step 2 and the rest of the oil phase dropwise-added phase prepared in the step 3, heating to 80-95 ℃, wherein the dropwise-adding reaction time is 4-6 hours, after the dropwise addition is finished, heating to 90-95 ℃, carrying out heat preservation reaction for 3-5 hours, sampling and detecting the conversion rate every 1-2 hours in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 60-70 ℃, adding 0.5-1.5 parts of stabilizer, 0.05-0.08 part of terminator and 0.1-0.2 part of neutralizer into the reaction system, stirring for reaction for 1-2 hours, and then vacuumizing for 1-2 hours;
6) preparing the adhesive for the lithium ion battery: and cooling to 30-40 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
In the preparation method of the adhesive for the lithium ion battery, the reactive anionic emulsifier is one or more of lithium acrylamido isopropyl sulfonate, lithium allyloxypropyl alkyl alcohol ether sulfosuccinate, lithium hydroxypropyl methacrylate sulfonate and lithium 2-acrylamide-2-methylpropanesulfonate.
In the above method for preparing an adhesive for a lithium ion battery, the reactive nonionic emulsifier is one or more of allyloxynonylphenol polyoxyethylene (10) ether, allyloxydecylpolyoxyethylene (10) ether and allyloxynonylphenoxypropanol polyoxyethylene (15) ether.
In the above preparation method of the adhesive for the lithium ion battery, the unsaturated fluoroacrylate is one or more of perfluorohexylethyl acrylate, perfluoroalkylethyl acrylate and 2,2,3,3,4,4, 4-heptafluorobutyl acrylate.
In the above preparation method of the binder for the lithium ion battery, the electrolyte is one or more of lithium chloride, lithium bromide and lithium iodide.
In the above method for preparing a binder for a lithium ion battery, the pH buffer is lithium bicarbonate and/or lithium carbonate.
In the above preparation method of the binder for the lithium ion battery, the unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid and maleic acid.
In the above method for preparing a binder for a lithium ion battery, the neutralizing agent is lithium hydroxide and/or lithium silicate.
In the above preparation method of the binder for the lithium ion battery, the stabilizer is one or more of lithium dodecyl sulfate, lithium laurate and lithium 4-methylbenzenesulfonate.
In the above preparation method of the adhesive for the lithium ion battery, in the step 4), the polymerization reaction kettle is firstly vacuumized.
In the preparation method of the adhesive for the lithium ion battery, in the step 4), the dropwise addition of the butadiene, the water phase pre-emulsion, the initiator dropwise addition phase and the oil phase dropwise addition phase for the second time are completed when the two dropwise addition phases are the same.
In the preparation method of the adhesive for the lithium ion battery, the chelating agent is one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and disodium hydroxyethylidene diphosphate.
In the preparation method of the adhesive for the lithium ion battery, the initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile and tert-butyl peroxybenzoate.
In the above preparation method of the adhesive for lithium ion batteries, the molecular weight regulator is one or more of tert-dodecyl mercaptan, 2, 4-diphenyl-4-methyl-1-pentene and mercaptoethanol.
In the above preparation method of the adhesive for the lithium ion battery, the terminator is one or more of sodium dimethyldithiocarbamate, hydroquinone and diethylhydroxylamine.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts the reactive emulsifier, introduces the raw materials of fluorine-containing monomer, halogen-containing electrolyte and the like into the molecule, and prepares the lithium ion battery adhesive with high strength, high bonding strength, high temperature resistance, flame retardance and excellent electrolytic property; the problems that the electrode material of the lithium ion battery is easy to fall off and the solvent is easy to volatilize and expand are solved.
(2) The present invention prepares polyelectrolyte type styrene-butadiene latex with excellent performance by using butadiene and styrene as main reaction monomers. When the styrene-butadiene latex is used as the lithium ion battery adhesive, the molecular structure of the latex has a good polyelectrolyte structure, the charge exchange inside the lithium ion battery can be promoted, the transmission rate of charges in an electrode material, the electrode activity and the conductivity are improved, and a large number of lithium ion structures exist in the latex, so that the lithium ion battery has higher charge density and energy density. In addition, the adhesive with the dosage can gradually reduce the use of micromolecular electrolyte and solvent in the lithium ion battery, and has the function of improving the safety performance of the lithium ion battery.
