CN114479713A - Composite conductive adhesive and preparation method and application thereof - Google Patents
Composite conductive adhesive and preparation method and application thereof Download PDFInfo
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- CN114479713A CN114479713A CN202210187311.8A CN202210187311A CN114479713A CN 114479713 A CN114479713 A CN 114479713A CN 202210187311 A CN202210187311 A CN 202210187311A CN 114479713 A CN114479713 A CN 114479713A
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- solution
- composite conductive
- coupling agent
- silane coupling
- alginate
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 239000000853 adhesive Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229920002098 polyfluorene Polymers 0.000 claims abstract description 21
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 60
- 235000010443 alginic acid Nutrition 0.000 claims description 58
- 229920000615 alginic acid Polymers 0.000 claims description 58
- 229940072056 alginate Drugs 0.000 claims description 57
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 229940095102 methyl benzoate Drugs 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000002322 conducting polymer Substances 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052710 silicon Inorganic materials 0.000 abstract description 30
- 239000010703 silicon Substances 0.000 abstract description 30
- 239000007773 negative electrode material Substances 0.000 abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000006258 conductive agent Substances 0.000 abstract description 6
- 238000010298 pulverizing process Methods 0.000 abstract description 4
- 239000011856 silicon-based particle Substances 0.000 abstract description 4
- 230000002238 attenuated effect Effects 0.000 abstract 1
- 239000005543 nano-size silicon particle Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 238000005303 weighing Methods 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000737 potassium alginate Substances 0.000 description 7
- 235000010408 potassium alginate Nutrition 0.000 description 7
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 7
- 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 description 6
- 239000011149 active material Substances 0.000 description 6
- 239000000661 sodium alginate Substances 0.000 description 6
- 235000010413 sodium alginate Nutrition 0.000 description 6
- 229940005550 sodium alginate Drugs 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920005598 conductive polymer binder Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/04—Alginic acid; Derivatives thereof
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
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- 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
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite conductive adhesive and a preparation method and application thereof, wherein the composite conductive adhesive comprises the following components: the conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative. Therefore, the composite conductive binder has good conductivity, bonding performance and protection on a silicon-based negative electrode SEI film, has good strength and toughness, can solve the problems that the existing lithium ion battery needs to use a conductive agent and a binder simultaneously, so that the energy density of a battery core and the first coulombic efficiency are low, and can also solve the problems that the existing binder molecules cannot restrict the falling and pulverization of micro-nano-scale silicon particles, so that poor electric contact is caused, the performance of a silicon-based negative electrode material is continuously deteriorated, and the cycle performance is finally quickly attenuated.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a composite conductive adhesive as well as a preparation method and application thereof.
Background
With the increasing prominence of global environmental problems and energy problems, lithium ion batteries are receiving more and more attention and application as clean and renewable secondary energy sources, and particularly in recent years, with the rapid development of electric automobiles, the lithium ion batteries are greatly developed and advanced, but even though new application scenes put higher requirements on rate capability, energy density, cycle life, coulombic efficiency and the like of the lithium ion batteries. The performance of the lithium ion battery depends on the quality of the positive and negative electrode active materials and the binder and other materials which form the battery.
At present, the actual specific capacity of the traditional graphite negative electrode material is close to the theoretical specific capacity 372mAh/g, and is gradually one of bottlenecks which restrict the continuous improvement of the energy density of the lithium ion battery. Meanwhile, the maximum theoretical specific capacity of the silicon negative electrode material which is expected for a long time can reach 4200mAh/g, and the silicon negative electrode material is concerned more and becomes one of few research hotspots which can last for years, which is not separated from the bright application prospect and the huge application challenge. The application challenges include: 1) during the charging and discharging process, the Li-Si alloying/dealloying can generate serious volume expansion/shrinkage which can reach more than 300 percent (Li)4.4Si), resulting in silicon particles cracking, pulverization, loss of activity, poor cycle performance; 2) the fragmentation of silicon particles in the charging and discharging process causes poor electrical contact between an active substance and a current collector to form an island effect and damage of an SEI film on a fracture surface, and a new SEI film is repeatedly formed, so that irreversible capacity loss and low coulombic efficiency are caused; 3) silicon is a semiconductor and exhibits low electrical conductivity (10)-5～10-3S·cm-1) And ion diffusion coefficient (10)-14～10-13cm2·s-1) Resulting in a decrease in the kinetic performance of lithium ion diffusion.
To promote the application of silicon cathodes, the scientific and industrial circles put forward many theories and many attempts have been made. With the continuous and deep recognition, some attempts have good effects, especially the proposal and application of measures such as silicon nanocrystallization, silicon-carbon recombination, carbon coating, pre-lithiation and the like, so that the silicon negative electrode material gradually enters practical application, and still has many problems to be solved.
