CN113429927B - Polyimide binder, preparation method thereof and silicon-carbon negative plate - Google Patents
Polyimide binder, preparation method thereof and silicon-carbon negative plate Download PDFInfo
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- CN113429927B CN113429927B CN202110515802.6A CN202110515802A CN113429927B CN 113429927 B CN113429927 B CN 113429927B CN 202110515802 A CN202110515802 A CN 202110515802A CN 113429927 B CN113429927 B CN 113429927B
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- Prior art keywords
- benzimidazole
- silicon
- polyimide binder
- polyimide
- polyamic acid
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 44
- 229920001721 polyimide Polymers 0.000 title claims abstract description 44
- 239000011230 binding agent Substances 0.000 title claims abstract description 41
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000004952 Polyamide Chemical class 0.000 claims abstract description 33
- 229920002647 polyamide Chemical class 0.000 claims abstract description 33
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 30
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000004985 diamines Chemical class 0.000 claims abstract description 19
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims abstract description 16
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- QCILMAMLEHOLRX-UHFFFAOYSA-N 2-(3-aminophenyl)-3h-benzimidazol-5-amine Chemical compound NC1=CC=CC(C=2NC3=CC(N)=CC=C3N=2)=C1 QCILMAMLEHOLRX-UHFFFAOYSA-N 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002388 carbon-based active material Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims 2
- 238000003756 stirring Methods 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- -1 PAA Salt Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyimide binder, which is prepared by copolymerizing benzimidazole polyamic acid salt and polyamide salt, wherein the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 8-9: 1-2; the raw materials for synthesizing the benzimidazole polyamic acid salt comprise: diamine monomer containing benzimidazole group structure, tetracarboxylic dianhydride monomer; the polyamide salt is synthesized by the following raw materials: diacid monomers and water-soluble diamine monomers. The invention also discloses a preparation method of the polyimide binder. The invention also discloses a silicon-carbon negative plate. The invention has good adhesion performance, can improve the expansion problem of the silicon-carbon cathode and improve the cycle performance of the battery.
Description
Technical Field
The invention relates to the technical field of binders, and particularly relates to a polyimide binder, a preparation method thereof and a silicon-carbon negative plate.
Background
In recent years, due to increasingly serious environmental problems and unavoidable energy crisis, demand for new energy electric vehicles has been increasing. Therefore, an energy storage device applied to an electric vehicle is receiving attention. The lithium ion battery has the advantages of high working voltage, high energy density, small volume, no memory effect and the like, and occupies the leading position in the fields of various mobile electronic devices and electric automobiles. However, the energy density of the energy storage device cannot meet the high requirement of energy storage of the future new energy electric vehicle.
The silicon-based negative electrode has a good effect of improving the energy density of the lithium ion battery. The silicon-based material has the theoretical specific capacity (4200mAh/g) which is 10 times that of graphite, the voltage platform is lower, the silicon reserves in the earth are abundant, and the development cost is low. The application of the silicon-based negative electrode can effectively improve the energy density of the single battery cell. However, the commercial application of silicon-based anode materials is still limited by several factors. Among them, the most important problem is that the volume change of silicon is large (300%) in the process of high-degree lithium intercalation, which easily causes the problems of silicon grain breakage and pulverization, electrode powder desorption and SEI film repeated growth, and the like, so that the silicon negative electrode has poor cycling stability and low coulombic efficiency.
The binder, one of the essential materials for battery fabrication, is present in very small amounts in the electrodes, but has an irreplaceable role. The main function of the binder is to bind the active material, the conductive agent and the current collector together, so as to shorten the lithium ion transmission path and stabilize the structure of the electrode material. The binders with different properties can directly influence the specific capacity, the coulombic efficiency, the stability of electrochemical performance and the like of the battery. The traditional binder polyvinylidene fluoride (PVDF) has high cost, poor environmental friendliness and weak acting force with active substances, and is not suitable for negative electrode materials with large silicon isovolumetric effect.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the polyimide binder, the preparation method thereof and the silicon-carbon negative electrode plate.
The invention provides a polyimide binder, which is prepared by copolymerizing benzimidazole polyamic acid salt and polyamide salt, wherein the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 8-9: 1-2;
the raw materials for synthesizing the benzimidazole polyamic acid salt comprise: diamine monomer containing benzimidazole group structure, tetracarboxylic dianhydride monomer; the polyamide salt is synthesized by the following raw materials: diacid monomers and water-soluble diamine monomers.