(3) The invention takes deionized water as a reaction system dispersion medium, butadiene and styrene as main reaction monomers, unsaturated carboxylic acid and unsaturated fluoroacrylate as functional monomers, and a reactive anionic emulsifier and a reactive nonionic emulsifier as self-emulsifiers of a polymerization system, and prepares the lithium ion battery adhesive with excellent performance under the combined action of an electrolyte, a chelating agent, a pH buffering agent, a neutralizer, a stabilizer and other auxiliaries. The latex has good fluidity, mechanical stability, chemical stability and adhesive property. The particle size is 200nm-250nm, the film forming material has good transparency and proper glass transition temperature, and when the film forming material is used as a lithium ion battery adhesive, a transition layer with good bonding strength and bonding force can be formed between the film forming material and an adhered object. Under the action of polar groups, unsaturated double bonds, fluorine substituent structures and reactive emulsifier monomers of the adhesive, a film forming material of the adhesive has proper swelling rate and swelling strength in a polar solvent and a non-polar solvent, and can form good infiltration, coating and bonding on an electrode material and a substrate, so that the ionization activity of the lithium ion battery is improved, and the activation time of the lithium ion battery is shortened.
(4) The large amount of metal ions introduced into the polymer molecules of the adhesive improves the capacity, charge density, energy density and conductivity of the electrode material of the lithium ion battery. In addition, the adhesive has the polyelectrolyte characteristic in the structure, so that the adhesive has the effect of polyelectrolyte, small molecular electrolyte in the lithium ion battery can be replaced or partially replaced, the use of organic solvent is reduced, the safety and convenience of the lithium ion battery are improved, and the lithium ion battery has better comprehensive performance.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
A preparation method of an adhesive for a lithium ion battery comprises the following steps of counting the components in parts by weight,
1) preparation of aqueous phase pre-emulsion: adding 40 parts of deionized water, 1 part of reactive anionic emulsifier, 1 part of reactive nonionic emulsifier, 1 part of unsaturated carboxylic acid monomer, 0.2 part of electrolyte, 0.1 part of neutralizer, 0.02 part of pH buffer and 0.01 part of chelating agent into a batching tank, and stirring for 1 hour to prepare aqueous pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 30 parts of deionized water and 0.5 part of initiator into a mixing tank, and stirring for 0.5 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: adding 30 parts of styrene, 1 part of unsaturated fluoroacrylate and 0.3 part of molecular weight regulator into a batching tank, and stirring for 1 hour to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: vacuumizing a polymerization reaction kettle, adding 20 parts of deionized water and 5 parts of butadiene into the polymerization reaction kettle, taking 20% of the aqueous phase pre-emulsion prepared in the step 1, taking 10% of the initiator dropwise addition phase prepared in the step 2 and taking 10% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 70 ℃, and carrying out heat preservation reaction for 0.5 hour;
after the heat preservation is finished, starting to dropwise add 90 parts of butadiene, the rest of the water phase pre-emulsion prepared in the step 1, the rest of the initiator dropwise-adding phase prepared in the step 2 and the rest of the oil phase dropwise-adding phase prepared in the step 3, when the two phases are the same, completing the dropwise addition, heating to 80 ℃, wherein the dropwise addition reaction time is 4 hours, after the dropwise addition is completed, heating to 90 ℃, carrying out the heat preservation reaction for 3 hours, sampling and detecting the conversion rate every 1 hour in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 60 ℃, adding 0.5 part of stabilizer, 0.05 part of terminator and 0.1 part of neutralizer into the reaction system, stirring for reaction for 1 hour, and then vacuumizing and degassing for 1 hour;
6) preparing the adhesive for the lithium ion battery: and cooling to 30 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
The reactive anionic emulsifier is lithium acrylamido isopropyl sulfonate. The reactive nonionic emulsifier is allyloxynonylphenol polyoxyethylene (10) ether. The unsaturated fluoroacrylate is perfluorohexylethyl acrylate. The electrolyte is lithium chloride. The pH buffer is lithium bicarbonate. The neutralizer is lithium hydroxide. The stabilizer is dodecyl lithium sulfate. The unsaturated carboxylic acid monomer is acrylic acid. The chelating agent is ethylenediaminetetraacetic acid tetrasodium salt. The initiator is potassium persulfate. The molecular weight regulator is 2, 4-diphenyl-4-methyl-1-pentene. The terminating agent is sodium dimethyldithiocarbamate.