In the lithium ion secondary battery, the volume change of the negative electrode material is positively correlated with the doping amount of silicon in the process of lithium extraction and lithium insertion. Therefore, with the increase of the silicon doping amount, the risks of peeling, falling, cracking and pulverization of the negative electrode material are increased along with the aggravation of volume expansion and shrinkage of the negative electrode end of the lithium battery during charging and discharging, and various application problems such as poor conductivity, structural damage of the battery, low coulombic efficiency, continuous reduction of irreversible capacity and the like are caused. Accordingly, the importance of a high-performance binder has been recognized, and it has been desired to develop a binder having excellent toughness, allowing a certain volume expansion of a negative electrode material, and having excellent binding and conductive properties. Obviously, the traditional binders for lithium battery negative electrodes in the market, namely Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC), are insufficient for new application scenarios, and new binders need to be developed to solve related problems. The solutions in the industry are mostly developed along two ideas, one idea is to modify and compound Styrene Butadiene Rubber (SBR) and sodium carboxymethyl cellulose (CMC), but according to the related results, the adhesive of the type still cannot solve the problem of adhesion with silicon materials, and the phenomena and the problems mentioned above are still serious; the other idea is to research and develop a conductive polymer binder, and try to make up and solve the problems that a silicon material is poor in conductivity, an SEI film is repeatedly formed and decomposed, and an active material is continuously consumed, but although the conductivity of a system is enhanced, the adhesion of the material to a current collector and the silicon-based material is weak, and the material is not satisfactory.
Therefore, there is a need to develop a high performance binder.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one object of the present invention is to provide a composite conductive adhesive, a preparation method and an application thereof, wherein the composite conductive adhesive has good conductivity, adhesive property and protection property on a silicon-based negative electrode SEI film, and has good strength and toughness, and can solve the problems of low cell energy density and low first coulombic efficiency caused by the need of using a conductive agent and an adhesive at the same time in the existing lithium ion battery, and also solve the problems of poor electrical contact, continuous deterioration of the performance of a silicon-based negative electrode material, rapid decay of cycle performance caused by the fact that the existing adhesive molecules cannot restrict the falling and pulverization of micro-nano-scale silicon particles, and the like.
In one aspect of the invention, a composite conductive adhesive is provided. According to an embodiment of the present invention, the composite conductive adhesive comprises: the conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative.
The composite conductive adhesive comprises a conductive polymer, alginate and a silane coupling agent, wherein the conductive polymer comprises at least one of polypyrene methacrylate, polypyrene methacrylate derivatives, polyfluorene-based polymers and polyfluorene-based polymer derivatives, the formation of a pyrene methyl ordered structure is promoted by the flexible skeleton structure of the polypyrene methacrylate and the derivatives thereof, so that the polymer generates excellent conductivity, the interaction between pyrene methyl and nano silicon particles is promoted, the polypyrene methyl and the nano silicon particles can be completely covered on the surface of a nano silicon particle or a silicon carbon negative electrode, and in the volume change process of lithium removal and embedding, the active material can be well covered, the contact between the nano silicon particles and an electrolyte is reduced, the continuous consumption of the electrolyte is prevented, and the stability of a negative electrode SEI film is improved; meanwhile, the polyfluorene-based polymer and the derivatives thereof have good thermal stability and good compatibility with electrolyte, and can react with polar groups on the surface of silicon to form strong chemical bonds, so that the mechanical integrity and good conductivity of the electrode after the charging and discharging process are really maintained. In addition, the alginate acid radical groups in the alginate have low swelling rate and good shape retention, the arrangement of carboxyl groups on a molecular chain is regular and uniform, the content is high, the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate acid radical groups can form a stable SEI film through hydrogen bonds with hydroxyl groups on the surfaces of nano silicon particles, so that the polarity is large, the adhesion force is stronger, the nano silicon particles can be effectively prevented from agglomerating and falling off, a proper amount of alginate acid radical groups can also generate a synergistic effect with part of conductive polymers on the protection SEI film, and the stability of the negative electrode SEI film is further improved. In addition, the silane coupling agent is used, so that on one hand, the binding force between the composite conductive adhesive and the nano silicon particles can be improved; on the other hand, the crosslinking of the conductive polymer and the alginate radical group can be promoted, so that the composite conductive adhesive forms an organic three-dimensional network structure; on the other hand, the strong adhesion property of the silane coupling agent and the metallic material can greatly improve the adhesion capability of the composite conductive adhesive on the current collector metal plate, fully show the crosslinking, reinforcing and toughening effects of the composite conductive adhesive, and integrate the current collector metal plate, the composite conductive adhesive and the silicon-based negative electrode material into an organic whole. In conclusion, the composite conductive binder has good conductivity, bonding performance and protection on a silicon-based negative electrode SEI film, and has good strength and toughness, so that the silicon-carbon negative electrode material can be ensured to be well used under the condition of higher silicon content, the specific capacity of the negative electrode material can be improved, the use of a conductive agent in a lithium battery negative electrode can be reduced or cancelled, the content of active substances in the silicon-carbon negative electrode is increased, the specific capacity of the negative electrode material is further improved, the energy density of a battery is increased, meanwhile, the composite conductive binder protects the SEI film, and the first coulombic efficiency and the cycle performance of the battery can be improved.
