CN115216245A - Binder, battery pole piece and preparation method thereof, and secondary battery - Google Patents
Binder, battery pole piece and preparation method thereof, and secondary battery Download PDFInfo
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- CN115216245A CN115216245A CN202110404761.3A CN202110404761A CN115216245A CN 115216245 A CN115216245 A CN 115216245A CN 202110404761 A CN202110404761 A CN 202110404761A CN 115216245 A CN115216245 A CN 115216245A
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- pole piece
- binder
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- battery pole
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- 239000011230 binding agent Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 62
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 26
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000006258 conductive agent Substances 0.000 claims description 33
- 230000001070 adhesive effect Effects 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000002033 PVDF binder Substances 0.000 claims description 26
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000011267 electrode slurry Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000007773 negative electrode material Substances 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- -1 nickel cobalt manganese aluminum Chemical compound 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002098 polyfluorene Polymers 0.000 claims description 6
- 125000006267 biphenyl group Chemical group 0.000 claims description 5
- 238000005056 compaction Methods 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 239000011866 silicon-based anode active material Substances 0.000 claims 1
- 229920005596 polymer binder Polymers 0.000 abstract description 22
- 239000002491 polymer binding agent Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 14
- 125000004122 cyclic group Chemical group 0.000 abstract description 11
- 239000011149 active material Substances 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 6
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 57
- 239000002002 slurry Substances 0.000 description 33
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 23
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 23
- 239000003292 glue Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000007787 solid Substances 0.000 description 17
- 238000005096 rolling process Methods 0.000 description 16
- 239000007772 electrode material Substances 0.000 description 12
- 239000011863 silicon-based powder Substances 0.000 description 12
- 230000008602 contraction Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 7
- 229920006255 plastic film Polymers 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000007770 graphite material Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 239000011871 silicon-based negative electrode active material Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical group C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000004069 differentiation Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000002409 silicon-based active material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QFYXSLAAXZTRLG-UHFFFAOYSA-N pyrrolidine-2,3-dione Chemical group O=C1CCNC1=O QFYXSLAAXZTRLG-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- 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
- C09J127/00—Adhesives based on homopolymers or 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 a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives based on homopolymers or 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives based on homopolymers or 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
-
- 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
-
- 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
- H01M4/139—Processes of manufacture
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明属于电池技术领域，尤其涉及一种粘结剂，以及一种电池极片及其制备方法，一种二次电池。其中，粘结剂包括：高分子粘结材料和导电聚合物，其中，所述导电聚合物选自式I、式II中的至少一种物质：
Description
技术领域technical field
本发明属于电池技术领域，尤其涉及一种粘结剂，以及一种电池极片及其制备方法，一种二次电池。The invention belongs to the technical field of batteries, and in particular relates to a binder, a battery pole piece and a preparation method thereof, and a secondary battery.
背景技术Background technique
锂离子电池由于其性能优势已成为电动汽车的主要动力电源，作为一种能量存储装置，其主要由正极，负极，隔膜，电解液等组成。电动汽车续航里程的提升倒逼电芯能量密度的提升，而正负极材料对于电芯的能量密度和其他电性能起着至关重要的作用。目前商业化的负极石墨材料其理论比容量为372mAh/g，阻碍了电芯能量密度的提升。因而硅负极材料走入人们视野，其理论比容量高达4200mAh/g，硅负极材料被认为是石墨负极材料的替代性产品具有重要应用前景。然而硅负极在嵌脱锂离子过程中，其体积膨胀高达100％-300％，造成材料颗粒破碎和极片粉化，极片导致电性能急剧下降使得循环性能差。目前，抑制硅基材料体积膨胀的重要方法之一是通过粘结剂的黏结性能降低极片的形变，防止掉粉等。常见的有粘结剂有聚丙烯酸、CMC/SBR、海藻酸钠、壳聚糖、聚酰亚胺等，这些粘结剂的粘附性能有待进一步提高，很容易在硅的反复膨胀收缩的过程中与体系脱离接触，破坏整个导电体系的完整性，引起的导电通路断开与极片分化等问题，导致硅基电池的循环性能大幅度下降。Lithium-ion batteries have become the main power source of electric vehicles due to their performance advantages. As an energy storage device, they are mainly composed of positive electrodes, negative electrodes, separators, and electrolytes. The increase in the cruising range of electric vehicles will force the improvement of the energy density of the battery cell, and the positive and negative electrode materials play a crucial role in the energy density and other electrical properties of the battery cell. The theoretical specific capacity of the currently commercialized anode graphite material is 372 mAh/g, which hinders the improvement of the energy density of the cell. Therefore, silicon anode materials have come into people's field of vision, and their theoretical specific capacity is as high as 4200mAh/g. Silicon anode materials are considered to be alternative products of graphite anode materials and have important application prospects. However, during the intercalation and deintercalation of lithium ions in the silicon negative electrode, the volume expansion is as high as 100%-300%, resulting in material particle breakage and pole piece pulverization. The pole piece leads to a sharp decline in electrical properties and poor cycle performance. At present, one of the important methods to suppress the volume expansion of silicon-based materials is to reduce the deformation of the pole piece through the bonding performance of the binder, and prevent the powder from falling off. Common binders include polyacrylic acid, CMC/SBR, sodium alginate, chitosan, polyimide, etc. The adhesion performance of these binders needs to be further improved, and it is easy to be in the process of repeated expansion and contraction of silicon. The middle and the system are out of contact, destroying the integrity of the entire conductive system, causing problems such as the disconnection of the conductive path and the polarization of the pole pieces, resulting in a significant decrease in the cycle performance of the silicon-based battery.
因此需要开发合适的粘结剂来解决硅负极循环膨胀收缩过程引起的导电通路断开与极片分化问题，改善其循环性能。Therefore, it is necessary to develop a suitable binder to solve the problems of conduction path disconnection and pole piece differentiation caused by the cyclic expansion and contraction of silicon anode, and to improve its cycle performance.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种粘结剂，以及一种电池极片及其制备方法，一种二次电池，旨在一定程度上解决现有硅基负极等电池极片在循环膨胀收缩过程中，容易引起导电通路断开，极片分化的问题。The purpose of the present invention is to provide a binder, a battery pole piece and a preparation method thereof, and a secondary battery, aiming to solve the problem of the existing silicon-based negative electrode and other battery pole pieces in the process of cyclic expansion and shrinkage to a certain extent. , it is easy to cause the disconnection of the conductive path and the problem of pole piece differentiation.
为实现上述申请目的，本发明采用的技术方案如下：For realizing above-mentioned application purpose, the technical scheme adopted in the present invention is as follows:
第一方面，本发明提供一种粘结剂，其特征在于，粘结剂包括：高分子粘结材料和导电聚合物，其中，导电聚合物选自式I、式II中的至少一种物质：
本发明第一方面提供的粘结剂包括高分子粘结材料和导电聚合物，其中，导电聚合物为主链含有吡咯烷二酮或者芴等芳香环的聚合物，不但使导电聚合物具有一定的粘结性能，而且主链上的芳香环具有共轭的大π键，使得聚合物同时具有导电性能。一方面，改善了电极片中活性材料之间的电子导电性，另一方面，改善了硅等电极活性材料在循环充放电过程中，因体积膨胀收缩对电极片导电通路完整性的影响，从而改善了电池极片的循环稳定性能。另外，高分子粘结材料具有优异的黏结性能，与电极活性物质和集流体之间的粘结力强，既可以提高极片的稳定性，也可以降低极片在循环充放电过程中的粉化、掉粉等现象。The binder provided by the first aspect of the present invention includes a polymer binder material and a conductive polymer, wherein the conductive polymer contains a polymer with aromatic rings such as pyrrolidinedione or fluorene in the main chain, which not only makes the conductive polymer have a certain Moreover, the aromatic ring on the main chain has a large conjugated π bond, which makes the polymer have conductive properties at the same time. On the one hand, the electronic conductivity between the active materials in the electrode sheet is improved; The cycle stability performance of the battery pole piece is improved. In addition, the polymer bonding material has excellent bonding performance and strong bonding force between the electrode active material and the current collector, which can not only improve the stability of the pole piece, but also reduce the powder of the pole piece during the cyclic charge and discharge process. phenomenon, such as fading, powder dropping, etc.
进一步地，Ar1、Ar2分别独立地选自：苯基、取代的苯基、联苯基、取代的联苯基、二苯醚、取代的二苯醚中的至少一种，这些芳香族基团均有大的共轭π键，可更好的提高聚合物的导电性能。Further, Ar1 and Ar2 are independently selected from: at least one of phenyl, substituted phenyl, biphenyl, substituted biphenyl, diphenyl ether, substituted diphenyl ether, these aromatic groups All have large conjugated π bonds, which can better improve the conductivity of the polymer.