Preferably, the diamine monomer containing the benzimidazole group structure is at least one of 2- (3-aminophenyl) -5-aminobenzimidazole and 2- (4-aminophenyl) -5-aminobenzimidazole.
Preferably, the diacid monomer is a water soluble diacid monomer.
The water-soluble diacid monomer can be: glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, and the like.
The water-soluble diamine monomer may be: at least one of hexamethylenediamine, decamethylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzimidazole, and the like.
The tetracarboxylic dianhydride monomer may include at least one of the following compounds:
the invention also provides a preparation method of the polyimide binder, which comprises the following steps:
s1, uniformly mixing the aqueous solution of the diamine monomer containing the catalyst and the benzimidazole group structure with the tetracarboxylic dianhydride monomer, and reacting to obtain the benzimidazole polyamic acid salt aqueous solution;
s2, mixing the benzimidazole polyamic acid salt aqueous solution and the polyamide salt aqueous solution uniformly, introducing inert gas, carrying out high-pressure copolymerization reaction, then reducing the pressure to normal pressure, continuing introducing the inert gas, then cooling to room temperature, and drying to obtain the polyimide binder.
Preferably, in S1, the catalyst is triethylamine.
Preferably, in S1, the reaction temperature is less than or equal to 30 ℃ and the reaction time is 1.5-2.5 h.
Preferably, in S1, the molar ratio of the catalyst, the diamine monomer containing the benzimidazole group structure and the tetracarboxylic dianhydride monomer is 2.6-2.8:1.07-1.1: 1.
Preferably, in S2, the pressure of the reaction is 1.5-2 MPa.
Preferably, in S2, the temperature of the copolymerization reaction is 190 ℃ to 210 ℃, and the reaction time is 3.5-4 h.
Preferably, in S2, the pressure is reduced to atmospheric pressure over 1 h.
Preferably, in S2, the inert gas is continuously introduced for 1-1.5 h.
Preferably, in S2, the pH of the aqueous polyamide salt solution is 6 to 6.5.
The above was dried in S2 under vacuum at 170-190 ℃.
The preparation method of the polyamide salt is a conventional method in the field, and the specific operation can be as follows: under the regulation of catalyst, diacid monomer and water-soluble diamine monomer are copolymerized to obtain; the reaction solvent is preferably water; the reaction temperature is preferably 40-60 ℃, the reaction time is preferably 3-5h, and the catalyst is preferably sodium hypophosphite and the like.
The water is deionized water.
The invention also provides a silicon-carbon negative plate, which comprises: a current collector and a negative electrode material adhered to a surface of the current collector, wherein the negative electrode material comprises: silicon carbon active material, conductive agent and adhesive, wherein the adhesive is the polyimide adhesive.
Preferably, the weight ratio of the silicon-carbon active material, the conductive agent and the binder is 70-75:23-27: 2-3.
The conductive agent may be: graphene, carbon nanotubes, conductive carbon black, conductive graphite, ketjen black, acetylene black, carbon fibers, carbon nanofibers, and the like.
In the silicon carbon active material, the carbon may be at least one of hard carbon, soft carbon, natural graphite, artificial graphite, and the like; the silicon may be at least one of micro silicon, nano silicon, sub silicon oxide, etc.
The raw materials for synthesizing the benzimidazole polyamide acid salt are 2- (3-aminophenyl) -5-aminobenzimidazole and 4,4' - (hexafluoro-isopropylidene) diphthalic anhydride; the synthesis raw materials of the polyamide salt are selected from adipic acid and hexamethylene diamine, and the synthesis route of the invention is as follows:
firstly, preparing a polyamide acid Salt (marked as PAA Salt) and a polyamide Salt (marked as PA Salt) containing benzimidazole groups, and then carrying out copolymerization reaction on the two, wherein the benzimidazole groups and the polyamide are introduced into polyimide; the benzimidazole group can improve the adhesive property of polyimide, so that the active substance, the conductive agent and the current collector are tightly adhered, and the problems that the volume of the silicon-carbon negative electrode is changed greatly, the silicon-carbon active substance and the conductive agent fall off and the like in the charging and discharging process are solved, so that the cycle performance of the battery is improved; in addition, a proper amount of polyamide structure is introduced into the polyimide, so that the flexibility of the binder can be improved, the problem of large volume change of the silicon-carbon cathode in the charging and discharging process can be further solved, and the acyl in the polyamide can form a hydrogen bond with a silicon-carbon active substance, so that the binding strength is further improved, the expansion problem of the silicon-carbon cathode is improved, and the cycle performance of the battery is improved.