In addition, the composite conductive adhesive according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the mass ratio of the conductive polymer to the alginate is (1: 3) to (6: 1). Therefore, the composite conductive adhesive has good conductivity, good adhesive property and good protection to a silicon-based negative electrode SEI film.
In some embodiments of the invention, the silane coupling agent comprises 0.1% to 10% of the total mass of the conductive polymer, the alginate, and the silane coupling agent. Therefore, the composite conductive adhesive has good conductivity, good adhesive property and good protection to a silicon-based negative electrode SEI film.
In some embodiments of the present invention, the polypyrene methacrylate derivative comprises at least one of polypyrene methacrylate-co-methacrylic acid and polypyrene methacrylate-co-trivinyloxymethylene methacrylate.
In some embodiments of the present invention, the polyfluorenyl polymer derivative comprises at least one of polyfluorenyl polymer-co-fluorenone and polyfluorenyl polymer-co-fluorenone-co-methylbenzoate.
In some embodiments of the invention, the silane coupling agent comprises at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and gamma- (methacryloyloxy) propyltriethoxysilane.
In a second aspect of the invention, the invention provides a method for preparing the composite conductive adhesive. According to an embodiment of the invention, the method comprises:
(1) mixing a conductive polymer, alginate and a solvent to obtain a mixed solution;
(2) and (3) carrying out mixing reaction on a silane coupling agent and the mixed solution so as to obtain the composite conductive adhesive.
According to the method for preparing the composite conductive adhesive, the conductive polymer, the alginate and the solvent are mixed to obtain a mixed solution containing the conductive polymer and the alginate; and then, carrying out mixing reaction on a silane coupling agent and the mixed solution, carrying out complex polymerization reaction on groups such as hydroxyl, carboxyl and the like generated by hydrolysis of the silane coupling agent and groups such as hydroxyl, carboxyl and the like of the conductive polymer and the alginate, and obtaining the composite conductive adhesive after the reaction is finished. The conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative, the flexible skeleton structure of the polypyrene methacrylate and the polypyrene methacrylate derivative promotes the formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, and also promotes the interaction between pyrene methyl and nano silicon particles, so that the polymer can completely cover the surface of a nano silicon particle or a silicon carbon negative electrode, and in the volume change process of lithium intercalation removal, the active material can be well covered, the contact between the nano silicon particle and an electrolyte is reduced, the continuous consumption of the electrolyte is prevented, and the stability of an SEI film of the negative electrode is improved; meanwhile, the polyfluorene-based polymer and the derivatives thereof have good thermal stability and good compatibility with electrolyte, and can react with polar groups on the surface of silicon to form strong chemical bonds, so that the mechanical integrity and good conductivity of the electrode after the charging and discharging process are really maintained. In addition, the alginate acid radical groups in the alginate have low swelling rate and good shape retention, the arrangement of carboxyl groups on a molecular chain is regular and uniform, the content is high, the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate acid radical groups can form a stable SEI film through hydrogen bonds with hydroxyl groups on the surfaces of nano silicon particles, so that the polarity is large, the adhesion force is stronger, the nano silicon particles can be effectively prevented from agglomerating and falling off, a proper amount of alginate acid radical groups can also generate a synergistic effect with part of conductive polymers on the protection SEI film, and the stability of the negative electrode SEI film is further improved. In addition, the silane coupling agent is used, so that on one hand, the binding force between the composite conductive adhesive and the nano silicon particles can be improved; on the other hand, the crosslinking of the conductive polymer and the alginate radical group can be promoted, so that the composite conductive adhesive forms an organic three-dimensional network structure; on the other hand, the strong adhesion property of the silane coupling agent and the metallic material can greatly improve the adhesion capability of the composite conductive adhesive on the current collector metal plate, fully show the crosslinking, reinforcing and toughening effects of the composite conductive adhesive, and integrate the current collector metal plate, the composite conductive adhesive and the silicon-based negative electrode material into an organic whole. To sum up, the composite conductive binder prepared by the method has good conductivity, bonding performance and protection on a silicon-based negative electrode SEI film, and has good strength and toughness, so that the silicon-carbon negative electrode material can be ensured to be well used under the condition of higher silicon content, the specific capacity of the negative electrode material can be favorably improved, the use of a conductive agent in a lithium battery negative electrode can be reduced or cancelled, the content of active substances in the silicon-carbon negative electrode is increased, the specific capacity of the negative electrode material is further improved, the energy density of a battery is increased, meanwhile, the composite conductive binder protects the SEI film, and the first coulomb efficiency and the cycle performance of the battery can be favorably improved.