进一步地，取代的苯基、取代的联苯基、取代的二苯醚中，取代基分别独立地选自：烷基、烷氧基中的至少一种。进一步地，取代的苯基、取代的联苯基、取代的二苯醚中，取代形式包括单取代或者多取代。烷基、烷氧基等取代基可在Ar1、Ar2任意位置进行单取代或者多取代，通过烷基或烷氧基的取代，提高导电聚合物的粘结性能，更好的抑制电极片中活性物质的体积膨胀Further, in the substituted phenyl group, the substituted biphenyl group and the substituted diphenyl ether, the substituents are independently selected from at least one of alkyl and alkoxy. Further, in the substituted phenyl group, the substituted biphenyl group and the substituted diphenyl ether, the substitution form includes mono-substitution or multi-substitution. Substituents such as alkyl and alkoxy can be singly or multi-substituted at any position of Ar1 and Ar2. The substitution of alkyl or alkoxy can improve the bonding performance of conductive polymers and better inhibit the activity in the electrode sheet. volume expansion of matter
进一步地，导电聚合物选自：均苯四甲酸二酐和对苯二胺的共聚酰亚胺聚合物、均苯四甲酸二酐和二氨基二苯醚的共聚酰亚胺聚合物、聚芴聚合物中的至少一种，这些导电聚合物同时具有良好的粘接性能和优异电导性能。Further, the conductive polymer is selected from: copolyimide polymer of pyromellitic dianhydride and p-phenylenediamine, copolyimide polymer of pyromellitic dianhydride and diaminodiphenyl ether, polyfluorene At least one of polymers, these conductive polymers have both good adhesive properties and excellent electrical conductivity.
进一步地，高分子粘结材料选自：聚偏氟乙烯、甲基纤维素钠、甲基纤维素、丁苯橡胶、乙基纤维素、聚丙烯酸、聚丙烯腈、聚丙烯盐、海藻酸钠中的至少一种，这些高分子粘结剂具有优异的粘结性能，粘度稳定，可以为粘结提供稳定的粘度和附着力。Further, the polymer bonding material is selected from: polyvinylidene fluoride, sodium methyl cellulose, methyl cellulose, styrene butadiene rubber, ethyl cellulose, polyacrylic acid, polyacrylonitrile, polypropylene salt, sodium alginate At least one of these polymer binders has excellent bonding performance and stable viscosity, which can provide stable viscosity and adhesion for bonding.
进一步地，高分子粘结材料和导电聚合物的质量比为1：(1～4)，该配比综合了粘结剂的粘接力度和导电性能。Further, the mass ratio of the polymer binding material and the conductive polymer is 1:(1-4), and the ratio combines the bonding strength and the conductive performance of the binder.
第二方面，本发明提供一种电池极片，电池极片包括：正极活性材料或者负极活性材料，导电剂和上述的粘结剂。In a second aspect, the present invention provides a battery pole piece, the battery pole piece includes: a positive electrode active material or a negative electrode active material, a conductive agent and the above-mentioned binder.
本发明第二方面提供的电池极片，包括正极活性材料或者负极活性材料，导电剂，以及上述同时具有优异的粘接性能和导电性能的粘结剂，该粘结剂不但粘结性能好，对电极活性材料和导电剂能起到分散作用、增稠及防沉降作用，而且可改善电极片中活性材料之间的电子导电性，改善硅等电极活性材料在循环充放电过程中因体积膨胀收缩对电极片导电通路完整性的影响。因而，本发明实施例电池极片与集流体粘结力强，极片循环稳定性好。The battery pole piece provided by the second aspect of the present invention includes a positive electrode active material or a negative electrode active material, a conductive agent, and the above-mentioned binder having both excellent bonding performance and conductivity. The binder not only has good bonding performance, It can disperse, thicken and prevent sedimentation of electrode active materials and conductive agents, and can improve the electronic conductivity between active materials in the electrode sheet, and improve the volume expansion of silicon and other electrode active materials during the cyclic charge and discharge process. The effect of shrinkage on the integrity of the conductive path of the electrode sheet. Therefore, in the embodiment of the present invention, the bonding force between the battery pole piece and the current collector is strong, and the cycle stability of the pole piece is good.
进一步地，电池极片中，粘结剂的含量为1～10％；导电剂的含量为0.5～10％；若导电剂含量过小，则电极片电阻过大；若导电剂含量过大，则降低了极片的容量，影响电芯容量。Further, in the battery pole piece, the content of the binder is 1-10%; the content of the conductive agent is 0.5-10%; if the content of the conductive agent is too small, the resistance of the electrode sheet is too large; if the content of the conductive agent is too large, It reduces the capacity of the pole piece and affects the capacity of the cell.
进一步地，导电剂包括：导电炭黑、科琴黑、导电碳纳米管、导电碳纤维中的至少一种，这些导电剂均具有优异的导电性，可显著提高极片的电导力。Further, the conductive agent includes at least one of conductive carbon black, Ketjen black, conductive carbon nanotubes, and conductive carbon fibers, all of which have excellent electrical conductivity and can significantly improve the electrical conductivity of the pole piece.
进一步地，电池极片为正极片，包括：镍钴锰三元材料、镍钴锰铝四元材料、镍钴铝三元材料、磷酸铁锂、磷酸锰铁锂、钴酸锂、锰酸锂中的至少一种正极活性材料，这些正极材料均具有较好的电化学性能。Further, the battery pole piece is a positive electrode piece, including: nickel-cobalt-manganese ternary material, nickel-cobalt-manganese-aluminum quaternary material, nickel-cobalt-aluminum ternary material, lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium manganate At least one of the positive electrode active materials, these positive electrode materials have good electrochemical performance.
进一步地，电池极片为负极片，包括：Si、SiO、SiO2中的至少一种硅基负极活性材料，这些硅基活性材料克容量高。Further, the battery pole piece is a negative electrode piece, comprising: at least one silicon-based negative electrode active material selected from Si, SiO, and SiO 2 , and these silicon-based active materials have high gram capacity.
进一步地，负极片的压实密度为1.50～1.85g/cm3；正极片的压实密度为3.2～3.8g/cm3，本发明电池极片的压实密度既确保了极片的能量密度，又避免极片压实过大导致极片在充放电时体积膨胀反弹过大。Further, the compacted density of the negative electrode sheet is 1.50-1.85 g/cm 3 ; the compacted density of the positive electrode sheet is 3.2-3.8 g/cm 3 , and the compacted density of the battery electrode sheet of the present invention not only ensures the energy density of the electrode sheet , and avoid the excessive compaction of the pole piece, which will cause the volume expansion and rebound of the pole piece to be too large during charging and discharging.
进一步地，负极片中还包括碳材料，碳材料与硅基负极活性材料的质量比为(80～95)：(5～20)，采用体积膨胀小的石墨材料与硅基负极材料以上述配比复合使用，既降低极片的体积膨胀，又提高极片的稳定性。Further, the negative electrode sheet also includes a carbon material, and the mass ratio of the carbon material to the silicon-based negative electrode active material is (80-95): (5-20). Compared with composite use, it not only reduces the volume expansion of the pole piece, but also improves the stability of the pole piece.
第三方面，本发明提供一种上述的电池极片的制备方法，包括步骤：将正极活性材料或者负极活性材料、导电剂和粘结剂分散在溶剂中形成电极浆料后，涂覆或沉积于集流体上，干燥得到电池极片。In a third aspect, the present invention provides a method for preparing the above-mentioned battery pole piece, comprising the steps of: dispersing a positive electrode active material or a negative electrode active material, a conductive agent and a binder in a solvent to form an electrode slurry, then coating or depositing the electrode slurry. On the current collector, the battery pole piece is obtained by drying.
本发明第三方面提供的电池极片的制备方法，通过将正极活性材料或者负极活性材料、导电剂和粘结剂分散在溶剂形成电极浆料后，涂覆或沉积在集流体上，干燥辊压即可得到负极片或者正极片，制备工艺简单，操作简便，适用于工业化大规模生产和应用。且制备的电池极片由于包含有上述具有优异的粘接性能和导电性能的粘结剂，不但使得电极浆料与集流体附着力强，而且可改善电极片中活性材料之间的电子导电性，提高导电通路的完整性。In the method for preparing a battery pole piece provided by the third aspect of the present invention, the positive electrode active material or the negative electrode active material, the conductive agent and the binder are dispersed in a solvent to form an electrode slurry, and then coated or deposited on the current collector, drying roller The negative electrode sheet or the positive electrode sheet can be obtained by pressing, the preparation process is simple, the operation is simple and convenient, and it is suitable for industrialized large-scale production and application. And the prepared battery pole piece contains the above-mentioned binder with excellent adhesion and electrical conductivity, which not only makes the electrode slurry and the current collector strong, but also improves the electronic conductivity between the active materials in the electrode piece. , improve the integrity of the conductive path.
第四方面，本发明提供一种二次电池，二次电池包含上述的电池极片，或者包含上述方法制备的电池极片。In a fourth aspect, the present invention provides a secondary battery. The secondary battery includes the above-mentioned battery pole piece, or the battery pole piece prepared by the above-mentioned method.