Detailed Description
The technical means of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a polyimide adhesive comprises the following steps:
s1, adding 5.2mmol of triethylamine and 2.2mmol of 2- (3-aminophenyl) -5-aminobenzimidazole into 800ml of deionized water, stirring and dissolving at 25 ℃, then adding 2mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, stirring and mixing uniformly, continuing stirring and reacting for 1.5h, and adjusting the solid content to 10 wt% to obtain a benzimidazole polyamic acid salt aqueous solution;
s2, dissolving 1mmol of hexamethylenediamine in 10ml of deionized water, adding 1.05mmol of adipic acid, mixing uniformly, adding 0.003mmol of sodium hypophosphite, stirring at 60 ℃ for reaction for 3 hours, adjusting the solid content to 50 wt%, and adjusting the pH value to 6.5 to obtain a polyamide salt aqueous solution;
uniformly mixing a benzimidazole polyamic acid salt aqueous solution and a polyamide salt aqueous solution (the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 4:1), transferring into a high-pressure kettle, introducing nitrogen, continuously stirring, gradually heating to 190 ℃, increasing the pressure to 2Mpa, stirring for reaction for 3.5h, then reducing the pressure to normal pressure within 1h, continuously introducing nitrogen for 1.5h to discharge small molecular products to promote the reaction, then cooling to room temperature, and then vacuum-drying at 170 ℃ for 10h to obtain the polyimide binder.
Example 2
A preparation method of a polyimide adhesive comprises the following steps:
s1, adding 5.6mmol of triethylamine and 2.14mmol of 2- (3-aminophenyl) -5-aminobenzimidazole into 800ml of deionized water, stirring and dissolving at 20 ℃, then adding 2mmol of 3,3',4,4' -biphenyltetracarboxylic dianhydride, stirring and uniformly mixing, continuing stirring and reacting for 2.5h, and adjusting the solid content to 10 wt% to obtain a benzimidazole polyamic acid salt aqueous solution;
s2, dissolving 1mmol of hexamethylenediamine in 10ml of deionized water, adding 1.05mmol of glutaric acid, mixing uniformly, adding 0.003mmol of sodium hypophosphite, stirring at 40 ℃ for reaction for 5 hours, adjusting the solid content to 50 wt%, and adjusting the pH value to 6 to obtain a polyamide salt aqueous solution;
uniformly mixing a benzimidazole polyamic acid salt aqueous solution and a polyamide salt aqueous solution (the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 9:1), transferring into a high-pressure kettle, introducing nitrogen, continuously stirring, gradually heating to 210 ℃, increasing the pressure to 1.5Mpa, stirring for reaction for 4 hours, then reducing the pressure to normal pressure within 1 hour, continuously introducing nitrogen for 1 hour to discharge small molecular products to promote the reaction, then cooling to room temperature, and then vacuum-drying at 190 ℃ for 10 hours to obtain the polyimide binder.
Example 3
A preparation method of a polyimide adhesive comprises the following steps:
s1, adding 5.4mmol of triethylamine and 2.18mmol of 2- (3-aminophenyl) -5-aminobenzimidazole into 800ml of deionized water, stirring and dissolving at 20 ℃, then adding 2mmol of 4,4' -oxydiphthalic anhydride, stirring and mixing uniformly, continuing stirring and reacting for 2 hours, and adjusting the solid content to 10 wt% to obtain a benzimidazole polyamic acid saline solution;
s2, dissolving 1mmol of decamethylenediamine in 10ml of deionized water, adding 1.05mmol of sebacic acid, mixing uniformly, adding 0.003mmol of sodium hypophosphite, stirring and reacting at 50 ℃ for 4 hours, adjusting the solid content to 50 wt%, and adjusting the pH to 6.2 to obtain a polyamide salt aqueous solution;
uniformly mixing a benzimidazole polyamic acid salt aqueous solution and a polyamide salt aqueous solution (the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 8.5:1.5), transferring into a high-pressure kettle, introducing nitrogen, continuously stirring, gradually heating to 200 ℃, increasing the pressure to 1.7Mpa, stirring for reaction for 3.8h, then reducing the pressure to normal pressure within 1h, continuously introducing nitrogen for 1.3h to discharge small molecular products to promote the reaction, then cooling to room temperature, and then drying in vacuum at 180 ℃ for 10h to obtain the polyimide binder.