In addition, the method for preparing the composite conductive adhesive according to the embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, step (1) further comprises: (i) mixing the conductive polymer with a first solvent to obtain a conductive polymer solution; (ii) mixing the alginate with a second solvent to obtain an alginate solution; (iii) mixing the conductive polymer solution with the alginate solution to obtain a mixed solution.
In some embodiments of the present invention, in the step (i), the mass concentration of the conductive polymer in the conductive polymer solution is 10% to 50%.
In some embodiments of the invention, in step (ii), the alginate solution has a mass concentration of alginate of 10% to 50%.
In some embodiments of the present invention, in the step (2), the temperature of the mixing reaction is 20 to 80 ℃.
In some embodiments of the invention, step (2) further comprises: (a) mixing the silane coupling agent with a third solvent to obtain a silane coupling agent solution; (b) and adding the silane coupling agent solution into the mixed solution, and standing for 1-24 hours to obtain the composite conductive adhesive.
In some embodiments of the invention, step (2) further comprises: (c) mixing the silane coupling agent with a third solvent to obtain a silane coupling agent solution; (d) mixing the silane coupling agent solution with an acidic solution to hydrolyze the silane coupling agent, and then adding an alkaline solution to adjust the pH value to 6-8 so as to obtain a pretreated solution; (e) and mixing the pretreated solution with the mixed solution to obtain the composite conductive adhesive.
In a third aspect of the invention, a negative electrode is presented. According to an embodiment of the invention, the negative electrode contains the composite conductive binder or the composite conductive binder prepared by the method. Therefore, the negative electrode has higher specific capacity, first coulombic efficiency and excellent cycle performance.
In a fourth aspect of the invention, a battery is provided. According to an embodiment of the present invention, the battery contains the above-described negative electrode. Therefore, the battery has higher specific capacity, first coulombic efficiency and excellent cycle performance.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing the composite conductive adhesive according to one embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method of preparing the composite conductive adhesive according to yet another embodiment of the present invention;
FIG. 3 is a schematic flow chart of a method of preparing the composite conductive adhesive according to yet another embodiment of the present invention;
fig. 4 is a flow chart illustrating a method of preparing the composite conductive adhesive according to yet another embodiment of the present invention.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In a first aspect of the invention, a composite conductive adhesive is provided. According to an embodiment of the present invention, the composite conductive adhesive includes: the conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative.
The inventor finds that the composite conductive adhesive comprises a conductive polymer, alginate and a silane coupling agent, wherein the conductive polymer comprises at least one of polypyrene methacrylate, polypyrene methacrylate derivatives, polyfluorene-based polymer and polyfluorene-based polymer derivatives, the flexible skeleton structure of the polypyrene methacrylate and the derivatives thereof promotes the formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, and also promotes the interaction between pyrene methyl and nano silicon particles, so that the polypyrene methyl and the nano silicon particles can be completely covered on the surface of a nano silicon particle or a silicon carbon negative electrode, and in the volume change process of lithium removal and embedding, the active material can be well covered, the contact between the nano silicon particles and an electrolyte is reduced, the continuous consumption of the electrolyte is prevented, and the stability of a negative electrode SEI film is improved; meanwhile, the polyfluorene-based polymer and the derivatives thereof have good thermal stability and good compatibility with electrolyte, and can react with polar groups on the surface of silicon to form strong chemical bonds, so that the mechanical integrity and good conductivity of the electrode after the charging and discharging process are really maintained. In addition, the alginate acid radical groups in the alginate have low swelling rate and good shape retention, the arrangement of carboxyl groups on a molecular chain is regular and uniform, the content is high, the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate acid radical groups can form a stable SEI film through hydrogen bonds with hydroxyl groups on the surfaces of nano silicon particles, so that the polarity is large, the adhesion force is stronger, the nano silicon particles can be effectively prevented from agglomerating and falling off, a proper amount of alginate acid radical groups can also generate a synergistic effect with part of conductive polymers on the protection SEI film, and the stability of the negative electrode SEI film is further improved. In addition, the silane coupling agent is used, so that on one hand, the binding force between the composite conductive adhesive and the nano silicon particles can be improved; on the other hand, the crosslinking of the conductive polymer and the alginate radical group can be promoted, so that the composite conductive adhesive forms an organic three-dimensional network structure; on the other hand, the strong adhesion property of the silane coupling agent and the metallic material can greatly improve the adhesion capability of the composite conductive adhesive on the current collector metal plate, fully show the crosslinking, reinforcing and toughening effects of the composite conductive adhesive, and integrate the current collector metal plate, the composite conductive adhesive and the silicon-based negative electrode material into an organic whole. In conclusion, the composite conductive binder has good conductivity, bonding performance and protection on a silicon-based negative electrode SEI film, and has good strength and toughness, so that the silicon-carbon negative electrode material can be ensured to be well used under the condition of higher silicon content, the specific capacity of the negative electrode material can be improved, the use of a conductive agent in a lithium battery negative electrode can be reduced or cancelled, the content of active substances in the silicon-carbon negative electrode is increased, the specific capacity of the negative electrode material is further improved, the energy density of a battery is increased, meanwhile, the composite conductive binder protects the SEI film, and the first coulombic efficiency and the cycle performance of the battery can be improved.