本发明第四方面提供的二次电池，由于包含有上述克容量高，循环稳定性好，导电性优异的正极片或者负极片，因而二次电池使用寿命长，安全性高。The secondary battery provided by the fourth aspect of the present invention contains the above positive electrode or negative electrode sheet with high gram capacity, good cycle stability and excellent electrical conductivity, so the secondary battery has a long service life and high safety.
具体实施方式Detailed ways
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
本发明中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。In the present invention, the term "and/or", which describes the association relationship between associated objects, indicates that there can be three kinds of relationships, for example, A and/or B can indicate that A exists alone, A and B exist at the same time, and B exists alone Happening. where A and B can be singular or plural. The character "/" generally indicates that the associated objects are an "or" relationship.
本发明中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a，b或c中的至少一项(个)”，或，“a，b和c中的至少一项(个)”，均可以表示：a，b，c，a-b(即a和b)，a-c，b-c，或a-b-c，其中a，b，c分别可以是单个，也可以是多个。In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one item(s) below" or similar expressions thereof refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (one) of a, b or c", or "at least one (one) of a, b and c", can mean: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, and c may be single or multiple, respectively.
应理解，在本发明的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本发明实施例的实施过程构成任何限定。It should be understood that, in various embodiments of the present invention, the size of the sequence numbers of the above-mentioned processes does not mean the sequence of execution, some or all of the steps may be executed in parallel or sequentially, and the execution sequence of each process should be based on its functions and It is determined by the internal logic and should not constitute any limitation on the implementation process of the embodiments of the present invention.
在本发明实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本发明。在本发明实施例和所附权利要求书中所使用的单数形式的“一种”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. As used in the embodiments of the present invention and the appended claims, the singular forms "a" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.
本发明实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本发明实施例说明书相关组分的含量按比例放大或缩小均在本发明实施例说明书公开的范围之内。具体地，本发明实施例说明书中所述的质量可以是μg、mg、g、kg等化工领域公知的质量单位。The weight of the relevant components mentioned in the description of the embodiment of the present invention can not only refer to the specific content of each component, but also can represent the proportional relationship between the weights of the components. It is within the scope disclosed in the description of the embodiments of the present invention that the content of the ingredients is scaled up or down. Specifically, the mass described in the description of the embodiment of the present invention may be a mass unit known in the chemical field, such as μg, mg, g, and kg.
术语“第一”、“第二”仅用于描述目的，用来将目的如物质彼此区分开，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本发明实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implying the number of indicated technical features. For example, without departing from the scope of the embodiments of the present invention, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, a feature defined as "first" or "second" may expressly or implicitly include one or more of that feature.
本发明实施例第一方面提供一种粘结剂，所述粘结剂包括：高分子粘结材料和导电聚合物，其中，所述导电聚合物选自式I、式II中的至少一种物质：A first aspect of the embodiments of the present invention provides an adhesive, the adhesive comprising: a polymer adhesive material and a conductive polymer, wherein the conductive polymer is selected from at least one of formula I and formula II substance:
本发明实施例第一方面提供的粘结剂包括高分子粘结材料和导电聚合物，其中，导电聚合物为主链含有吡咯烷二酮或者芴等芳香环的聚合物，不但使导电聚合物具有一定的粘结性能，而且主链上的芳香环具有共轭的大π键，使得聚合物同时具有导电性能。一方面，改善了电极片中活性材料之间的电子导电性，另一方面，改善了硅等电极活性材料在循环充放电过程中，因体积膨胀收缩对电极片导电通路完整性的影响，从而改善了电池极片的循环稳定性能。另外，高分子粘结材料具有优异的黏结性能，与电极活性物质和集流体之间的粘结力强，既可以提高极片的稳定性，也可以降低极片在循环充放电过程中的粉化、掉粉等现象。The adhesive provided in the first aspect of the embodiment of the present invention includes a polymer adhesive material and a conductive polymer, wherein the conductive polymer contains a polymer containing aromatic rings such as pyrrolidinedione or fluorene in the main chain, which not only makes the conductive polymer It has certain bonding properties, and the aromatic ring on the main chain has a large conjugated π bond, which makes the polymer have electrical conductivity at the same time. On the one hand, the electronic conductivity between the active materials in the electrode sheet is improved; The cycle stability performance of the battery pole piece is improved. In addition, the polymer bonding material has excellent bonding performance and strong bonding force between the electrode active material and the current collector, which can not only improve the stability of the pole piece, but also reduce the powder of the pole piece during the cyclic charge and discharge process. phenomenon, such as fading, powder dropping, etc.
本发明实施例导电聚合物的式I、式II中n为100～1000的整数，m为100～1000的整数，若n或m过小，则导电聚合物的聚合度不够，影响导电聚合物的粘结能力，若n或m过大，则导电聚合物分子量过大，粘结性能过大，会影响导电粘结剂的导电性能，也不利于导电粘结剂在粘结剂中应用。In the formulas I and II of the conductive polymers in the embodiments of the present invention, n is an integer from 100 to 1000, and m is an integer from 100 to 1000. If n or m is too small, the degree of polymerization of the conductive polymer is insufficient, which affects the conductive polymer. If n or m is too large, the molecular weight of the conductive polymer will be too large, and the bonding performance will be too large, which will affect the conductive performance of the conductive adhesive and is not conducive to the application of the conductive adhesive in the adhesive.
在一些具体实施例中，本发明实施例粘结剂中高分子粘结材料和导电聚合物在使用的时候再将两者混合均匀后应用到电极材料中。In some specific embodiments, the polymer binder material and the conductive polymer in the binder of the embodiment of the present invention are mixed evenly and then applied to the electrode material.
在一些实施例中，所述导电聚合物选自式I、式II中的至少一种物质：
在一些实施例中，式I主链中Ar1、Ar2分别独立地选自：苯基、取代的苯基、联苯基、取代的联苯基、二苯醚、取代的二苯醚中的至少一种，这些芳香族基团均有大的共轭π键，可更好的提高聚合物的导电性能。当粘结剂应用到电极片后，可更好地改善硅等电极活性材料在循环充放电过程中，因体积膨胀收缩对电极片导电通路完整性的影响，在电极活性材料之间形成导电通路。In some embodiments, Ar1 and Ar2 in the main chain of formula I are independently selected from at least one of: phenyl, substituted phenyl, biphenyl, substituted biphenyl, diphenyl ether, and substituted diphenyl ether One, these aromatic groups have large conjugated π bonds, which can better improve the conductivity of the polymer. When the binder is applied to the electrode sheet, it can better improve the influence of volume expansion and contraction on the integrity of the conductive path of the electrode sheet during the cyclic charge and discharge process of electrode active materials such as silicon, and form a conductive path between the electrode active materials. .
在一些实施例中，所述取代的苯基、所述取代的联苯基、所述取代的二苯醚中，取代基分别独立地选自：烷基、烷氧基中的至少一种。在一些实施例中，所述取代的苯基、所述取代的联苯基、所述取代的二苯醚中，取代形式包括单取代或者多取代，且本发明实施例对取代位置不做具体限定。当Ar1、Ar2芳香族基团连接到式I主链中后，烷基、烷氧基等取代基可在Ar1、Ar2任意位置进行单取代或者多取代，通过烷基或烷氧基的取代，提高导电聚合物的粘结性能，更好的抑制电极片中活性物质的体积膨胀。In some embodiments, in the substituted phenyl group, the substituted biphenyl group, and the substituted diphenyl ether, the substituents are each independently selected from at least one of an alkyl group and an alkoxy group. In some embodiments, in the substituted phenyl group, the substituted biphenyl group, and the substituted diphenyl ether, the substitution form includes mono-substitution or polysubstitution, and the substitution position is not specific in the embodiments of the present invention limited. When the Ar1 and Ar2 aromatic groups are connected to the main chain of formula I, substituents such as alkyl and alkoxy can be mono- or poly-substituted at any position of Ar1 and Ar2, through the substitution of alkyl or alkoxy, Improve the bonding performance of the conductive polymer, and better suppress the volume expansion of the active material in the electrode sheet.
在一些实施例中，烷基、烷氧基等取代基团的碳链长度优选1-8，该链长的取代基即可有效提高导电聚合物的粘接性能，又避免聚合物分子量过大，黏度过大，分散困难，不利于在电极片中应用。In some embodiments, the carbon chain length of substituent groups such as alkyl groups and alkoxy groups is preferably 1-8. The chain length of the substituent groups can effectively improve the adhesive performance of the conductive polymer, and avoid the polymer molecular weight from being too large. , the viscosity is too large and the dispersion is difficult, which is not conducive to the application in the electrode sheet.