Example 2
A preparation method of an adhesive for a lithium ion battery comprises the following steps of counting the components in parts by weight,
1) preparation of aqueous phase pre-emulsion: adding 50 parts of deionized water, 3 parts of reactive anionic emulsifier, 3 parts of reactive nonionic emulsifier, 5 parts of unsaturated carboxylic acid monomer, 0.5 part of electrolyte, 0.3 part of neutralizer, 0.05 part of pH buffer and 0.05 part of chelating agent into a proportioning tank, and stirring for 2 hours to prepare aqueous pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 40 parts of deionized water and 1.1 parts of initiator into a batching tank, and stirring for 1 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: 50 parts of styrene, 3 parts of unsaturated fluoroacrylate and 0.7 part of molecular weight regulator are added into a batching tank, and stirred for 2 hours to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: vacuumizing a polymerization reaction kettle, adding 30 parts of deionized water and 10 parts of butadiene into the polymerization reaction kettle, taking 30% of the aqueous phase pre-emulsion prepared in the step 1, taking 20% of the initiator dropwise addition phase prepared in the step 2 and taking 20% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 90 ℃, and carrying out heat preservation reaction for 1.5 hours;
after the heat preservation is finished, starting to dropwise add 95 parts of butadiene, the rest of the water phase pre-emulsion prepared in the step 1, the rest of the initiator dropwise-adding phase prepared in the step 2 and the rest of the oil phase dropwise-adding phase prepared in the step 3, heating to 95 ℃, completing the dropwise addition at the same time, wherein the dropwise addition reaction time is 6 hours, heating to 95 ℃ after the dropwise addition is completed, carrying out heat preservation reaction for 5 hours, sampling and detecting the conversion rate every 2 hours in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 70 ℃, adding 1.5 parts of stabilizer, 0.08 parts of terminator and 0.2 parts of neutralizer into the reaction system, stirring for reaction for 2 hours, and then vacuumizing and degassing for 2 hours;
6) preparing the adhesive for the lithium ion battery: and cooling to 40 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
The reactive anionic emulsifier is allyloxypropyl alkyl alcohol ether lithium sulfosuccinate and methacrylic acid lithium hydroxypropyl sulfonate. The reactive nonionic emulsifiers were allyloxydecylpolyoxyethylene (10) ether and allyloxydonylphenoxypropanol polyoxyethylene (15) ether. The unsaturated fluoroacrylate is perfluoroalkylethyl acrylate and 2,2,3,3,4,4, 4-heptafluorobutyl acrylate. The electrolyte is lithium bromide and lithium iodide. The pH buffer is lithium carbonate. The neutralizing agent is lithium silicate. The stabilizer is lithium laurate and lithium 4-methyl benzene sulfonate. The unsaturated carboxylic acid monomer is methacrylic acid. The chelating agent is disodium edetate. The initiator is ammonium persulfate. The molecular weight regulator is tert-dodecyl mercaptan. The terminating agent is hydroquinone and diethylhydroxylamine.