Further, the mass ratio of the conductive polymer to the alginate is (1: 3) to (6: 1). The inventors found that if the mass ratio is too small, the conductivity of the composite conductive adhesive will be weakened; if the mass ratio is too large, the adhesion of the composite conductive adhesive will be weakened. Only if the two are in a proper ratio, the optimum overall performance can be produced. Further, the silane coupling agent accounts for 0.1-10% of the total mass of the conductive polymer, the alginate and the silane coupling agent. The inventor finds that if the silane coupling agent is added too little, a good cross-linking network and a three-dimensional structure are difficult to form, and the bonding capability of the composite conductive adhesive is reduced; if the silane coupling agent is added too much, the conductivity of the composite conductive adhesive is affected. Therefore, the composite conductive adhesive prepared by adopting the addition amount of the silane coupling agent has good conductive performance and adhesive performance.
It should be noted that, the specific types of the polypyrene methacrylate derivatives, polyfluorene-based polymer derivatives, alginates and silane coupling agents can be selected by those skilled in the art according to actual needs, for example, the polypyrene methacrylate derivatives include at least one of polypyrene methacrylate-co-methacrylic acid and polypyrene methacrylate-co-triethylene methyl ether oxide methacrylate; the polyfluorenyl polymer derivative comprises at least one of polyfluorenyl polymer-co-fluorenone and polyfluorenyl polymer-co-fluorenone-co-methylbenzoate; the alginate comprises at least one of sodium alginate, potassium alginate and lithium alginate; the silane coupling agent includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and gamma- (methacryloyloxy) propyltriethoxysilane.
In a second aspect of the invention, the invention provides a method for preparing the composite conductive adhesive. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing conductive polymer, alginate and solvent
In the step, a mixed solution containing the conductive polymer and the alginate can be obtained by mixing the conductive polymer, the alginate and the solvent. It should be noted that the specific types and mixing ratios of the conductive polymer and the alginate are the same as those described above, and are not described herein again. Specifically, referring to fig. 2, first, a conductive polymer is mixed with a first solvent to obtain a conductive polymer solution with a mass concentration of 10% to 50%, and simultaneously, an alginate is mixed with a second solvent to obtain an alginate solution with a mass concentration of 10% to 50%, and then, the conductive polymer solution and the alginate solution are mixed and stirred uniformly to obtain the mixed solution. It is noted that the specific type of the first solvent and the second solvent is the same, including but not limited to at least one of deionized water, alcohols, ketones, esters, and hydrocarbons.