在一些具体实施例中，所述导电聚合物选自：均苯四甲酸二酐和对苯二胺的共聚酰亚胺聚合物(Ar1和Ar2为苯环)、均苯四甲酸二酐和二氨基二苯醚的共聚酰亚胺聚合物(Ar1为苯环，Ar2为苯环上面带甲基(-CH3)或带乙基(-CH2CH3)等)、聚芴聚合物(R1，R2分别为甲基(-CH3)为乙基(-CH2CH3)或丙基(-CH2CH2CH3)等)中的至少一种，这些导电聚合物同时具有良好的粘接性能和优异电导性能。In some specific embodiments, the conductive polymer is selected from the group consisting of: a copolyimide polymer of pyromellitic dianhydride and p-phenylenediamine (Ar1 and Ar2 are benzene rings), pyromellitic dianhydride and diamine Amino diphenyl ether copolyimide polymer (Ar1 is a benzene ring, Ar2 is a methyl group (-CH3) or an ethyl group (-CH2CH3) on the benzene ring, etc.), polyfluorene polymer (R1, R2 are respectively Methyl group (-CH3) is at least one of ethyl group (-CH2CH3) or propyl group (-CH2CH2CH3), etc.), and these conductive polymers have both good adhesion properties and excellent electrical conductivity properties.
在一些实施例中，所述高分子粘结材料选自：聚偏氟乙烯、甲基纤维素钠、甲基纤维素、丁苯橡胶、乙基纤维素、聚丙烯酸、聚丙烯腈、聚丙烯盐、海藻酸钠中的至少一种，这些高分子粘结剂具有优异的粘结性能，粘度稳定，可以为粘结提供稳定的粘度和附着力。同时，当粘结剂应用到电极片中时，这些高分子粘结材料还对电极活性材料及导电剂起到分散作用、增稠及防沉降作用；稳定电极浆料的加工性能，提高电极片的剥离强度等，从而提高电池的循环性能。In some embodiments, the polymer bonding material is selected from the group consisting of: polyvinylidene fluoride, sodium methyl cellulose, methyl cellulose, styrene butadiene rubber, ethyl cellulose, polyacrylic acid, polyacrylonitrile, polypropylene At least one of salt and sodium alginate, these polymer binders have excellent bonding properties, stable viscosity, and can provide stable viscosity and adhesion for bonding. At the same time, when the binder is applied to the electrode sheet, these polymer binder materials also play a dispersing, thickening and anti-settling effect on the electrode active material and the conductive agent; stabilize the processing performance of the electrode slurry and improve the electrode sheet. peel strength, etc., thereby improving the cycle performance of the battery.
在一些实施例中，粘结剂中，高分子粘结材料和所述导电聚合物的质量比为1：(1～4)，若粘结剂中高分子粘结材料含量过低，则粘结剂的粘结力度不够，应用到电极片后对极片中活性物质及导电剂粘结性能不佳，且极片柔韧性差，极片过脆；若粘结剂中导电聚合物含量过低，则粘结剂的导电性能不佳，应用到电极片后，难以在电极活性材料之间形成导电通路，对极片因体积膨胀收缩产生的分化改善效果不佳。在一些具体实施例中，高分子粘结材料和所述导电聚合物的质量比可以是1：1、1:2、1:3或者1:4等。In some embodiments, in the binder, the mass ratio of the polymer binder material and the conductive polymer is 1: (1-4). If the content of the polymer binder material in the binder is too low, the binder will The bonding strength of the agent is not enough, the bonding performance of the active material and the conductive agent in the electrode sheet is not good after being applied to the electrode sheet, and the flexibility of the electrode sheet is poor, and the electrode sheet is too brittle; if the conductive polymer content in the binder is too low, Then, the electrical conductivity of the binder is not good. After being applied to the electrode sheet, it is difficult to form a conductive path between the electrode active materials, and the effect of improving the differentiation of the electrode sheet due to volume expansion and contraction is not good. In some specific embodiments, the mass ratio of the polymer binding material and the conductive polymer may be 1:1, 1:2, 1:3, or 1:4, etc.
本发明实施例第二方面提供一种电池极片，其特征在于，所述电池极片包括：正极活性材料或者负极活性材料，导电剂和上述的粘结剂。A second aspect of the embodiments of the present invention provides a battery pole piece, characterized in that, the battery pole piece includes: a positive electrode active material or a negative electrode active material, a conductive agent and the above-mentioned binder.
本发明实施例第二方面提供的电池极片，包括正极活性材料或者负极活性材料，导电剂，以及上述同时具有优异的粘接性能和导电性能的粘结剂，该粘结剂不但粘结性能好，对电极活性材料和导电剂能起到分散作用、增稠及防沉降作用，而且可改善电极片中活性材料之间的电子导电性，改善硅等电极活性材料在循环充放电过程中因体积膨胀收缩对电极片导电通路完整性的影响。因而，本发明实施例电池极片与集流体粘结力强，极片循环稳定性好。The battery pole piece provided in the second aspect of the embodiment of the present invention includes a positive electrode active material or a negative electrode active material, a conductive agent, and the above-mentioned binder having both excellent bonding performance and conductivity. The binder not only has bonding performance Good, it can disperse, thicken and prevent sedimentation of electrode active materials and conductive agents, and can improve the electronic conductivity between active materials in the electrode sheet, and improve the effect of silicon and other electrode active materials in the process of cyclic charge and discharge. The effect of volume expansion and contraction on the integrity of the conductive path of the electrode sheet. Therefore, in the embodiment of the present invention, the bonding force between the battery pole piece and the current collector is strong, and the cycle stability of the pole piece is good.
在一些实施例中，所述电池极片中，所述粘结剂的含量为1～10％；所述导电剂的含量为0.5～10％。本发明实施例电池极片中，导电剂可显著提高极片的导电性，若导电剂含量过小，则电极片电阻过大；若导电剂含量过大，则降低了极片的容量，影响电芯容量。电池极片中粘结剂的含量有效确保了极片的稳定性和导电性能，若粘结剂含量过小，则粘结强度过低，对极片体积膨胀的抑制效果差；若粘结剂含量过大，则影响极片中锂离子传输和电性能。在一些实施例中，电池极片中粘结剂的含量可以是1％、2％、3％、4％、5％、6％、7％、8％、9％或者10％等，导电剂的含量可以是0.5％、2％、4％、6％、8％或者10％等。In some embodiments, in the battery pole piece, the content of the binder is 1-10%; the content of the conductive agent is 0.5-10%. In the battery pole piece of the embodiment of the present invention, the conductive agent can significantly improve the conductivity of the pole piece. If the content of the conductive agent is too small, the resistance of the electrode piece will be too large; if the content of the conductive agent is too large, the capacity of the pole piece will be reduced, affecting the Cell capacity. The content of the binder in the battery pole piece can effectively ensure the stability and conductivity of the pole piece. If the binder content is too small, the bonding strength will be too low, and the effect of inhibiting the volume expansion of the pole piece will be poor; If the content is too large, it will affect the lithium ion transport and electrical properties in the pole piece. In some embodiments, the content of the binder in the battery pole piece may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc. The conductive agent The content can be 0.5%, 2%, 4%, 6%, 8% or 10% and so on.
在一些实施例中，所述导电剂包括：导电炭黑、科琴黑、导电碳纳米管、导电碳纤维中的至少一种，这些导电剂均具有优异的导电性，可显著提高极片的电导力。In some embodiments, the conductive agent includes at least one of conductive carbon black, ketjen black, conductive carbon nanotubes, and conductive carbon fibers, all of which have excellent conductivity and can significantly improve the conductivity of the pole piece force.
在一些实施例中，所述电池极片为正极片，包括：镍钴锰(NCM)三元材料，镍钴锰铝(NCMA)四元材料，镍钴铝(NCA)三元材料，磷酸铁锂(LFP)磷酸锰铁锂(LFMP)，钴酸锂(LCO)，锰酸锂(LMO)等正极材料中的至少一种正极活性材料，这些正极材料均具有较好的电化学性能。本发明实施例电池极片为正极片，极片中粘结剂可有效解决镍钴锰三元多晶等正极材料，在循环充放电过程中颗粒破裂引起的容量迅速下降问题。在一些具体实施例中，镍钴锰三元材料中，镍钴锰比例可以是424、333、523、701、515等。In some embodiments, the battery pole piece is a positive electrode piece, including: nickel-cobalt-manganese (NCM) ternary material, nickel-cobalt-manganese-aluminum (NCMA) quaternary material, nickel-cobalt-aluminum (NCA) ternary material, iron phosphate Lithium (LFP) Lithium Iron Manganese Phosphate (LFMP), Lithium Cobaltate (LCO), Lithium Manganate (LMO) and other cathode materials at least one cathode active material, these cathode materials have good electrochemical performance. The battery pole piece of the embodiment of the present invention is a positive pole piece, and the binder in the pole piece can effectively solve the problem of the rapid decrease of capacity caused by particle cracking during the cyclic charge and discharge process of positive pole materials such as nickel-cobalt-manganese ternary polycrystalline. In some specific embodiments, in the nickel-cobalt-manganese ternary material, the nickel-cobalt-manganese ratio may be 424, 333, 523, 701, 515, and the like.
