CN116478640A - Biomass/polyacrylate composite binder and preparation method and application thereof - Google Patents
Biomass/polyacrylate composite binder and preparation method and application thereof Download PDFInfo
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- CN116478640A CN116478640A CN202310465974.6A CN202310465974A CN116478640A CN 116478640 A CN116478640 A CN 116478640A CN 202310465974 A CN202310465974 A CN 202310465974A CN 116478640 A CN116478640 A CN 116478640A
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- biomass
- polyacrylate
- composite binder
- polyacrylate composite
- mixed solution
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 88
- 239000011230 binding agent Substances 0.000 title claims abstract description 62
- 239000002028 Biomass Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005303 weighing Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001263 FEMA 3042 Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- 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 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 241000220479 Acacia Species 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002593 electrical impedance tomography Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a biomass/polyacrylate composite binder, and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, weighing 0.01 to 0.1 weight part of biomass material, dissolving 0.001 to 0.010 weight part of metal salt in 8 to 15 weight parts of deionized water, and uniformly stirring to obtain a mixed solution; step 2, transferring the polyacrylate emulsion into a reactor with a condenser tube, taking the mixed solution obtained in the step 1, slowly dripping the mixed solution into the polyacrylate emulsion according to the mass of the biomass material accounting for 0.1-1% of the polyacrylate, and stirring and reacting for 6-10 h at 20-80 ℃ to obtain the biomass/polyacrylate composite binder; the prepared biomass/polyacrylate composite binder not only maintains good flexibility of polyacrylate, but also effectively improves adhesion performance, mechanical performance and electrochemical performance, and has the advantages of simple preparation method, safety, environmental protection and low cost by taking water as a solvent.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a composite binder, and in particular relates to a biomass/polyacrylate composite binder, and a preparation method and application thereof.
Background
Under the push of the increasing power demands of energy storage systems such as electronic products and electric vehicles, research on lithium ion batteries with high energy density has been continuously conducted for the past few decades. Silicon is considered to be a promising negative electrode material because of its high theoretical specific capacity. However, during the cycling, silicon undergoes a large volume change, causing the silicon particles to shatter and the electrodes to delaminate, resulting in a rapid decay of the capacity. The polymer binder can provide cohesion between the active material and the conductive agent, maintain the structural integrity of the electrode, and further improve the service life and cycle performance of the battery.
The aqueous binder has the characteristics of no solvent release, low cost, high safety and the like, and has become the development direction of the lithium ion battery binder. The polyacrylate binder has good film forming property and electrochemical property, can well inhibit expansion of the silicon-based negative electrode, and improves the cycle performance of the battery. However, the polyacrylate binder also has the defects of low adhesion, low mechanical strength and the like, so that the electrochemical performance of the silicon-based negative electrode still has a large improvement space. The composite binder can overcome the defect of a single binder and has great significance for promoting the industrialized application of the silicon-based negative electrode.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a biomass/polyacrylate composite binder, and a preparation method and application thereof, which not only reserves good flexibility of polyacrylate, but also effectively improves adhesive property, mechanical property and electrochemical property.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the biomass/polyacrylate composite binder comprises the following steps:
step 1, weighing 0.01 to 0.1 weight part of biomass material, dissolving 0.001 to 0.010 weight part of metal salt in 8 to 15 weight parts of deionized water, and uniformly stirring to obtain a mixed solution;
and 2, transferring the polyacrylate emulsion into a reactor with a condenser tube, taking the mixed solution obtained in the step 1, slowly dripping the mixed solution into the polyacrylate emulsion according to the mass of the biomass material accounting for 0.1-1% of the polyacrylate, and stirring and reacting for 6-10 h at 20-80 ℃ to obtain the biomass/polyacrylate composite binder.
The invention also has the following technical characteristics:
preferably, the biomass material in step 1 comprises any one or a mixture of a plurality of sodium alginate, tannic acid, acacia, xanthan gum and chitosan in any proportion.
Preferably, the metal salt in step 1 comprises a mixture of one or more of copper chloride, ferric chloride, zinc chloride and calcium chloride in any proportion.