Example 4
A preparation method of a polyimide adhesive comprises the following steps:
s1, adding 5.3mmol of triethylamine and 2.16mmol of 2- (3-aminophenyl) -5-aminobenzimidazole into 800ml of deionized water, stirring and dissolving at 20 ℃, then adding 2mmol of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, stirring and mixing uniformly, continuing stirring and reacting for 2.2 hours, and adjusting the solid content to 10 wt% to obtain a benzimidazole polyamic acid salt aqueous solution;
s2, dissolving 1mmol of hexamethylenediamine in 10ml of deionized water, adding 1.05mmol of dodecanedioic acid, uniformly mixing, adding 0.003mmol of sodium hypophosphite, stirring at 50 ℃ for reacting for 4.5 hours, adjusting the solid content to 50 wt%, and adjusting the pH value to 6.3 to obtain a polyamide salt aqueous solution;
uniformly mixing a benzimidazole polyamic acid salt aqueous solution and a polyamide salt aqueous solution (the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 8.3:1.7), transferring the mixture into a high-pressure kettle, introducing nitrogen, continuously stirring, gradually heating to 200 ℃, increasing the pressure to 1.7Mpa, stirring for reaction for 3.8h, then reducing the pressure to normal pressure within 1h, continuously introducing nitrogen for 1.3h to discharge small molecular products to promote the reaction, then cooling to room temperature, and then carrying out vacuum drying at 190 ℃ for 10h to obtain the polyimide binder.
Example 5
A preparation method of a polyimide adhesive comprises the following steps:
the diamine monomer containing a benzimidazole group structure was 2- (4-aminophenyl) -5-aminobenzimidazole, and the other operations were the same as in example 1.
Example 6
A preparation method of a polyimide adhesive comprises the following steps:
the diamine monomer containing a benzimidazole group structure was 2- (4-aminophenyl) -5-aminobenzimidazole, and the other operations were the same as in example 2.
Example 7
A preparation method of a polyimide adhesive comprises the following steps:
the diamine monomer containing a benzimidazole group structure was 2- (4-aminophenyl) -5-aminobenzimidazole, and the other operations were the same as in example 3.
Example 8
A preparation method of a polyimide adhesive comprises the following steps:
the diamine monomer containing benzimidazole group structure was 2- (4-aminophenyl) -5-aminobenzimidazole, and the other operations were the same as in example 4.
Experiment 1
The polyimide binders prepared in the examples 1 to 8 were used to prepare silicon-carbon negative electrode sheets respectively and assembled into batteries, and the specific operations were as follows:
adding a polyimide binder into N-methyl pyrrolidone, and fully stirring at 25 ℃ to obtain a glue solution with the solid content of 10 wt%; then according to the silicon-carbon active material: conductive carbon black: adding a silicon-carbon negative electrode material and conductive carbon black into the binder at a mass ratio of 70:27:3, fully grinding, and adjusting the viscosity to 12000mPa & s to obtain negative electrode slurry; uniformly scraping the negative electrode slurry on a copper foil, and drying at 60 ℃ in vacuum to obtain a silicon-carbon negative electrode plate;
and (3) assembling a button cell by using a silicon-carbon negative plate and a lithium plate as electrodes, Celgard 2400 as a diaphragm and a mixed solution of EC and EMC (v/v is 1:1) of 1mol/L LiPF6 as an electrolyte solution.
Comparative example 1
A battery was assembled as in experiment 1 using polyvinylidene fluoride as the binder.
Comparative example 2
A preparation method of a polyimide adhesive comprises the following steps:
adding 5.2mmol of triethylamine and 2.2mmol of 2- (3-aminophenyl) -5-aminobenzimidazole into 800ml of deionized water, stirring and dissolving at 25 ℃, then adding 2mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, stirring and mixing uniformly, continuing stirring and reacting for 1.5h, and adjusting the solid content to 10 wt% to obtain a benzimidazole polyamic acid salt aqueous solution;
s2, transferring the aqueous solution of the benzimidazole polyamic acid salt into a high-pressure kettle, introducing nitrogen, continuously stirring, gradually heating to 190 ℃, increasing the pressure to 2Mpa, stirring for reaction for 3.5h, then reducing the pressure to normal pressure within 1h, continuously introducing nitrogen for 1.5h to discharge small molecular products to promote the reaction, then cooling to room temperature, and then vacuum-drying at 170 ℃ for 10h to obtain the polyimide binder; the cell was assembled as in experiment 1.