在一些实施例中，所述电池极片为负极片，包括：Si、SiO、SiO2中的至少一种硅基负极活性材料，这些硅基活性材料克容量高，但在循环充放电过程中体积膨胀收缩形变很大，导致硅基材料颗粒易粉碎，极片脱落，导电通路断开，循环性能下降，通过本发明实施例电池极片中粘结剂可有效改善硅基活性材料在循环充放电过程中因体积膨胀收缩对电极片导电通路完整性的影响，改善电极片中硅基活性材料之间的电子导电性。In some embodiments, the battery pole piece is a negative electrode piece, including: at least one silicon-based negative electrode active material selected from Si, SiO, and SiO 2 . These silicon-based active materials have a high gram capacity, but can be used during cyclic charge and discharge. The volume expansion, contraction and deformation are very large, which leads to the easy crushing of silicon-based material particles, the falling off of the pole piece, the disconnection of the conductive path, and the decrease of the cycle performance. The influence of volume expansion and contraction on the integrity of the conductive path of the electrode sheet during the discharge process improves the electronic conductivity between the silicon-based active materials in the electrode sheet.
在一些实施例中，所述负极片的压实密度为1.50-1.85g/cm3；所述正极片的压实密度为3.2～3.8g/cm3。本发明实施例电池极片的压实密度既确保了极片的能量密度，又避免极片压实过大导致极片在充放电时体积膨胀反弹过大。若压实密度过小，则影响电芯厚度与能量密度，同时也不利于电性能；若压实密度过大，则极片被过压造成孔隙率低，影响电性能与循环性能，且充放电时体积膨胀反弹过大。In some embodiments, the compacted density of the negative electrode sheet is 1.50-1.85 g/cm 3 ; the compacted density of the positive electrode sheet is 3.2-3.8 g/cm 3 . The compaction density of the battery pole piece in the embodiment of the present invention not only ensures the energy density of the pole piece, but also prevents the pole piece from being too compacted and causing the pole piece to expand and rebound too much during charging and discharging. If the compaction density is too small, it will affect the thickness and energy density of the cell, and it is also not conducive to the electrical performance; if the compaction density is too large, the pole piece will be over-pressed, resulting in low porosity, affecting the electrical performance and cycle performance, and charging The volume expansion rebounds too much during discharge.
在一些实施例中，所述负极片中还包括碳材料，所述碳材料与所述硅基负极活性材料的质量比为(80～95)：(5～20)。在一些具体实施例中，碳材料包括人造石墨、天然石墨等石墨材料。本发明实施例负极片中由于硅基负极活性材料相比石墨类材料有很大的体积膨胀，会使得电池极片厚度超标，体积能量密度下降，同时体积膨胀大使得负极活性材料更易从集流体上脱落，造成电池循环性能快速下降，也不利于电池的安全性能。因而采用体积膨胀小的石墨材料与硅基负极材料以上述配比复合使用，降低极片的体积膨胀，提高极片的稳定性。若负极片中，硅基材料含量过低，则负极片容量太低，若硅基材料含量过高，则负极片体积膨胀率大，循环稳定性差。In some embodiments, the negative electrode sheet further includes a carbon material, and the mass ratio of the carbon material to the silicon-based negative electrode active material is (80-95):(5-20). In some specific embodiments, the carbon material includes graphite materials such as artificial graphite and natural graphite. In the negative electrode sheet of the embodiment of the present invention, since the silicon-based negative electrode active material has a large volume expansion compared with graphite materials, the thickness of the battery electrode sheet exceeds the standard, and the volumetric energy density decreases. The upper part falls off, resulting in a rapid decline in the battery cycle performance, which is also not conducive to the safety performance of the battery. Therefore, a graphite material with a small volume expansion and a silicon-based negative electrode material are used in combination with the above-mentioned ratio to reduce the volume expansion of the pole piece and improve the stability of the pole piece. If the content of silicon-based material in the negative electrode sheet is too low, the capacity of the negative electrode sheet is too low; if the content of silicon-based material is too high, the volume expansion rate of the negative electrode sheet is large and the cycle stability is poor.
本申请实施例电极片可通过以下实施例方法制得。The electrode sheets of the embodiments of the present application can be prepared by the following methods.
本发明实施例第三方面提供一种上述的电池极片的制备方法，包括步骤：将正极活性材料或者负极活性材料、导电剂和粘结剂分散在溶剂中形成电极浆料后，涂覆或沉积于集流体上，干燥得到电池极片。A third aspect of the embodiments of the present invention provides a method for preparing the above-mentioned battery pole piece, comprising the steps of: dispersing a positive electrode active material or a negative electrode active material, a conductive agent and a binder in a solvent to form an electrode slurry, coating or It is deposited on the current collector and dried to obtain a battery pole piece.
本发明实施例第三方面提供的电池极片的制备方法，通过将正极活性材料或者负极活性材料、导电剂和粘结剂分散在溶剂形成电极浆料后，涂覆或沉积在集流体上，干燥辊压即可得到负极片或者正极片，制备工艺简单，操作简便，适用于工业化大规模生产和应用。且制备的电池极片由于包含有上述具有优异的粘接性能和导电性能的粘结剂，不但使得电极浆料与集流体附着力强，而且可改善电极片中活性材料之间的电子导电性，提高导电通路的完整性。In the method for preparing a battery pole piece provided by the third aspect of the embodiment of the present invention, the positive electrode active material or the negative electrode active material, the conductive agent and the binder are dispersed in a solvent to form an electrode slurry, and then coated or deposited on the current collector, The negative electrode sheet or the positive electrode sheet can be obtained by dry rolling, the preparation process is simple, the operation is simple, and it is suitable for industrialized large-scale production and application. And the prepared battery pole piece contains the above-mentioned binder with excellent adhesion and electrical conductivity, which not only makes the electrode slurry and the current collector strong, but also improves the electronic conductivity between the active materials in the electrode piece. , improve the integrity of the conductive path.
在一些实施例中，将正极活性材料或者负极活性材料、导电剂和粘结剂分散在溶剂中形成电极浆料的步骤包括：In some embodiments, the step of dispersing the positive electrode active material or the negative electrode active material, the conductive agent and the binder in a solvent to form an electrode slurry includes:
将高分子粘结材料溶解在溶剂中并以1000-3000rpm的转速进行搅拌，搅拌均匀后添加导电聚合物，胶液固含量控制在10wt％(有利于后续告诉搅拌混合)，并在2000-4000rpm的转速下继续搅拌30-60分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。然后，添加导电剂并以2000-4000rpm的转速搅拌1-2小时。再添加硅基粉末等电极活性材料，以500～1000rpm的转速搅拌10～20分钟后，添加石墨粉末材料，以500～1000rpm的转速搅拌10～30分钟。然后，加入适量的溶剂，浆料固含量控制在50-70wt％(有利于后续告诉搅拌混合)，并在2000-4000rpm的转速下继续搅拌1-2小时，调整固含量到35-50wt％，再以500～1000rpm搅拌10～30分钟，控制电极浆料粘度在3000-9000cps，浆料粘度过大或过小都不利于涂布的控制。控制浆料的细度在40um以下，细度过大说明分散不充分，涂布易出现堵料且涂布精度不易控制。抽真空去掉气泡，使用150目筛网过滤，即制得电极浆料。Dissolve the polymer bonding material in the solvent and stir at a speed of 1000-3000rpm. After stirring evenly, add conductive polymer. Continue stirring for 30-60 minutes at a high speed to disperse the conductive adhesive evenly, and vacuumize to remove air bubbles to prepare the adhesive slurry. Then, the conductive agent is added and stirred at 2000-4000 rpm for 1-2 hours. Then add electrode active materials such as silicon-based powder, stir at 500-1000 rpm for 10-20 minutes, add graphite powder material, and stir at 500-1000 rpm for 10-30 minutes. Then, add an appropriate amount of solvent, the solid content of the slurry is controlled at 50-70wt% (conducive to the subsequent stirring and mixing), and continue to stir at 2000-4000rpm for 1-2 hours to adjust the solid content to 35-50wt%, Stir at 500 to 1000 rpm for 10 to 30 minutes, and control the electrode slurry viscosity to 3000-9000 cps. Too large or too small slurry viscosity is not conducive to coating control. Control the fineness of the slurry below 40um. If the fineness is too large, the dispersion is insufficient, and the coating is prone to blockage and the coating accuracy is not easy to control. Evacuate to remove air bubbles, and filter with a 150-mesh screen to obtain electrode slurry.
在一些实施例中，将分散均匀稳定的电极浆料通过涂布等方式沉积在集流体上，涂布速度可以是1～3m/min，涂布车间水分含量低于10％，避免水分对极片浆料的影响。然后在温度为80-110℃的条件下进行干燥，并对干燥后的极片进行辊压，得到稳定的电池极片。辊压后的极片可按照既定冲片模具制成设计需要的尺寸大小。In some embodiments, the electrode slurry with uniform and stable dispersion is deposited on the current collector by coating or other methods. The coating speed can be 1-3 m/min. Influence of flake slurry. Then, it is dried at a temperature of 80-110° C., and the dried pole piece is rolled to obtain a stable battery pole piece. The pole piece after rolling can be made into the size required by the design according to the established punching die.