S200: mixing silane coupling agent and mixed solution for reaction
In the step, a silane coupling agent and the mixed solution obtained in the step S100 are mixed and reacted, and the composite conductive adhesive can be obtained after the reaction is finished. It should be noted that the specific type and addition amount of the silane coupling agent are the same as those described above, and are not described herein again. Further, the temperature of the mixing reaction is 20-80 ℃. The inventor finds that if the reaction temperature is too low, the agglomeration phenomenon of each component is serious, and the hydrolysis speed of the silane coupling agent is slow; if the reaction temperature is too high, the solvent is seriously volatilized, which is not favorable for obtaining the stable and uniform composite conductive adhesive. Therefore, by adopting the reaction temperature, the components can be prevented from agglomerating, the hydrolysis of the silane coupling agent is accelerated, and the stable and uniform composite conductive adhesive is obtained. Specifically, referring to fig. 3, a silane coupling agent is mixed with a third solvent to obtain a silane coupling agent solution with a mass concentration of 10% -40%, and then the silane coupling agent solution is added into the mixed solution and stands for 1-24 hours to obtain the composite conductive adhesive. Preferably, referring to fig. 4, adding 5 to 10 drops of an acidic solution with a concentration of 0.15mol/L to 0.25mol/L, preferably 0.2mol/L, to the silane coupling agent solution to fully hydrolyze the silane coupling agent, then adding an alkaline solution to adjust the pH to 6 to 8, so as to facilitate formation of a good three-dimensional cross-linked network during a later mixing reaction, obtaining a pretreated solution, finally mixing the pretreated solution with the mixed solution, and performing a complex polymerization reaction on groups such as hydroxyl groups and carboxyl groups generated by hydrolysis of the silane coupling agent and groups such as hydroxyl groups and carboxyl groups of a conductive polymer and alginate, thereby obtaining the composite conductive adhesive. It should be noted that the specific types of the acidic solution and the basic solution can be selected by those skilled in the art according to actual needs, for example, the acidic solution includes at least one of acetic acid and acetic anhydride; the alkaline solution includes at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide, and the specific type of the third solvent is the same as that of the first solvent, which is not described herein again.
The inventors found that by mixing a conductive polymer, an alginate, and a solvent, a mixed solution containing the conductive polymer and the alginate is obtained; and then, carrying out mixing reaction on a silane coupling agent and the mixed solution, carrying out complex polymerization reaction on groups such as hydroxyl, carboxyl and the like generated by hydrolysis of the silane coupling agent and groups such as hydroxyl, carboxyl and the like of the conductive polymer and the alginate, and obtaining the composite conductive adhesive after the reaction is finished. The conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative, the flexible skeleton structure of the polypyrene methacrylate and the polypyrene methacrylate derivative promotes the formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, and also promotes the interaction between pyrene methyl and nano silicon particles, so that the polymer can completely cover the surface of a nano silicon particle or a silicon carbon negative electrode, and in the volume change process of lithium intercalation removal, the active material can be well covered, the contact between the nano silicon particle and an electrolyte is reduced, the continuous consumption of the electrolyte is prevented, and the stability of an SEI film of the negative electrode is improved; meanwhile, the polyfluorene-based polymer and the derivatives thereof have good thermal stability and good compatibility with electrolyte, and can react with polar groups on the surface of silicon to form strong chemical bonds, so that the mechanical integrity and good conductivity of the electrode after the charging and discharging process are really maintained. In addition, the alginate acid radical groups in the alginate have low swelling rate and good shape retention, the arrangement of carboxyl groups on a molecular chain is regular and uniform, the content is high, the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate acid radical groups can form a stable SEI film through hydrogen bonds with hydroxyl groups on the surfaces of nano silicon particles, so that the polarity is large, the adhesion force is stronger, the nano silicon particles can be effectively prevented from agglomerating and falling off, a proper amount of alginate acid radical groups can also generate a synergistic effect with part of conductive polymers on the protection SEI film, and the stability of the negative electrode SEI film is further improved. In addition, the silane coupling agent is used, so that on one hand, the binding force between the composite conductive adhesive and the nano silicon particles can be improved; on the other hand, the crosslinking of the conductive polymer and the alginate radical group can be promoted, so that the composite conductive adhesive forms an organic three-dimensional network structure; on the other hand, the strong adhesion characteristic of the silane coupling agent and the metallic material can greatly improve the adhesion capability of the composite conductive adhesive on the current collector metal plate, fully show the crosslinking, reinforcing and toughening effects of the composite conductive adhesive, and integrate the current collector metal plate, the composite conductive adhesive and the silicon-based negative electrode material into an organic whole. To sum up, the composite conductive binder prepared by the method has good conductivity, bonding performance and protection on a silicon-based negative electrode SEI film, and has good strength and toughness, so that the silicon-carbon negative electrode material can be ensured to be well used under the condition of higher silicon content, the specific capacity of the negative electrode material can be favorably improved, the use of a conductive agent in a lithium battery negative electrode can be reduced or cancelled, the content of active substances in the silicon-carbon negative electrode is increased, the specific capacity of the negative electrode material is further improved, the energy density of a battery is increased, meanwhile, the composite conductive binder protects the SEI film, and the first coulomb efficiency and the cycle performance of the battery can be favorably improved.
