CN114479713B - Composite conductive adhesive and preparation method and application thereof - Google Patents

Composite conductive adhesive and preparation method and application thereof Download PDF

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Publication number
CN114479713B
CN114479713B CN202210187311.8A CN202210187311A CN114479713B CN 114479713 B CN114479713 B CN 114479713B CN 202210187311 A CN202210187311 A CN 202210187311A CN 114479713 B CN114479713 B CN 114479713B
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solution
coupling agent
silane coupling
alginate
conductive adhesive
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CN114479713A (en
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张建立
江宏富
曹军
田新
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Jiangsu Xinhua Semiconductor Technology Co ltd
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Jiangsu Xinhua Semiconductor Technology Co ltd
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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
    • 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
    • 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

Abstract

The invention discloses a composite conductive adhesive and a preparation method and application thereof, wherein the composite conductive adhesive comprises the following components: a conductive polymer, an alginate, and a silane coupling agent, the conductive polymer including at least one of a polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer, and a polyfluorene-based polymer derivative. Therefore, the composite conductive adhesive has good conductivity, bonding performance and protection to a silicon-based negative electrode SEI film, has good strength and toughness, can solve the problems that the current lithium ion battery needs to use the conductive agent and the adhesive at the same time, so that the energy density of a battery core and the initial coulombic efficiency are low, and can also solve the problems that the current adhesive molecules cannot bind micro-nano silicon particles to fall off and pulverize, so that poor electrical contact is caused, the performance of the silicon-based negative electrode material is continuously deteriorated, and the cycle performance is finally rapidly attenuated.

Description

Composite conductive adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a composite conductive adhesive and 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 a clean and renewable secondary energy source, and particularly in recent years, with the rapid development of electric automobiles, lithium ion batteries are further getting a great deal of development and progress, but in spite of this, new application scenes put higher demands on the rate performance, energy density, cycle life, coulombic efficiency and the like of lithium ion batteries. The performance of lithium ion batteries is largely determined by the positive and negative electrode active materials and binders.
At present, the actual specific capacity of the traditional graphite cathode material is close to the theoretical specific capacity of 372mAh/g, and the actual specific capacity is one of the bottlenecks for restricting the continuous improvement of the energy density of the lithium ion battery. Meanwhile, the highest theoretical specific capacity of the silicon anode material which is expected to be up to 4200mAh/g for a long time is paid more attention, and the silicon anode material becomes one of the research hotspots which can last for many years, and is indistinguishable from the bright application prospect and the huge application challenges. The application challenges include: 1) During charge and discharge, the Li-Si alloying/dealloying can generate serious volume expansion/shrinkage, which can reach more than 300 percent (Li 4.4 Si), resulting in fragmentation, pulverization, deactivation of the silicon particles, poor cycle performance; 2) In the charge and discharge process, silicon particles are cracked, so that an island effect is formed due to poor electric contact between an active substance and a current collector, an SEI film on a fracture surface is destroyed, and a new SEI film is repeatedly formed, so that irreversible capacity loss and low coulomb efficiency are caused; 3) Silicon is a semiconductor, with a low electrical conductivity (10 -5 ～10 -3 S·cm -1 ) And ion diffusion coefficient (10) -14 ～10 -13 cm 2 ·s -1 ) Resulting in a decrease in the diffusion kinetics of lithium ions.
Numerous theories and attempts have been made in the scientific and industrial world to facilitate the application of silicon cathodes. Along with the continuous deep understanding, some attempts have good effects, and are provided and applied with measures such as silicon nanocrystallization, silicon-carbon recombination, carbon coating, prelithiation and the like, so that a silicon anode material gradually enters practical application, but a plurality of problems still need to be solved.
In the lithium ion secondary battery, the change of the volume of the anode material is positively correlated with the doping amount of silicon in the process of lithium intercalation. Therefore, with the increase of the silicon doping amount, the increase of the volume expansion and contraction of the negative electrode end of the lithium battery is often accompanied during charging and discharging, so that the risks of stripping, falling, fragmentation and pulverization of the negative electrode material are increased, and various application problems such as poor conduction, structural damage of the battery, low coulomb efficiency, continuous reduction of irreversible capacity and the like are caused. It is therefore recognized that the importance of high performance binders is desirable to develop a binder that has both good toughness, allows for some volumetric expansion of the anode material, and good adhesion and electrical conductivity. Obviously, the traditional binders of styrene-butadiene rubber (SBR) and sodium carboxymethylcellulose (CMC) for lithium battery cathodes on the market are not adequate for new application scenarios, and new binders need to be developed to solve the related problems. The current solutions in the industry are mostly developed along two ideas, one is to modify and compound Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC), but according to the related results, the adhesive can not solve the problem of adhesion with silicon materials, and the aforementioned phenomena and problems are still serious; another idea is to develop conductive polymer binders in an attempt to make up and solve the problems of poor conductivity of silicon materials, repeated formation and decomposition of SEI films, and continuous consumption of active materials, but although such materials enhance the conductivity of the system, the adhesion between the materials and current collectors and silicon-based materials is often weak, which is not satisfactory.