在一些实施例中，溶剂可以是N-甲基吡咯烷(NMP)、酮醇、丙酮、水等。实际制备过程中可根据粘结剂的理化特性，选择溶解性好的溶剂制备电极浆料。In some embodiments, the solvent may be N-methylpyrrolidine (NMP), ketone alcohol, acetone, water, and the like. In the actual preparation process, according to the physical and chemical properties of the binder, a solvent with good solubility can be selected to prepare the electrode slurry.
本发明实施例第四方面提供一种二次电池，所述二次电池包含上述的电池极片，或者包含上述方法制备的电池极片。A fourth aspect of the embodiments of the present invention provides a secondary battery, wherein the secondary battery includes the above-mentioned battery pole piece, or includes the battery pole piece prepared by the above-mentioned method.
本发明实施例第四方面提供的二次电池，由于包含有上述克容量高，循环稳定性好，导电性优异的正极片或者负极片，因而二次电池使用寿命长，安全性高。The secondary battery provided by the fourth aspect of the embodiment of the present invention includes the above positive electrode or negative electrode sheet with high gram capacity, good cycle stability and excellent electrical conductivity, so the secondary battery has a long service life and high safety.
为使本发明上述实施细节和操作能清楚地被本领域技术人员理解，以及本发明实施例粘结剂、电池极片及其制备方法、二次电池的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。In order that the above-mentioned implementation details and operations of the present invention can be clearly understood by those skilled in the art, and the adhesives, battery pole pieces and preparation methods thereof, and the improved performance of the secondary batteries in the embodiments of the present invention can be clearly embodied, the following is through a number of Examples are given to illustrate the above technical solutions.
实施例1Example 1
一种粘结剂，包括质量比为1：1的PVDF高分子粘结材料和共聚酰亚胺聚合物导电聚合物：
一种负极片，其制备包括步骤：A negative electrode sheet, the preparation of which comprises the steps:
①将2份PVDF添加到溶剂NMP中进行并以2000rpm的转速进行搅拌，在搅拌均匀后添加2份的导电聚合物，控制胶液固含量在10wt％，并在3000rpm的转速下继续搅拌40分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 2 parts of PVDF to the solvent NMP and stir at a speed of 2000rpm. After stirring evenly, add 2 parts of conductive polymer, control the solid content of the glue to 10wt%, and continue to stir at a speed of 3000rpm for 40 minutes The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以3000rpm的转速搅拌2小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 2 hours at a rotation speed of 3000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入14份的硅粉末材料，以500rpm的转速搅拌10分钟后，加入80份的石墨粉末材料，以500rpm的转速搅拌10分钟，然后加入适量的NMP溶剂，浆料固含量控制在60wt％，并在3000rpm的转速下继续搅拌2小时，加入NMP调整固含量在42wt％，再以500rpm搅拌10分钟，控制负极浆料粘度在6000cps。3. Add 14 parts of silicon powder material to the above conductive glue, stir at 500rpm for 10 minutes, add 80 parts of graphite powder material, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, the slurry solidifies. The content was controlled at 60 wt%, and the stirring was continued at 3000 rpm for 2 hours. NMP was added to adjust the solid content to 42 wt%, and then stirred at 500 rpm for 10 minutes to control the negative electrode slurry viscosity at 6000 cps.
④将过筛网后的浆料涂布于铜箔集流体上进行烘干，烘箱温度在100℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the sieved slurry on the copper foil current collector for drying. The oven temperature is between 100°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的负极片进行辊压，控制极片的辊压密度在1.70g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到负极片。5. Rolling the above-mentioned coated negative electrode sheet, controlling the rolling density of the electrode sheet to be 1.70 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a negative electrode sheet .
一种二次电池，将负极片、NCM三元正极材料、隔膜一起进行层叠、封装、注液、化成、老化、分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。The utility model relates to a secondary battery. The negative electrode sheet, the NCM ternary positive electrode material, and the separator are laminated, packaged, liquid injected, chemically formed, aged, and capacity separated to obtain a soft-packed battery cell. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
实施例2Example 2
一种粘结剂，包括质量比为1：2的PVDF高分子粘结材料和共聚酰亚胺聚合物导电聚合物：
一种负极片，其制备包括步骤：A negative electrode sheet, the preparation of which comprises the steps:
①将1份PVDF添加到溶剂NMP中进行并以2000rpm的转速进行搅拌，在搅拌均匀后添加2份的导电聚合物，控制胶液固含量在10wt％，并在4000rpm的转速下继续搅拌30分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 1 part of PVDF to the solvent NMP and stir at a speed of 2000rpm. After stirring evenly, add 2 parts of conductive polymer to control the solid content of the glue at 10wt%, and continue to stir at a speed of 4000rpm for 30 minutes The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以4000rpm的转速搅拌1小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 1 hour at a rotation speed of 4000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入15份的硅粉末材料，以500rpm的转速搅拌10分钟后，加入80份的石墨粉末材料，以500rpm的转速搅拌10分钟，然后加入适量的NMP溶剂，浆料固含量控制在50wt％，并在4000rpm的转速下继续搅拌1小时，加入NMP调整固含量在35wt％，再以500rpm搅拌10分钟，控制负极浆料粘度在3000cps。③ Add 15 parts of silicon powder material to the above conductive glue, stir at 500rpm for 10 minutes, add 80 parts of graphite powder material, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, the slurry is solidified. The content was controlled at 50 wt%, and the stirring was continued at 4000 rpm for 1 hour. NMP was added to adjust the solid content to 35 wt%, and then stirred at 500 rpm for 10 minutes to control the viscosity of the negative electrode slurry at 3000 cps.
④将过筛网后的浆料涂布于铜箔集流体上进行烘干，烘箱温度在80℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the sieved slurry on the copper foil current collector for drying. The oven temperature is between 80°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的负极片进行辊压，控制极片的辊压密度在1.65g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到负极片。5. Rolling the above-mentioned coated negative electrode sheet, controlling the rolling density of the electrode sheet to be 1.65 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a negative electrode sheet .
一种二次电池，将负极片、NCM三元正极材料、隔膜一起进行层叠、封装、注液、化成、老化、分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。The utility model relates to a secondary battery. The negative electrode sheet, the NCM ternary positive electrode material, and the separator are laminated, packaged, liquid injected, chemically formed, aged, and capacity separated to obtain a soft-packed battery cell. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
实施例3Example 3
一种粘结剂，包括质量比为1：4的PVDF高分子粘结材料和共聚酰亚胺聚合物导电聚合物：
一种负极片，其制备包括步骤：A negative electrode sheet, the preparation of which comprises the steps:
①将1份PVDF添加到溶剂NMP中进行并以1000rpm的转速进行搅拌，在搅拌均匀后添加4份的导电聚合物，控制胶液固含量在10wt％，并在2000rpm的转速下继续搅拌60分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 1 part of PVDF to the solvent NMP and stir at a speed of 1000rpm. After stirring evenly, add 4 parts of conductive polymer to control the solid content of the glue to 10wt%, and continue to stir for 60 minutes at a speed of 2000rpm. The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以2000rpm的转速搅拌2小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 2 hours at a rotation speed of 2000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入14份的硅粉末材料，以500rpm的转速搅拌10分钟后，加入79份的石墨粉末材料，以500rpm的转速搅拌10分钟，然后加入适量的NMP溶剂，浆料固含量控制在70wt％，并在2000rpm的转速下继续搅拌2小时，加入NMP调整固含量在50wt％，再以500rpm搅拌10分钟，控制负极浆料粘度在9000cps。③ Add 14 parts of silicon powder material to the above conductive glue, stir at 500rpm for 10 minutes, add 79 parts of graphite powder material, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, the slurry is solidified. The content was controlled at 70 wt%, and the stirring was continued at 2000 rpm for 2 hours. NMP was added to adjust the solid content to 50 wt%, and then stirred at 500 rpm for 10 minutes to control the viscosity of the negative electrode slurry at 9000 cps.
④将过筛网后的浆料涂布于铜箔集流体上进行烘干，烘箱温度在110℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the slurry after screening on the copper foil current collector for drying. The oven temperature is between 110°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的负极片进行辊压，控制极片的辊压密度在1.60g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到负极片。5. Rolling the above-mentioned coated negative electrode sheet, controlling the rolling density of the polar sheet to be 1.60 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a negative electrode sheet .