In a third aspect of the invention, a negative electrode is presented. According to an embodiment of the invention, the negative electrode contains the composite conductive binder or the composite conductive binder prepared by the method. Therefore, the negative electrode has higher specific capacity, first coulombic efficiency and excellent cycle performance. It should be noted that the specific types of the active material and the current collector of the negative electrode and the specific preparation manner of the negative electrode are conventional in the art, and the features and advantages described above for the composite conductive binder and the preparation method thereof are also applicable to the negative electrode, and are not described herein again.
In a fourth aspect of the invention, a battery is provided. According to an embodiment of the present invention, the battery contains the above-described negative electrode. Therefore, the battery has higher specific capacity, first coulombic efficiency and excellent cycle performance. It should be noted that the specific types of the positive electrode, the electrolyte and the separator of the battery and the specific assembly manner of the battery are conventional in the art, and the features and advantages described above for the negative electrode also apply to the battery, and are not described herein again.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Weighing 100g of water and 200g of acetone, mixing and stirring uniformly, heating to 60 ℃, then weighing 100g of conductive polymer polypyrene methacrylate, adding the conductive polymer polypyrene methacrylate into a mixed solvent consisting of the water and the acetone, and fully stirring uniformly to prepare a polypyrene methacrylate solution with the mass concentration of 25%.
(2) Weighing 200g of water and 100g of acetone, mixing and stirring uniformly, heating to 60 ℃, then weighing 100g of potassium alginate, adding the potassium alginate into a mixed solvent consisting of the water and the acetone, and stirring uniformly to prepare a potassium alginate solution with the mass concentration of 25%.
(3) Then mixing and stirring the two solutions uniformly to obtain a mixed solution, and keeping the temperature at 60 ℃.
(4) Weighing 10g of water and 10g of acetone, mixing and stirring uniformly, heating to 40 ℃, then weighing 5g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, adding the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a mixed solvent consisting of the water and the acetone, and stirring uniformly to prepare a silane coupling agent solution with the mass concentration of 20%.
(5) Adding 8 drops of 0.2mol/L acetic acid solution into the silane coupling agent solution, hydrolyzing for about 30 minutes under the stirring condition to fully hydrolyze the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, then adding a little of 0.2mol/L sodium hydroxide solution into the hydrolyzed silane coupling agent solution, adjusting the pH value to 7, adding the mixture into the mixed solution, and stirring uniformly to obtain the composite conductive adhesive 1.
Example 2
(1) Weighing 150g of water and 250g of ethanol, mixing and stirring uniformly, heating to 50 ℃, then weighing 150g of conductive polymer polypyrene methacrylate-co-methacrylic acid, adding the conductive polymer polypyrene methacrylate-co-methacrylic acid into a mixed solvent consisting of water and ethanol, and stirring uniformly to prepare a polypyrene methacrylate solution with the mass concentration of 27.3%.
(2) Weighing 150g of water and 100g of ethanol, mixing and stirring uniformly, heating to 50 ℃, then weighing 70g of sodium alginate, adding the sodium alginate into a mixed solvent consisting of the water and the ethanol, and stirring uniformly to prepare an alginate solution with the mass concentration of 21.9%.
(3) Then mixing and stirring the two solutions uniformly to obtain a mixed solution, and keeping the temperature at 50 ℃.
(4) Weighing 10g of water and 10g of ethanol, mixing and stirring uniformly, heating to 40 ℃, then weighing 3g of vinyl trimethoxy silane, adding into a mixed solvent consisting of water and ethanol, and stirring uniformly to prepare a silane coupling agent solution with the mass concentration of 13%.
(5) Directly adding the modified silane coupling agent solution which is just prepared into the mixed solution, fully mixing, uniformly stirring, and standing for 12 hours under the condition of keeping the temperature at 50 ℃ to obtain the composite conductive adhesive 2.
Example 3
The polypyrene methacrylate in example 1 was replaced with polyfluorenyl polymer-co-fluorenone, and a composite conductive adhesive 3 was prepared in the same manner as in example 1.
Example 4
A composite conductive adhesive 4 was prepared in the same manner as in example 2 except that the polypyrene methacrylate-co-methacrylic acid in example 2 was replaced with the polyfluorenyl polymer-co-fluorenone-co-methylbenzoate.
Comparative example 1
(1) Weighing 100g of water and 200g of acetone, mixing and stirring uniformly, heating to 60 ℃, then weighing 100g of conductive polymer polypyrene methacrylate, adding the conductive polymer polypyrene methacrylate into a mixed solvent consisting of the water and the acetone, and fully stirring uniformly to prepare a polypyrene methacrylate solution with the mass concentration of 25%.
(2) Weighing 200g of water and 100g of acetone, mixing and stirring uniformly, heating to 60 ℃, then weighing 100g of potassium alginate, adding the potassium alginate into a mixed solvent consisting of the water and the acetone, and stirring uniformly to prepare a potassium alginate solution with the mass concentration of 25%.