Therefore, there is a need to develop a high performance adhesive.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a composite conductive adhesive, and a preparation method and an application thereof, where the composite conductive adhesive has good conductivity, adhesion performance and protection to a silicon-based negative electrode SEI film, and has good strength and toughness, so as to solve the problems of low energy density and first coulombic efficiency of a battery core caused by using the conductive adhesive and the adhesive at the same time in the existing lithium ion battery, and solve the problems of poor electrical contact, continuous deterioration of the performance of the silicon-based negative electrode material, and rapid decay of the cycle performance caused by the fact that the existing adhesive molecules cannot bind the shedding and powdering of micro-nano silicon particles.
In one aspect of the invention, a composite conductive adhesive is provided. According to an embodiment of the present invention, the composite conductive adhesive includes: a conductive polymer, an alginate, and a silane coupling agent, the conductive polymer including at least one of a 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, a polypyrene methacrylate derivative, a polyfluorene polymer and a polyfluorene polymer derivative, the flexible skeleton structure of the polypyrene methacrylate and the polyfluorene polymer derivative promotes formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, interaction between pyrene methyl and nano silicon particles is promoted, the polymer can be completely covered on the surfaces of nano silicon particles or silicon carbon negative electrodes, active materials can be well covered in the volume change process of lithium removal, contact between the nano silicon particles and electrolyte is reduced, continuous consumption of the electrolyte is hindered, and stability of the negative electrode SEI film is improved; meanwhile, the polyfluorene polymer and the derivative 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 charge and discharge process are truly maintained. In addition, the alginate radical in the alginate has low swelling rate, good shape retention, regular and uniform arrangement of carboxyl groups on a molecular chain and higher content, so that the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate radical can form a stable SEI film through forming a hydrogen bond with the hydroxyl group on the surface of the nano silicon particle, has high polarity and stronger adhesive force, can effectively prevent the agglomeration and the falling-off of the nano silicon particle, and a proper amount of the alginate radical can also generate a synergistic effect with part of conductive polymer on the SEI film, so that the stability of the negative SEI film is further improved. Moreover, the use of the silane coupling agent can improve the binding force between the composite conductive adhesive and the nano silicon particles on one hand; on the other hand, the crosslinking of the conductive polymer and the alginate radical 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 anode material into an organic whole. In summary, the composite conductive adhesive has good conductivity, bonding performance and protection to the silicon-based negative electrode SEI film, and has good strength and toughness, so that good use of the silicon-carbon negative electrode material under the condition of higher silicon content can be ensured, the specific capacity of the negative electrode material can be improved, the use of the conductive agent in the negative electrode of the lithium battery can be reduced or canceled, the content of active substances in the silicon-carbon negative electrode can be increased, the specific capacity of the negative electrode material can be further improved, the energy density of the battery can be increased, and meanwhile, the composite conductive adhesive 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 have the following additional technical features:
in some embodiments of the invention, the mass ratio of the conductive polymer to the alginate is (1:3) - (6:1). Therefore, the composite conductive adhesive has good conductivity, adhesion performance and protection to the 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, adhesion performance and protection to the silicon-based negative electrode SEI film.
In some embodiments of the invention, the polypyrene methacrylate derivatives include at least one of polypyrene methacrylate-co-methacrylic acid and polypyrene methacrylate-co-triethylene oxide methyl ether methacrylate.
In some embodiments of the invention, the polyfluorene-based polymer derivative includes at least one of polyfluorene-co-fluorenone and polyfluorene-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 present invention, the present invention provides a method of preparing the above-described composite conductive adhesive. According to an embodiment of the invention, the method comprises:
(1) Mixing a conductive polymer, an alginate and a solvent to obtain a mixed solution;
(2) And mixing the silane coupling agent with the mixed solution for reaction so as to obtain the composite conductive adhesive.