一种二次电池，将负极片、NCM三元正极材料、隔膜一起进行层叠、封装、注液、化成、老化、分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。The utility model relates to a secondary battery. The negative electrode sheet, the NCM ternary positive electrode material, and the separator are laminated, packaged, liquid injected, chemically formed, aged, and capacity separated to obtain a soft-packed battery cell. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
实施例4Example 4
一种粘结剂，包括质量比为1：1的PVDF高分子粘结材料和聚芴聚合物导电聚合物：
一种负极片，其制备包括步骤：A negative electrode sheet, the preparation of which comprises the steps:
①将2份PVDF添加到溶剂NMP中进行并以2000rpm的转速进行搅拌，在搅拌均匀后添加2份的导电聚合物，控制胶液固含量在10wt％，并在3000rpm的转速下继续搅拌40分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 2 parts of PVDF to the solvent NMP and stir at a speed of 2000rpm. After stirring evenly, add 2 parts of conductive polymer, control the solid content of the glue to 10wt%, and continue to stir at a speed of 3000rpm for 40 minutes The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以3000rpm的转速搅拌2小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 2 hours at a rotation speed of 3000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入14份的硅粉末材料，以500rpm的转速搅拌10分钟后，加入80份的石墨粉末材料，以500rpm的转速搅拌10分钟，然后加入适量的NMP溶剂，浆料固含量控制在60wt％，并在3000rpm的转速下继续搅拌2小时，加入NMP调整固含量在42wt％，再以500rpm搅拌10分钟，控制负极浆料粘度在6000cps。3. Add 14 parts of silicon powder material to the above conductive glue, stir at 500rpm for 10 minutes, add 80 parts of graphite powder material, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, the slurry solidifies. The content was controlled at 60 wt%, and the stirring was continued at 3000 rpm for 2 hours. NMP was added to adjust the solid content to 42 wt%, and then stirred at 500 rpm for 10 minutes to control the negative electrode slurry viscosity at 6000 cps.
④将过筛网后的浆料涂布于铜箔集流体上进行烘干，烘箱温度在100℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the sieved slurry on the copper foil current collector for drying. The oven temperature is between 100°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的负极片进行辊压，控制极片的辊压密度在1.70g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到负极片。5. Rolling the above-mentioned coated negative electrode sheet, controlling the rolling density of the electrode sheet to be 1.70 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a negative electrode sheet .
一种二次电池，将负极片、NCM三元正极材料、隔膜一起进行层叠、封装、注液、化成、老化、分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。The utility model relates to a secondary battery. The negative electrode sheet, the NCM ternary positive electrode material, and the separator are laminated, packaged, liquid injected, chemically formed, aged, and capacity separated to obtain a soft-packed battery cell. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
实施例5Example 5
一种粘结剂，包括质量比为1：2的PVDF高分子粘结材料和聚芴聚合物导电聚合物：
一种负极片，其制备包括步骤：A negative electrode sheet, the preparation of which comprises the steps:
①将1份PVDF添加到溶剂NMP中进行并以2000rpm的转速进行搅拌，在搅拌均匀后添加2份的导电聚合物，控制胶液固含量在10wt％，并在4000rpm的转速下继续搅拌30分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 1 part of PVDF to the solvent NMP and stir at a speed of 2000rpm. After stirring evenly, add 2 parts of conductive polymer to control the solid content of the glue at 10wt%, and continue to stir at a speed of 4000rpm for 30 minutes The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以4000rpm的转速搅拌1小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 1 hour at a rotation speed of 4000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入15份的硅粉末材料，以500rpm的转速搅拌10分钟后，加入80份的石墨粉末材料，以500rpm的转速搅拌10分钟，然后加入适量的NMP溶剂，浆料固含量控制在50wt％，并在4000rpm的转速下继续搅拌1小时，加入NMP调整固含量在35wt％，再以500rpm搅拌10分钟，控制负极浆料粘度在3000cps。③ Add 15 parts of silicon powder material to the above conductive glue, stir at 500rpm for 10 minutes, add 80 parts of graphite powder material, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, the slurry is solidified. The content was controlled at 50 wt%, and the stirring was continued at 4000 rpm for 1 hour. NMP was added to adjust the solid content to 35 wt%, and then stirred at 500 rpm for 10 minutes to control the viscosity of the negative electrode slurry at 3000 cps.
④将过筛网后的浆料涂布于铜箔集流体上进行烘干，烘箱温度在80℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the sieved slurry on the copper foil current collector for drying. The oven temperature is between 80°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的负极片进行辊压，控制极片的辊压密度在1.65g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到负极片。5. Rolling the above-mentioned coated negative electrode sheet, controlling the rolling density of the electrode sheet to be 1.65 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a negative electrode sheet .
一种二次电池，将负极片、NCM三元正极材料、隔膜一起进行层叠、封装、注液、化成、老化、分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。The utility model relates to a secondary battery. The negative electrode sheet, the NCM ternary positive electrode material, and the separator are laminated, packaged, liquid injected, chemically formed, aged, and capacity separated to obtain a soft-packed battery cell. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
实施例6Example 6
一种粘结剂，包括质量比为1：4的PVDF高分子粘结材料和聚芴聚合物导电聚合物：
一种负极片，其制备包括步骤：A negative electrode sheet, the preparation of which comprises the steps:
①将1份PVDF添加到溶剂NMP中进行并以1000rpm的转速进行搅拌，在搅拌均匀后添加4份的导电聚合物，控制胶液固含量在10wt％，并在2000rpm的转速下继续搅拌60分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 1 part of PVDF to the solvent NMP and stir at a speed of 1000rpm. After stirring evenly, add 4 parts of conductive polymer to control the solid content of the glue to 10wt%, and continue to stir for 60 minutes at a speed of 2000rpm. The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以2000rpm的转速搅拌2小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 2 hours at a rotation speed of 2000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入14份的硅粉末材料，以500rpm的转速搅拌10分钟后，加入79份的石墨粉末材料，以500rpm的转速搅拌10分钟，然后加入适量的NMP溶剂，浆料固含量控制在70wt％，并在2000rpm的转速下继续搅拌2小时，加入NMP调整固含量在50wt％，再以500rpm搅拌10分钟，控制负极浆料粘度在9000cps。③ Add 14 parts of silicon powder material to the above conductive glue, stir at 500rpm for 10 minutes, add 79 parts of graphite powder material, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, the slurry is solidified. The content was controlled at 70 wt%, and the stirring was continued at 2000 rpm for 2 hours. NMP was added to adjust the solid content to 50 wt%, and then stirred at 500 rpm for 10 minutes to control the viscosity of the negative electrode slurry at 9000 cps.
④将过筛网后的浆料涂布于铜箔集流体上进行烘干，烘箱温度在110℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the slurry after screening on the copper foil current collector for drying. The oven temperature is between 110°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的负极片进行辊压，控制极片的辊压密度在1.60g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到负极片。5. Rolling the above-mentioned coated negative electrode sheet, controlling the rolling density of the polar sheet to be 1.60 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a negative electrode sheet .
一种二次电池，将负极片、NCM三元正极材料、隔膜一起进行层叠、封装、注液、化成、老化、分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。The utility model relates to a secondary battery. The negative electrode sheet, the NCM ternary positive electrode material, and the separator are laminated, packaged, liquid injected, chemically formed, aged, and capacity separated to obtain a soft-packed battery cell. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
实施例7Example 7
一种粘结剂，包括质量比为1：1的PVDF高分子粘结材料和共聚酰亚胺聚合物导电聚合物：
一种正极片，其制备包括步骤：A positive electrode sheet, the preparation of which comprises the steps:
①将2份PVDF添加到溶剂NMP中进行并以2000rpm的转速进行搅拌，在搅拌均匀后添加2份的导电聚合物，控制胶液固含量在10wt％，并在3000rpm的转速下继续搅拌40分钟使导电粘结剂分散均匀，抽真空去掉气泡制得粘结剂浆料。①Add 2 parts of PVDF to the solvent NMP and stir at a speed of 2000rpm. After stirring evenly, add 2 parts of conductive polymer, control the solid content of the glue to 10wt%, and continue to stir at a speed of 3000rpm for 40 minutes The conductive adhesive is uniformly dispersed, and the air bubbles are removed by vacuuming to prepare the adhesive slurry.
②向粘结剂浆料中加入2份的乙炔黑以3000rpm的转速搅拌2小时，得到导电胶液。②Add 2 parts of acetylene black to the binder slurry and stir for 2 hours at a rotation speed of 3000 rpm to obtain a conductive glue solution.
③向上述导电胶液中加入94份的NCM811三元多晶材料，以500rpm的转速搅拌10分钟后，然后加入适量的NMP溶剂，浆料固含量控制在80wt％，并在3000rpm的转速下继续搅拌2小时，加入NMP调整固含量在70wt％，再以500rpm搅拌10分钟，控制正极浆料粘度在6000cps。③ Add 94 parts of NCM811 ternary polycrystalline material to the above conductive glue, stir at 500rpm for 10 minutes, then add an appropriate amount of NMP solvent, control the solid content of the slurry at 80wt%, and continue at 3000rpm Stir for 2 hours, add NMP to adjust the solid content at 70 wt %, and stir at 500 rpm for 10 minutes to control the viscosity of the positive electrode slurry at 6000 cps.