(3) And then mixing and uniformly stirring the two solutions to obtain a mixed solution, adjusting the pH value of the mixed solution to 8 by using sodium hydroxide, and obtaining a contrast binder 1 without modifying by using a silane coupling agent.
Comparative example 2
Weighing 600g of water, heating to 60 ℃, then weighing 200g of sodium alginate, adding the sodium alginate into hot water, fully stirring to prepare a sodium alginate solution with the mass concentration of 25%, and adjusting the pH value of the composite conductive adhesive to 6 by using sodium hydroxide to obtain a contrast adhesive 2.
Comparative example 3
Weighing 600g of water, heating to 60 ℃, then weighing 150g of sodium carboxymethylcellulose (CMC) and 50g of Styrene Butadiene Rubber (SBR), adding the weighed sodium carboxymethylcellulose and styrene butadiene rubber into hot water in sequence, and fully stirring to obtain the contrast binder 3.
Comparative example 4
600g of water is weighed, heated to 60 ℃, and then 200g of sodium carboxymethylcellulose (CMC) is weighed, added into hot water, and fully stirred to obtain the contrast binder 4.
Performance testing and analysis
According to the silicon-based material: flake graphite: adhesive: the mass ratio of the asphalt is 4:12:1:3 (the binder is the binder with the same solid content in the above examples and comparative examples), the silicon-carbon negative electrode material is prepared under the same parameters of pressure, temperature and the like, and then electrochemical performance test (counter electrode: pure lithium sheet, electrolyte: New Zebra LBC-A28) and mechanical peeling test are respectively carried out, and the test results are shown in tables 1 and 2:
TABLE 1 electrochemical Performance test results of button cells prepared in examples and comparative examples
Table 2 results of mechanical peeling test of negative electrodes manufactured in examples and comparative examples
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A composite conductive adhesive, comprising: the conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative.
2. The composite conductive adhesive according to claim 1, wherein the mass ratio of the conductive polymer to the alginate is (1: 3) - (6: 1).
3. The composite conductive adhesive as claimed in claim 1 or 2, wherein the silane coupling agent accounts for 0.1-10% of the total mass of the conductive polymer, the alginate and the silane coupling agent.
4. The composite conductive adhesive according to claim 3, wherein the polypyrene methacrylate derivative comprises at least one of polypyrene methacrylate-co-methacrylic acid and polypyrene methacrylate-co-triethenoxymethyl ether methacrylate;
optionally, the polyfluorenyl polymer derivative comprises at least one of polyfluorenyl polymer-co-fluorenone and polyfluorenyl polymer-co-fluorenone-co-methylbenzoate;
optionally, the silane coupling agent includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and gamma- (methacryloyloxy) propyltriethoxysilane.
5. A method for preparing the composite conductive adhesive according to any one of claims 1 to 4, comprising:
(1) mixing a conductive polymer, alginate and a solvent to obtain a mixed solution;
(2) and (3) carrying out mixing reaction on a silane coupling agent and the mixed solution so as to obtain the composite conductive adhesive.
6. The method of claim 5, wherein step (1) further comprises: (i) mixing the conductive polymer with a first solvent to obtain a conductive polymer solution; (ii) mixing the alginate with a second solvent to obtain an alginate solution; (iii) mixing the conductive polymer solution with the alginate solution to obtain a mixed solution,
optionally, in step (i), the mass concentration of the conducting polymer in the conducting polymer solution is 10% to 50%;
optionally, in the step (ii), the mass concentration of alginate in the alginate solution is 10-50%;
optionally, in the step (2), the temperature of the mixing reaction is 20-80 ℃.
7. The method of claim 5 or 6, wherein step (2) further comprises: (a) mixing the silane coupling agent with a third solvent to obtain a silane coupling agent solution; (b) and adding the silane coupling agent solution into the mixed solution, and standing for 1-24 hours to obtain the composite conductive adhesive.
8. The method of claim 5 or 6, wherein step (2) further comprises: (c) mixing the silane coupling agent with a third solvent to obtain a silane coupling agent solution; (d) mixing the silane coupling agent solution with an acidic solution to hydrolyze the silane coupling agent, and then adding an alkaline solution to adjust the pH to 6-8 so as to obtain a pretreated solution; (e) and mixing the pretreated solution with the mixed solution to obtain the composite conductive adhesive.
9. A negative electrode, characterized in that the negative electrode contains the composite conductive binder of any one of claims 1 to 4 or the composite conductive binder prepared by the method of any one of claims 5 to 8.
10. A battery comprising the negative electrode according to claim 9.
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