According to the method for preparing the composite conductive adhesive, disclosed by the embodiment of the invention, the conductive polymer, the alginate and the solvent are mixed to obtain a mixed solution containing the conductive polymer and the alginate; and then mixing the silane coupling agent with the mixed solution to react, wherein the hydroxyl, carboxyl and other groups generated by hydrolysis of the silane coupling agent and the hydroxyl, carboxyl and other groups of the conductive polymer and the alginate undergo complex polymerization reaction, and the composite conductive adhesive can be obtained after the reaction is finished. The conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene polymer and a polyfluorene polymer derivative, wherein the flexible skeleton structure of the polypyrene methacrylate and the polyfluorene polymer derivative promotes formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, promotes interaction between pyrene methyl and nano silicon particles, enables the polymer to completely cover the surface of the nano silicon particles or silicon carbon negative electrode, can well cover an active material in the volume change process of lithium removal, reduces contact between the nano silicon particles and electrolyte, prevents continuous consumption of the electrolyte, and improves the stability of the negative electrode SEI film; meanwhile, the polyfluorene polymer and the derivative 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 charge and discharge process are truly maintained. In addition, the alginate radical in the alginate has low swelling rate, good shape retention, regular and uniform arrangement of carboxyl groups on a molecular chain and higher content, so that the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate radical can form a stable SEI film through forming a hydrogen bond with the hydroxyl group on the surface of the nano silicon particle, has high polarity and stronger adhesive force, can effectively prevent the agglomeration and the falling-off of the nano silicon particle, and a proper amount of the alginate radical can also generate a synergistic effect with part of conductive polymer on the SEI film, so that the stability of the negative SEI film is further improved. Moreover, the use of the silane coupling agent can improve the binding force between the composite conductive adhesive and the nano silicon particles on one hand; on the other hand, the crosslinking of the conductive polymer and the alginate radical 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 anode material into an organic whole. In summary, the composite conductive adhesive prepared by the method has good conductivity, bonding performance and protection to the 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 used well under the condition of higher silicon content, the specific capacity of the negative electrode material is improved, the use of the conductive agent in the negative electrode of the lithium battery can be reduced or canceled, 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 the battery is increased, and meanwhile, the composite conductive adhesive protects the SEI film, and the first coulombic efficiency and the cycle performance of the battery are improved.
In addition, the method for preparing 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 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 invention, in 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 invention, in 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 to 6-8 so as to obtain a pretreated solution; (e) And mixing the pretreated solution with the mixed solution so as to obtain the composite conductive adhesive.
In a third aspect of the invention, the invention provides a negative electrode. According to an embodiment of the present invention, the negative electrode contains the above-described composite conductive binder or the composite conductive binder prepared by the above-described method. Thus, the negative electrode has high specific capacity, high first coulombic efficiency and excellent cycle performance.
In a fourth aspect of the invention, the invention provides a battery. According to an embodiment of the present invention, the battery contains the above-described negative electrode. Thus, the battery has high specific capacity and 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 foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic flow chart of a method for preparing the above composite conductive adhesive according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for preparing the above composite conductive adhesive according to still another embodiment of the present invention;
fig. 3 is a schematic flow chart of a method for preparing the above composite conductive adhesive according to yet another embodiment of the present invention;
fig. 4 is a flow chart of a method for preparing the above composite conductive adhesive according to still another embodiment of the present invention.
Detailed Description
The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In a first aspect of the invention, the invention provides a composite conductive adhesive. According to an embodiment of the present invention, the above composite conductive adhesive includes: the conductive polymer comprises at least one of a polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative, an alginate and a silane coupling agent.
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, a polypyrene methacrylate derivative, a polyfluorene polymer and a polyfluorene polymer derivative, the flexible skeleton structure of the polypyrene methacrylate and the polyfluorene polymer derivative promotes the formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, also promotes the interaction between pyrene methyl and nano silicon particles, enables the polymer to completely cover the surface of nano silicon particles or silicon carbon negative electrode, can well cover active materials in the volume change process of lithium removal, reduces the contact between nano silicon particles and electrolyte, blocks the continuous consumption of the electrolyte, and improves the stability of the negative electrode SEI film; meanwhile, the polyfluorene polymer and the derivative 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 charge and discharge process are truly maintained. In addition, the alginate radical in the alginate has low swelling rate, good shape retention, regular and uniform arrangement of carboxyl groups on a molecular chain and higher content, so that the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate radical can form a stable SEI film through forming a hydrogen bond with the hydroxyl group on the surface of the nano silicon particle, has high polarity and stronger adhesive force, can effectively prevent the agglomeration and the falling-off of the nano silicon particle, and a proper amount of the alginate radical can also generate a synergistic effect with part of conductive polymer on the SEI film, so that the stability of the negative SEI film is further improved. Moreover, the use of the silane coupling agent can improve the binding force between the composite conductive adhesive and the nano silicon particles on one hand; on the other hand, the crosslinking of the conductive polymer and the alginate radical 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 anode material into an organic whole. In summary, the composite conductive adhesive has good conductivity, bonding performance and protection to the silicon-based negative electrode SEI film, and has good strength and toughness, so that good use of the silicon-carbon negative electrode material under the condition of higher silicon content can be ensured, the specific capacity of the negative electrode material can be improved, the use of the conductive agent in the negative electrode of the lithium battery can be reduced or canceled, the content of active substances in the silicon-carbon negative electrode can be increased, the specific capacity of the negative electrode material can be further improved, the energy density of the battery can be increased, and meanwhile, the composite conductive adhesive 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; and 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 optimal combination performance can be produced. Further, the silane coupling agent accounts for 0.1 to 10 percent 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-linked 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 excessively added, the conductivity of the composite conductive adhesive may be affected. Therefore, the prepared composite conductive adhesive has good conductive performance and adhesive performance by adopting the addition amount of the silane coupling agent.