Preferably, one end of the polyacrylate in the step 2 is a hydrophilic chain segment containing polar groups; the other end is a hydrophobic chain segment of an ABA structure.
Further, the polar group includes a carboxyl group and an amide group.
Further, A is polymethyl methacrylate chain segment or polystyrene chain segment, and the polymerization degree is 100-350.
Further, the B is any one of a polyethyl acrylate chain segment, a polybutyl acrylate chain segment and a isooctyl acrylate chain segment, and the polymerization degree is as follows: 300 to 700.
The invention also protects the biomass/polyacrylate composite binder prepared by the method and application of the biomass/polyacrylate composite binder in the silicon-based negative electrode of the lithium ion battery.
Compared with the prior art, the invention has the following technical effects:
the invention comprises carboxyl andthe polyamide-based polyacrylate is taken as a main chain, and is crosslinked with polar groups in metal ions and biomass materials through interaction of metal coordination bonds and hydrogen bonds to obtain a composite binder with a three-dimensional network structure, and through the synergistic effect among the metal ions, the biomass materials and the polyacrylate, good flexibility of the polyacrylate is reserved, and the composite binder is applied to a silicon-based negative electrode of a lithium ion battery, has good adhesion performance, mechanical property and electrochemical property, the stripping force can reach 0.7N, and the first discharge specific capacity of the battery reaches 534.90 mAh.g under the 0.1C multiplying power -1 Coulombic efficiency was 93.59%;
the composite binder and the active substance have rich binding sites, so that the binder and the active substance have stronger interfacial binding capacity, and the silicon-based negative electrode can better bear the volume change in the charge and discharge processes of the electrode;
the preparation method is simple, uses water as a solvent, and is safe, environment-friendly and low in cost.
Drawings
FIG. 1 is a graph showing peel strength test of the biomass/polyacrylate composite adhesive prepared in example 5 as a silicon oxygen negative electrode;
FIG. 2 is a stress-strain curve of the biomass/polyacrylate composite adhesive prepared in example 5;
FIG. 3 is an electrochemical impedance test chart of the biomass/polyacrylate composite adhesive prepared in example 5;
FIG. 4 is a first charge and discharge curve of the biomass/polyacrylate composite binder prepared in example 5;
fig. 5 is the coulombic efficiency of the biomass/polyacrylate composite binder prepared in example 5.
Detailed Description
The following examples illustrate the invention in further detail.
In the following examples, one end of the polyacrylate is a hydrophilic chain segment containing a polar group; the other end is a hydrophobic chain segment of an ABA structure; polar groups include carboxyl and amide groups; a is polymethyl methacrylate chain segment or polystyrene chain segment, and the polymerization degree is: 100-350 parts; b is any one of a polyethyl acrylate chain segment, a polybutyl acrylate chain segment and a isooctyl acrylate chain segment, and the polymerization degree is as follows: 300 to 700.
Example 1
The embodiment provides a preparation method of a biomass/polyacrylate composite binder, which comprises the following steps:
step 1, weighing 0.01 part by weight of guar gum, dissolving 0.010 part by weight of copper chloride in 15 parts by weight of deionized water, and uniformly stirring to obtain a mixed solution;
and 2, weighing 1 part by weight of polyacrylate emulsion, transferring the polyacrylate emulsion into a reactor with a condenser pipe, slowly dropwise adding the mixed solution obtained in the step 1 into the polyacrylate emulsion, and stirring at 20 ℃ for reaction for 6 hours to obtain the biomass/polyacrylate composite binder.
Example 2
The embodiment provides a preparation method of a biomass/polyacrylate composite binder, which comprises the following steps:
step 1, weighing 0.03 weight part of sodium alginate, dissolving 0.008 weight part of zinc chloride in 15 weight parts of deionized water, and uniformly stirring to obtain a mixed solution;
and 2, weighing 30 parts by weight of polyacrylate emulsion, transferring the polyacrylate emulsion to a reactor with a condenser pipe, slowly dropwise adding the mixed solution obtained in the step 1 into the polyacrylate emulsion, and stirring and reacting for 10 hours at 30 ℃ to obtain the biomass/polyacrylate composite binder.