Example 3
A preparation method of an adhesive for a lithium ion battery comprises the following steps of counting the components in parts by weight,
1) preparation of aqueous phase pre-emulsion: adding 45 parts of deionized water, 2 parts of reactive anionic emulsifier, 2 parts of reactive nonionic emulsifier, 3 parts of unsaturated carboxylic acid monomer, 0.3 part of electrolyte, 0.2 part of neutralizer, 0.03 part of pH buffer and 0.03 part of chelating agent into a batching tank, and stirring for 1.5 hours to prepare aqueous phase pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 35 parts of deionized water and 0.8 part of initiator into a batching tank, and stirring for 0.8 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: adding 40 parts of styrene, 2 parts of unsaturated fluoroacrylate and 0.5 part of molecular weight regulator into a mixing tank, and stirring for 1.5 hours to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: vacuumizing a polymerization reaction kettle, adding 25 parts of deionized water and 8 parts of butadiene into the polymerization reaction kettle, taking 25% of the aqueous phase pre-emulsion prepared in the step 1, taking 15% of the initiator dropwise addition phase prepared in the step 2 and taking 15% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 80 ℃, and carrying out heat preservation reaction for 1 hour;
after the heat preservation is finished, starting to dropwise add 93 parts of butadiene, the residual water phase pre-emulsion prepared in the step 1, the residual initiator dropwise-adding phase prepared in the step 2 and the residual oil phase dropwise-adding phase prepared in the step 3, heating to 88 ℃, wherein the dropwise-adding reaction time is 5 hours, after the dropwise addition is finished, heating to 93 ℃, carrying out heat preservation reaction for 4 hours, sampling and detecting the conversion rate every 1.5 hours in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 65 ℃, adding 1 part of stabilizer, 0.06 part of terminator and 0.15 part of neutralizer into the reaction system, stirring for reaction for 1.5 hours, and then vacuumizing and degassing for 1.5 hours;
6) preparing the adhesive for the lithium ion battery: and cooling to 35 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
The reactive anionic emulsifier is 2-acrylamide-2-methyl propane lithium sulfonate. The reactive nonionic emulsifier is allyloxydecylpolyoxyethylene (10) ether. The unsaturated fluoroacrylate is perfluoroalkylethyl acrylate. The electrolyte is lithium bromide. The pH buffer is lithium bicarbonate and lithium carbonate. The neutralizer is lithium hydroxide and lithium silicate. The stabilizer is lithium laurate. The unsaturated carboxylic acid monomer is maleic acid. The chelating agent is disodium hydroxyethylidene diphosphate. The initiator is sodium persulfate. The molecular weight regulator is mercaptoethanol. The terminating agent is diethylhydroxylamine.
Example 4
A preparation method of an adhesive for a lithium ion battery comprises the following steps of counting the components in parts by weight,
1) preparation of aqueous phase pre-emulsion: adding 41 parts of deionized water, 1.5 parts of reactive anionic emulsifier, 1.5 parts of reactive nonionic emulsifier, 2 parts of unsaturated carboxylic acid monomer, 0.25 part of electrolyte, 0.15 part of neutralizer, 0.025 part of pH buffer and 0.02 part of chelating agent into a batching tank, and stirring for 1.2 hours to prepare aqueous phase pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 32 parts of deionized water and 0.6 part of initiator into a batching tank, and stirring for 0.6 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: adding 32 parts of styrene, 1.5 parts of unsaturated fluoroacrylate and 0.4 part of molecular weight regulator into a batching tank, and stirring for 1.2 hours to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: vacuumizing a polymerization reaction kettle, adding 22 parts of deionized water and 6 parts of butadiene into the polymerization reaction kettle, taking 21% of the aqueous phase pre-emulsion prepared in the step 1, taking 12% of the initiator dropwise addition phase prepared in the step 2 and taking 12% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 75 ℃, and carrying out heat preservation reaction for 0.6 hour;
after the heat preservation is finished, starting to dropwise add 92 parts of butadiene, the rest of the water phase pre-emulsion prepared in the step 1, the rest of the initiator dropwise-adding phase prepared in the step 2 and the rest of the oil phase dropwise-adding phase prepared in the step 3, raising the temperature to 82 ℃, simultaneously completing the dropwise addition, wherein the dropwise addition reaction time is 4.5 hours, after the dropwise addition is completed, raising the temperature to 91 ℃, carrying out the heat preservation reaction for 3.5 hours, sampling and detecting the conversion rate every 1.2 hours in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 62 ℃, adding 0.6 part of stabilizer, 0.06 part of terminator and 0.15 part of neutralizer into the reaction system, stirring for reaction for 1.2 hours, and then vacuumizing and degassing for 1.2 hours;
6) preparing the adhesive for the lithium ion battery: and cooling to 32 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
The reactive anionic emulsifier is acrylamide isopropyl lithium sulfonate, allyloxypropyl alkyl alcohol ether sulfo lithium succinate, methacrylic acid hydroxypropyl lithium sulfonate and 2-acrylamide-2-methyl lithium sulfonate. Reactive nonionic emulsifiers are allyloxynonylphenol polyoxyethylene (10) ether, allyloxydecylpolyoxyethylene (10) ether and allyloxynonylphenoxypropanol polyoxyethylene (15) ether. The unsaturated fluoroacrylate is 2,2,3,3,4,4, 4-heptafluorobutylacrylate. The electrolyte is lithium iodide. The pH buffer is lithium carbonate. The neutralizing agent is lithium silicate. The stabilizer is 4-methyl benzene lithium sulfonate. The unsaturated carboxylic acid monomer is methacrylic acid and maleic acid. The chelating agent is tetrasodium ethylenediamine tetraacetate and disodium hydroxyethylidene diphosphate. The initiator is azodiisobutyronitrile and tert-butyl peroxybenzoate. The molecular weight regulator is tert-dodecyl mercaptan. The terminating agent is sodium dimethyldithiocarbamate.