④将过筛网后的浆料涂布于铝箔集流体上进行烘干，烘箱温度在100℃间，涂布速度在2m/min，涂布车间水分含量低于10％。④ Coat the slurry after screening on the aluminum foil current collector for drying. The oven temperature is between 100°C, the coating speed is 2m/min, and the moisture content in the coating workshop is less than 10%.
⑤将上述涂布后的正极片进行辊压，控制极片的辊压密度在3.50g/cm3，将辊压后的极片按照既定冲片模具制成设计需要的尺寸大小，得到正极片。⑤ Rolling the above-mentioned coated positive electrode sheet, controlling the rolling density of the electrode sheet to be 3.50 g/cm 3 , and making the rolled electrode sheet into the size required by the design according to a predetermined punching die to obtain a positive electrode sheet .
一种二次电池，将正极片，硅基材料混石墨制得的负极片，隔膜一起进行层叠，封装，注液，化成，老化，分容等工序，制得软包电芯。其中隔膜厚度为16um，封装铝塑膜的厚度为152um。A secondary battery, a positive electrode sheet, a negative electrode sheet prepared by mixing a silicon-based material with graphite, and a separator are laminated together, encapsulated, liquid injected, chemically formed, aged, and divided into volumes to obtain a soft-packed battery core. The thickness of the diaphragm is 16um, and the thickness of the packaging aluminum-plastic film is 152um.
对比例1Comparative Example 1
对比例1与实施例1的区别在于：粘结剂仅含有PVDF高分子粘结材料；负极片中含有3份PVDF高分子粘结材料、2份导电剂和15份硅粉末材料。The difference between Comparative Example 1 and Example 1 is that the binder only contains PVDF polymer binder material; the negative electrode sheet contains 3 parts of PVDF polymer binder material, 2 parts of conductive agent and 15 parts of silicon powder material.
对比例2Comparative Example 2
对比例2与实施例1的区别在于：粘结剂仅含有PVDF高分子粘结材料；负极片中含有12份PVDF高分子粘结材料、2份导电剂和6份硅粉末材料。The difference between Comparative Example 2 and Example 1 is that the binder only contains PVDF polymer binder material; the negative electrode sheet contains 12 parts of PVDF polymer binder material, 2 parts of conductive agent and 6 parts of silicon powder material.
对比例3Comparative Example 3
对比例3与实施例1的区别在于：负极片中含有4份PVDF高分子粘结材料、8份导电聚合物、2份导电剂和6份硅粉末材料。The difference between Comparative Example 3 and Example 1 is that the negative electrode sheet contains 4 parts of PVDF polymer binder material, 8 parts of conductive polymer, 2 parts of conductive agent and 6 parts of silicon powder material.
对比例4Comparative Example 4
对比例4与实施例3的区别在于：粘结剂中PVDF与共聚酰亚胺聚合物导电聚合物的质量比为1：8；负极片中含有0.5份的PVDF，4份的导电聚合物，2份的导电剂和14份的硅粉末材料。The difference between Comparative Example 4 and Example 3 is that the mass ratio of PVDF and copolyimide polymer conductive polymer in the binder is 1:8; the negative electrode sheet contains 0.5 parts of PVDF, 4 parts of conductive polymer, 2 parts of conductive agent and 14 parts of silicon powder material.
对比例5Comparative Example 5
对比例5与实施例3的区别在于：粘结剂中PVDF与共聚酰亚胺聚合物导电聚合物的质量比为3:1；负极片中含有3份的PVDF，1份的导电聚合物，2份的导电剂和14份的硅粉末材料。The difference between Comparative Example 5 and Example 3 is that the mass ratio of PVDF and copolyimide polymer conductive polymer in the binder is 3:1; the negative electrode sheet contains 3 parts of PVDF, 1 part of conductive polymer, 2 parts of conductive agent and 14 parts of silicon powder material.
对比例6Comparative Example 6
对比例6与实施例1的区别在于：n为1100～2000的整数。The difference between Comparative Example 6 and Example 1 is that n is an integer of 1100-2000.
进一步的，为了验证本发明实施例的进步性，对上述实施例和对比例制备的电池极片及二次电池进行了如下表1性能测试，统计各个实施例1～7中电池极片的欧姆阻抗、剥离强度，以及成品软包电池室温条件下1/3C的循环性能与DCR(直流阻抗)增长情况，循环电压范围为2.5-4.25V。Further, in order to verify the progress of the embodiments of the present invention, the battery pole pieces and secondary batteries prepared in the above-mentioned examples and comparative examples were subjected to the following performance tests in Table 1, and the ohmic values of the battery pole pieces in each of Examples 1 to 7 were counted. Impedance, peel strength, 1/3C cycle performance and DCR (direct current resistance) growth of the finished soft pack battery at room temperature, and the cycle voltage range is 2.5-4.25V.
表1Table 1
由上表1测试结果可知，实施例1～7制备的负极片、正极片均有较高极片剥离强度，面电阻小，电池容量保持率高，循环稳定好，DCR直流阻抗增长率小，综合性能优异。需要说明的是，实施例7的正极极片本身的粘结性比实施例1～6的负极片好，此外，正极片的面电阻也一般比负极片要大很多，因为负极片中负极材料中有较多量的石墨材料，导电性更好。From the test results in Table 1 above, it can be seen that the negative electrode sheets and positive electrode sheets prepared in Examples 1 to 7 have high polar sheet peeling strength, small surface resistance, high battery capacity retention rate, good cycle stability, and small DCR DC impedance growth rate. Excellent overall performance. It should be noted that the adhesion of the positive electrode sheet itself in Example 7 is better than that of the negative electrode sheets in Examples 1 to 6. In addition, the surface resistance of the positive electrode sheet is generally much larger than that of the negative electrode sheet, because the negative electrode material in the negative electrode sheet There is a larger amount of graphite material, and the conductivity is better.
通过实施例1～6和对比例1比较可知，对比例1粘结剂中未加入导电聚合物制作的硅基负极极片的剥离强度，明显小于实施例1～6粘结剂中导电聚合物的硅基负极极片。同时，对比例1极片的面电阻比实施例的面电阻要高；循环性能测试结果表明，对比例1在1/3C循环300圈后，其容量保持率在71％-73％，容量保持率小于实施例，且软包电芯的DCR增长率大于实施例。本发明实施例1～6粘结剂中导电聚合物，具有导电特性同时还具有粘结作用，一方面改善了硅与石墨间的电子导电性，同时也改善了硅在循环膨胀收缩过程中的导电通路完整性，改善了从而改善了硅负极电池的循环性能。By comparing Examples 1 to 6 with Comparative Example 1, it can be seen that the peel strength of the silicon-based negative electrode piece made of no conductive polymer added to the binder of Comparative Example 1 is significantly lower than that of the conductive polymer in the binders of Examples 1 to 6. The silicon-based negative pole piece. At the same time, the sheet resistance of the comparative example 1 is higher than that of the example; the cycle performance test results show that the capacity retention rate of the comparative example 1 is 71%-73% after 300 cycles at 1/3C, and the capacity retention The rate is smaller than that of the embodiment, and the DCR growth rate of the soft-packed cell is larger than that of the embodiment. The conductive polymers in the binders in Examples 1 to 6 of the present invention have conductive properties and also have a bonding effect. On the one hand, the electronic conductivity between silicon and graphite is improved, and at the same time, it also improves the performance of silicon in the process of cyclic expansion and contraction. The integrity of the conductive path is improved thereby improving the cycle performance of the silicon anode battery.
通过实施例1～6和对比例2～3比较可知，当电池极片中粘结剂含量过高时，虽然能在一定程度上增加极片的剥离强度，但极片的面电阻增加，电池的容量保持率下降，DCR增长率增大。By comparing Examples 1 to 6 with Comparative Examples 2 to 3, it can be seen that when the binder content in the battery pole piece is too high, although the peel strength of the pole piece can be increased to a certain extent, the surface resistance of the pole piece increases, and the battery The capacity retention rate decreased and the DCR growth rate increased.
通过实施例1～6和对比例4～5比较可知，当粘结剂中高分子粘结材料含量过高，或者导电聚合物含量过高时，电池容量保持率下降，DCR增长率增大，同样不利于提高电池的循环稳定性。By comparing Examples 1 to 6 with Comparative Examples 4 to 5, it can be seen that when the content of polymer binder in the binder is too high, or the content of conductive polymer is too high, the battery capacity retention rate decreases and the DCR growth rate increases. Similarly It is not conducive to improving the cycle stability of the battery.
通过实施例1～6和对比例6比较可知，当粘结剂中导电聚合物分子量过大时，电池容量保持率下降，DCR增长率增大，同样不利于提高电池的循环稳定性。By comparing Examples 1 to 6 with Comparative Example 6, it can be seen that when the molecular weight of the conductive polymer in the binder is too large, the battery capacity retention rate decreases and the DCR growth rate increases, which is also unfavorable to improve the battery cycle stability.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
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