Example 3
The embodiment provides a preparation method of a biomass/polyacrylate composite binder, which comprises the following steps:
step 1, weighing 0.1 part by weight of tannic acid, dissolving 0.001 part by weight of calcium chloride in 10 parts by weight of deionized water, and uniformly stirring to obtain a mixed solution;
and step 2, weighing 55 parts by weight of polyacrylate emulsion, transferring the polyacrylate emulsion into a reactor with a condenser pipe, slowly dripping the mixed solution obtained in the step 1 into the polyacrylate emulsion, and stirring and reacting for 8 hours at 40 ℃ to obtain the biomass/polyacrylate composite binder.
Example 4
The embodiment provides a preparation method of a biomass/polyacrylate composite binder, which comprises the following steps:
step 1, weighing 0.05 part by weight of xanthan gum, dissolving 0.005 part by weight of ferric chloride in 8 parts by weight of deionized water, and uniformly stirring to obtain a mixed solution;
and 2, weighing 100 parts by weight of polyacrylate emulsion, transferring the polyacrylate emulsion to a reactor with a condenser pipe, slowly dripping the mixed solution obtained in the step 1 into the polyacrylate emulsion, and stirring at 80 ℃ for reaction for 6 hours to obtain the biomass/polyacrylate composite binder.
Example 5
The embodiment provides a preparation method of a biomass/polyacrylate composite binder, which comprises the following steps:
step 1, weighing 0.05 part by weight of tannic acid, dissolving 0.002 part by weight of ferric chloride in 15 parts by weight of deionized water, and uniformly stirring to obtain a mixed solution;
and 2, weighing 50 parts by weight of polyacrylate emulsion, transferring the polyacrylate emulsion into a reactor with a condenser pipe, slowly dropwise adding the mixed solution obtained in the step 1 into the polyacrylate emulsion, and stirring at 60 ℃ for reacting for 8 hours to obtain the biomass/polyacrylate composite binder.
The biomass/polyacrylate composite binder prepared in example 5 is used as a silicon-oxygen negative electrode binder, is mixed with a silicon-oxygen active material, a conductive agent and CMC according to the conventional proportion in the prior art to prepare slurry, is coated on a copper foil and dried to prepare an electrode slice, and is subjected to a peeling test according to the national standard GB/T2792-2014, the peeling force can reach 0.7N as shown in figure 1, and compared with the polyacrylate binder, the peeling strength is greatly improved, so that the biomass/polyacrylate composite binder prepared in example 5 can better bond the active material, the conductive agent and the copper foil together.
The biomass/polyacrylate composite adhesive prepared in example 5 was formed into a film, and the mechanical properties of the dried latex film were measured at room temperature with a stretching speed of 25mm/min and a weighing sensor of 50 kgf. As shown in FIG. 2, the mechanical strength and elongation at break of the biomass/polyacrylate composite adhesive can reach 17.86MPa and 349.57%, which are 7.29 times and 1.28 times that of the polyacrylate adhesive respectively. The biomass material and the polyacrylate are crosslinked to form a three-dimensional network structure due to the synergistic effect of the hydrogen bond and the metal coordination bond, so that the connection between molecular chains is enhanced, and the mechanical property of the adhesive is improved.