And 4) finishing the dropwise adding when the dropwise adding of the butadiene, the water phase pre-emulsion, the initiator dropwise adding phase and the oil phase is the same.
Example 5
A preparation method of an adhesive for a lithium ion battery comprises the following steps of counting the components in parts by weight,
1) preparation of aqueous phase pre-emulsion: adding 48 parts of deionized water, 2.5 parts of reactive anionic emulsifier, 2.5 parts of reactive nonionic emulsifier, 4 parts of unsaturated carboxylic acid monomer, 0.4 part of electrolyte, 0.25 part of neutralizer, 0.04 part of pH buffer and 0.04 part of chelating agent into a proportioning tank, and stirring for 1.8 hours to prepare an aqueous phase pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 38 parts of deionized water and 1 part of initiator into a batching tank, and stirring for 0.8 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: adding 48 parts of styrene, 2.5 parts of unsaturated fluoroacrylate and 0.6 part of molecular weight regulator into a mixing tank, and stirring for 1.8 hours to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: vacuumizing a polymerization reaction kettle, adding 29 parts of deionized water and 9 parts of butadiene into the polymerization reaction kettle, taking 28% of the aqueous phase pre-emulsion prepared in the step 1, taking 19% of the initiator dropwise addition phase prepared in the step 2 and 19% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 85 ℃, and carrying out heat preservation reaction for 1.4 hours;
after the heat preservation is finished, beginning to dropwise add 94 parts of butadiene, the rest of the water phase pre-emulsion prepared in the step 1, the rest of the initiator dropwise-added phase prepared in the step 2 and the rest of the oil phase dropwise-added phase prepared in the step 3, raising the temperature to 90 ℃, wherein the dropwise-adding reaction time is 5 hours, after the dropwise addition is finished, raising the temperature to 94 ℃, carrying out heat preservation reaction for 4.5 hours, sampling and detecting the conversion rate every 1.8 hours in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 68 ℃, adding 1.2 parts of stabilizer, 0.07 part of terminator and 0.18 part of neutralizer into the reaction system, stirring for reaction for 1.8 hours, and then vacuumizing and degassing for 1.8 hours;
6) preparing the adhesive for the lithium ion battery: and cooling to 39 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
The reactive anionic emulsifier is one or more of acrylamide isopropyl lithium sulfonate, allyloxypropyl alkyl alcohol ether lithium sulfosuccinate, methacrylic acid hydroxypropyl lithium sulfonate and 2-acrylamide-2-methyl lithium sulfonate. The reactive nonionic emulsifier is allyloxydecylpolyoxyethylene (10) ether. The unsaturated fluoroacrylate is perfluoroalkylethyl acrylate. The electrolyte is lithium iodide. The pH buffer is lithium carbonate. The neutralizing agent is lithium silicate. The stabilizer is lithium laurate. The unsaturated carboxylic acid monomers are acrylic acid, methacrylic acid and maleic acid. The chelating agent is disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and disodium hydroxy ethylidene diphosphate. The initiator is ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and tert-butyl peroxybenzoate. The molecular weight regulator is 2, 4-diphenyl-4-methyl-1-pentene and mercaptoethanol. The terminating agent is hydroquinone and diethylhydroxylamine.
Comparative example
The comparative example is substantially the same as example 5 except that ethylene carbonate is used as the electrolyte in step 1). In step 3) no unsaturated fluoroacrylate is added.