Comparative example 3
A preparation method of a polyimide adhesive,
dissolving 2.2mmol of 4,4 '-diaminodiphenyl ether in 20ml of N, N-dimethylacetamide solvent under nitrogen atmosphere, stirring until the solution is completely dissolved, adding 2mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, continuously stirring until the solution is completely dissolved, and reacting for 8 hours at 5 ℃ to obtain a polyamic acid solution;
heating a polyamic acid solution to 180 ℃, reacting at a constant temperature for 18 hours, imidizing, cooling to room temperature, slowly adding the polyamic acid solution into a flask filled with methanol, precipitating, filtering, washing, and drying in vacuum to obtain a polyimide binder; the cell was assembled as in experiment 1.
The charge and discharge tests were performed on each button cell, and the results are shown in table 1.
TABLE 1 test results
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (13)
1. The polyimide binder is characterized by being prepared by copolymerizing benzimidazole polyamic acid salt and polyamide salt, wherein the weight ratio of the benzimidazole polyamic acid salt to the polyamide salt is 8-9: 1-2;
the raw materials for synthesizing the benzimidazole polyamic acid salt comprise: diamine monomer containing benzimidazole group structure, tetracarboxylic dianhydride monomer; the polyamide salt is synthesized by the following raw materials: diacid monomers and diamine monomers;
the diacid monomer is: at least one of glutaric acid, adipic acid, sebacic acid, and dodecanedioic acid;
the diamine monomer is: at least one of hexamethylene diamine and decamethylene diamine.
2. The polyimide binder according to claim 1, wherein the diamine monomer having a benzimidazole group structure is at least one of 2- (3-aminophenyl) -5-aminobenzimidazole and 2- (4-aminophenyl) -5-aminobenzimidazole.
3. A method for preparing the polyimide adhesive according to claim 1 or 2, comprising the steps of:
s1, uniformly mixing the aqueous solution of the diamine monomer containing the catalyst and the benzimidazole group structure with the tetracarboxylic dianhydride monomer, and reacting to obtain the benzimidazole polyamic acid salt aqueous solution;
s2, mixing the benzimidazole polyamic acid salt aqueous solution and the polyamide salt aqueous solution uniformly, introducing inert gas, carrying out high-pressure copolymerization reaction, then reducing the pressure to normal pressure, continuing introducing the inert gas, then cooling to room temperature, and drying to obtain the polyimide binder.
4. The method for preparing a polyimide binder according to claim 3, wherein in S1, the catalyst is triethylamine.
5. The method for preparing polyimide binder according to claim 3, wherein in S1, the reaction temperature is 30 ℃ or less and the reaction time is 1.5-2.5 hours.
6. The method for preparing a polyimide binder according to claim 3, wherein the molar ratio of the catalyst to the diamine monomer containing a benzimidazole group structure to the tetracarboxylic dianhydride monomer in S1 is 2.6-2.8:1.07-1.1: 1.
7. The method for preparing polyimide binder according to claim 3, wherein the reaction pressure is 1.5 to 2Mpa in S2.
8. The method for preparing polyimide binder as claimed in claim 3, wherein the temperature of copolymerization reaction in S2 is 190-210 ℃ and the reaction time is 3.5-4 h.
9. The method for preparing a polyimide binder according to claim 3, wherein the pressure is reduced to normal pressure within 1 hour in S2.
10. The method for preparing polyimide binder according to claim 3, wherein the inert gas is continuously introduced for 1 to 1.5 hours in S2.
11. The method for producing a polyimide binder according to claim 3, wherein the aqueous solution of polyamide salt has a pH =6-6.5 in S2.
12. A silicon-carbon negative electrode sheet, comprising: a current collector and a negative electrode material adhered to a surface of the current collector, wherein the negative electrode material comprises: a silicon carbon active material, a conductive agent and a binder, wherein the binder is the polyimide binder in the claim 1 or 2.
13. The silicon-carbon negative electrode sheet according to claim 12, wherein the weight ratio of the silicon-carbon active material to the conductive agent to the binder is 70-75:23-27: 2-3.
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Denomination of invention: A polyimide adhesive and its preparation method, silicon carbon negative electrode plate Effective date of registration: 20231114 Granted publication date: 20220531 Pledgee: China Merchants Bank Co.,Ltd. Jinhua Branch Pledgor: Zhejiang Zhongke Jiuyuan New Material Co.,Ltd. Registration number: Y2023980065179 |