The biomass/polyacrylate composite binder prepared in example 5 was used as a silicon-oxygen negative electrode binder to prepare a lithium ion battery, and the electrochemical performance of the lithium ion battery was tested at 25 ℃. FIG. 3 is a graph showing electrochemical impedance measurements of polyacrylate binder and biomass/polyacrylate composite binder, from which it can be seen that R is the electrode prepared from biomass/polyacrylate composite binder ct 、R SEI The preparation method is smaller than that of the polyacrylate binder for preparing the battery, because the formation of the three-dimensional network structure improves the mechanical strength of the binder, the preparation method can better adapt to large volume change of a silicon-oxygen negative electrode, maintain the stable structure of the electrode, and promote the transmission of lithium ions due to the formation of the network structure, thereby reducing the impedance of the battery. FIG. 4 shows the first charge and discharge curves of the polyacrylate binder, the biomass/polyacrylate composite binder and the styrene-butadiene latex (SBR) binder at 0.1C rate, and it can be seen from FIG. 4 that the first discharge capacity of the biomass/polyacrylate composite binder can reach 534.90 mAh.g -1 Fig. 5 shows the coulombic efficiency of the polyacrylate binder, the biomass/polyacrylate composite binder and the styrene-butadiene latex (SBR) binder at 0.1C magnification, and as can be seen from fig. 5, the coulombic efficiency is improved by 5.6% compared with the polyacrylate binder, is 93.59%, and is higher than that of the SBR binder, and the better electrochemical performance is shown.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the technical solutions according to the embodiments of the present invention.
Claims (9)
1. The preparation method of the biomass/polyacrylate composite binder is characterized by comprising the following steps of:
step 1, weighing 0.01 to 0.1 weight part of biomass material, dissolving 0.001 to 0.010 weight part of metal salt in 8 to 15 weight parts of deionized water, and uniformly stirring to obtain a mixed solution;
and 2, transferring the polyacrylate emulsion into a reactor with a condenser tube, taking the mixed solution obtained in the step 1, slowly dripping the mixed solution into the polyacrylate emulsion according to the mass of the biomass material accounting for 0.1-1% of the polyacrylate, and stirring and reacting for 6-10 h at 20-80 ℃ to obtain the biomass/polyacrylate composite binder.
2. The method for preparing a biomass/polyacrylate composite binder according to claim 1, wherein the biomass material in step 1 comprises any one or a mixture of a plurality of sodium alginate, tannic acid, acacia, xanthan gum and chitosan in any proportion.
3. The method for preparing a biomass/polyacrylate composite binder according to claim 1, wherein the metal salt in step 1 comprises a mixture of one or more of copper chloride, ferric chloride, zinc chloride and calcium chloride in any ratio.
4. The method for preparing a biomass/polyacrylate composite binder according to claim 1, wherein one end of the polyacrylate in the step 2 is a hydrophilic chain segment containing polar groups; the other end is a hydrophobic chain segment of an ABA structure.
5. The method of preparing a biomass/polyacrylate composite binder according to claim 4, wherein the polar groups include carboxyl groups and amide groups.
6. The method for preparing a biomass/polyacrylate composite binder according to claim 4, wherein A is polymethyl methacrylate segment or polystyrene segment, and the polymerization degree is 100-350.
7. The method for preparing a biomass/polyacrylate composite binder according to claim 4, wherein B is any one of a poly (ethyl acrylate) segment, a poly (butyl acrylate) segment and a poly (isooctyl acrylate) segment, and the degree of polymerization is: 300 to 700.
8. A biomass/polyacrylate composite binder prepared according to the method of any one of claims 1 to 7.
9. Use of the biomass/polyacrylate composite binder according to claim 8 in a silicon-based negative electrode of a lithium ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116804138A (en) * | 2023-08-18 | 2023-09-26 | 广东工业大学 | Polyacrylic acid and sodium lignin sulfonate composite binder for silicon-based negative electrode of lithium ion battery, and preparation method and application thereof |
| CN118652380A (en) * | 2024-08-19 | 2024-09-17 | 安庆瑞泰化工有限公司 | Guar gum silane prepolymer modified solid acrylic resin and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116804138A (en) * | 2023-08-18 | 2023-09-26 | 广东工业大学 | Polyacrylic acid and sodium lignin sulfonate composite binder for silicon-based negative electrode of lithium ion battery, and preparation method and application thereof |
| CN116804138B (en) * | 2023-08-18 | 2023-12-08 | 广东工业大学 | Polyacrylic acid and sodium lignin sulfonate composite binder for silicon-based negative electrode of lithium ion battery, and preparation method and application thereof |
| CN118652380A (en) * | 2024-08-19 | 2024-09-17 | 安庆瑞泰化工有限公司 | Guar gum silane prepolymer modified solid acrylic resin and preparation method thereof |
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