The results of physical property tests of the binders for lithium ion batteries prepared by the methods of examples 1 to 5 and the binder for lithium ion batteries of comparative example are shown in the following table.
TABLE 1
As can be seen from the above table, the adhesive for the lithium ion battery prepared by the mixture ratio and the method of the invention has good particle size distribution, excellent fluidity, excellent bonding strength, good mechanical stability and good chemical stability. Meanwhile, the composite material has good mechanical strength and ionization performance, can be used as an adhesive and polyelectrolyte of the lithium ion battery, so that the process for manufacturing the lithium ion battery is simpler and safer, and the manufactured lithium ion battery has longer service life.
Application example
Lithium batteries were produced using the binders for lithium ion batteries obtained in examples 1 to 5 and the binders for lithium ion batteries obtained in the comparative documents. The lithium cells were subjected to charge and discharge tests, in comparison with the lithium ion cells produced with the binder of the comparative examples.
TABLE 2
As can be seen from the above table, the lithium ion batteries produced by the binders in examples 1 to 5 have less tendency to fall off the electrode material, slow volatilization of the solvent, and less tendency to swell compared to the lithium ion batteries produced by the binders in the comparative examples. The adhesive has excellent wetting, coating and bonding strength to electrode materials and base materials, has good polyelectrolyte property, high temperature resistance and flame retardant property, has obvious effects on improving the safety of the lithium ion battery, prolonging the service life and the like, and can be widely applied to the production and the manufacture of the lithium ion battery.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of the adhesive for the lithium ion battery is characterized by comprising the following steps: the components are calculated according to parts by weight and comprise the following steps,
1) preparation of aqueous phase pre-emulsion: adding 40-50 parts of deionized water, 1-3 parts of reactive anionic emulsifier, 1-3 parts of reactive nonionic emulsifier, 1-5 parts of unsaturated carboxylic acid monomer, 0.2-0.5 part of electrolyte, 0.1-0.3 part of neutralizer, 0.02-0.05 part of pH buffer and 0.01-0.05 part of chelating agent into a batching tank, and stirring for 1-2 hours to prepare an aqueous phase pre-emulsion for later use;
2) preparation of an initiator dropwise addition phase: adding 30-40 parts of deionized water and 0.5-1.1 parts of an initiator into a batching tank, and stirring for 0.5-1 hour to prepare an initiator dropwise adding phase for later use;
3) preparation of oil phase dropwise addition phase: adding 30-50 parts of styrene, 1-3 parts of unsaturated fluoroacrylate and 0.3-0.7 part of molecular weight regulator into a batching tank, and stirring for 1-2 hours to prepare an oil phase dropwise adding phase for later use;
4) preparation of an initial product: adding 20-30 parts of deionized water and 5-10 parts of butadiene into a polymerization reaction kettle, taking 20-30% of the aqueous phase pre-emulsion prepared in the step 1, taking 10-20% of the initiator dropwise addition phase prepared in the step 2 and taking 10-20% of the oil phase dropwise addition phase prepared in the step 3, adding the mixture into the polymerization reaction kettle, heating to 70-90 ℃, and carrying out heat preservation reaction for 0.5-1.5 hours;
after the heat preservation is finished, starting to dropwise add 90-95 parts of butadiene, the rest of the water phase pre-emulsion prepared in the step 1, the rest of the initiator dropwise-added phase prepared in the step 2 and the rest of the oil phase dropwise-added phase prepared in the step 3, heating to 80-95 ℃, wherein the dropwise-adding reaction time is 4-6 hours, simultaneously heating to 90-95 ℃ after the dropwise-adding is finished, carrying out heat preservation reaction for 3-5 hours, sampling and detecting the conversion rate every 1-2 hours in the heat preservation process, and stopping the heat preservation reaction when the conversion rate reaches more than 95%;
5) termination of the reaction: cooling to 60-70 ℃, adding 0.5-1.5 parts of stabilizer, 0.05-0.08 part of terminator and 0.1-0.2 part of neutralizer into the reaction system, stirring for reaction for 1-2 hours, and then vacuumizing for 1-2 hours;
6) preparing the adhesive for the lithium ion battery: and cooling to 30-40 ℃, discharging, and filtering to obtain the adhesive for the lithium ion battery.
2. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the reactive anionic emulsifier is one or more of acrylamide isopropyl lithium sulfonate, allyloxypropyl alkyl alcohol ether lithium sulfosuccinate, methacrylic acid hydroxypropyl lithium sulfonate and 2-acrylamide-2-methyl lithium sulfonate.
3. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the reactive nonionic emulsifier is one or more of allyloxynonylphenol polyoxyethylene (10) ether, allyloxydecylpolyoxyethylene (10) ether and allyloxynonylphenoxypropanol polyoxyethylene (15) ether.
4. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the unsaturated fluoroacrylate is one or more of perfluorohexylethyl acrylate, perfluoroalkyl ethyl acrylate and 2,2,3,3,4,4, 4-heptafluorobutyl acrylate.
5. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the electrolyte is one or more of lithium chloride, lithium bromide and lithium iodide.
6. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the pH buffer is lithium bicarbonate and/or lithium carbonate.
7. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid and maleic acid.
8. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the neutralizing agent is lithium hydroxide and/or lithium silicate.
9. The method for preparing the binder for lithium ion batteries according to claim 1, wherein: the stabilizer is one or more of lithium dodecyl sulfate, lithium laurate and lithium 4-methylbenzenesulfonate.
10. The method for preparing the binder for lithium ion batteries according to any one of claims 1 to 9, wherein: in the step 4), the polymerization reaction kettle is firstly vacuumized.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346328A (en) * | 2013-07-16 | 2013-10-09 | 中国科学院青岛生物能源与过程研究所 | High-potential-resistant window lithium-ion secondary battery binder and preparation method thereof |
| CN105576284A (en) * | 2016-02-18 | 2016-05-11 | 福建蓝海黑石科技有限公司 | Anode aqueous binder of lithium ion battery and preparation method thereof |
| CN107384261A (en) * | 2017-07-21 | 2017-11-24 | 中国乐凯集团有限公司 | A kind of lithium ion battery separator refractory layer aqueous binder, preparation method and applications |
| CN110364735A (en) * | 2019-07-04 | 2019-10-22 | 中国乐凯集团有限公司 | A kind of lithium ion battery silicon-carbon cathode adhesive, preparation and its application |
| CN110407983A (en) * | 2018-04-26 | 2019-11-05 | 中国石油化工股份有限公司 | Carboxylic styrene butadiene latex and its preparation method and application |
| CN111253534A (en) * | 2019-12-30 | 2020-06-09 | 深圳市研一新材料有限责任公司 | Preparation method of aqueous lithium supplement binder and positive plate for lithium ion battery |
| CN111825804A (en) * | 2020-07-27 | 2020-10-27 | 日照广大建筑材料有限公司 | Copolymer latex for lithium ion secondary battery cathode, preparation method and application |
-
2020
- 2020-11-04 CN CN202011217699.9A patent/CN112321761A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346328A (en) * | 2013-07-16 | 2013-10-09 | 中国科学院青岛生物能源与过程研究所 | High-potential-resistant window lithium-ion secondary battery binder and preparation method thereof |
| CN105576284A (en) * | 2016-02-18 | 2016-05-11 | 福建蓝海黑石科技有限公司 | Anode aqueous binder of lithium ion battery and preparation method thereof |
| CN107384261A (en) * | 2017-07-21 | 2017-11-24 | 中国乐凯集团有限公司 | A kind of lithium ion battery separator refractory layer aqueous binder, preparation method and applications |
| CN110407983A (en) * | 2018-04-26 | 2019-11-05 | 中国石油化工股份有限公司 | Carboxylic styrene butadiene latex and its preparation method and application |
| CN110364735A (en) * | 2019-07-04 | 2019-10-22 | 中国乐凯集团有限公司 | A kind of lithium ion battery silicon-carbon cathode adhesive, preparation and its application |
| CN111253534A (en) * | 2019-12-30 | 2020-06-09 | 深圳市研一新材料有限责任公司 | Preparation method of aqueous lithium supplement binder and positive plate for lithium ion battery |
| CN111825804A (en) * | 2020-07-27 | 2020-10-27 | 日照广大建筑材料有限公司 | Copolymer latex for lithium ion secondary battery cathode, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 张洋 等, 北京：中国轻工业出版社 * |
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