It should be noted that, the specific types of the above-mentioned polypyrene methacrylate derivatives, polyfluorene-based polymer derivatives, alginate and silane coupling agent may 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 oxide methyl ether methacrylate; the polyfluorene-based polymer derivative comprises at least one of polyfluorene-co-fluorenone and polyfluorene-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 present invention, the present invention provides a method of preparing the above-described composite conductive adhesive. Referring to fig. 1, according to an embodiment of the present invention, the method includes:
s100: mixing conductive polymer, alginate and solvent
In this step, a mixed solution containing a conductive polymer and an alginate is obtained by mixing the conductive polymer, the alginate, and a 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 will not be repeated here. Specifically, referring to fig. 2, a conductive polymer is first mixed with a first solvent to obtain a conductive polymer solution with a mass concentration of 10% -50%, and at the same time, an alginate is mixed with a second solvent to obtain an alginate solution with a mass concentration of 10% -50%, and then the conductive polymer solution and the alginate solution are mixed and stirred uniformly to obtain the mixed solution. The specific types of the first solvent and the second solvent are the same, including but not limited to at least one of deionized water, alcohol, ketone, ester, and hydrocarbon.
S200: mixing silane coupling agent and mixed solution for reaction
In the step, the silane coupling agent and the mixed solution obtained in the step S100 are mixed to react, and the composite conductive adhesive is obtained after the reaction is finished. It should be noted that the specific types and the addition amounts of the silane coupling agents are the same as those described above, and are not repeated here. Further, the temperature of the mixing reaction is 20 to 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 low; if the reaction temperature is too high, the solvent is seriously volatilized, which is unfavorable for obtaining a stable and uniform composite conductive adhesive. Therefore, by adopting the reaction temperature, aggregation of each component can be avoided, and hydrolysis of the silane coupling agent is accelerated, so that the stable and uniform composite conductive adhesive is obtained. Specifically, referring to fig. 3, a silane coupling agent is first mixed with a third solvent to obtain a silane coupling agent solution with a mass concentration of 10% -40%, then the silane coupling agent solution is added into the mixed solution, and the mixture is left stand for 1-24 hours to obtain the composite conductive adhesive. Preferably, referring to fig. 4, 5 to 10 drops of an acidic solution with a concentration of 0.15mol/L to 0.25mol/L, preferably 0.2mol/L, is added to the silane coupling agent solution to allow the silane coupling agent to be fully hydrolyzed, then an alkaline solution is added to adjust the pH to 6 to 8, so as to facilitate the formation of an excellent three-dimensional crosslinked network during a post-mixing reaction, a pre-treated solution is obtained, and finally the pre-treated solution is mixed with the mixed solution, and a complex polymerization reaction is performed between hydroxyl, carboxyl and other groups generated by the hydrolysis of the silane coupling agent and hydroxyl, carboxyl and other groups of the conductive polymer and alginate, so as to obtain the composite conductive adhesive. It should be noted that, a person skilled in the art may select the specific type of the above acidic solution and the basic solution 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 meanwhile, the specific type of the third solvent is the same as the first solvent described above, and will not be described here 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 mixing the silane coupling agent with the mixed solution to react, wherein the hydroxyl, carboxyl and other groups generated by hydrolysis of the silane coupling agent and the hydroxyl, carboxyl and other groups of the conductive polymer and the alginate undergo complex polymerization reaction, and the composite conductive adhesive can be obtained after the reaction is finished. The conductive polymer comprises at least one of polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene polymer and a polyfluorene polymer derivative, wherein the flexible skeleton structure of the polypyrene methacrylate and the polyfluorene polymer derivative promotes formation of a pyrene methyl ordered structure, so that the polymer generates excellent conductivity, promotes interaction between pyrene methyl and nano silicon particles, enables the polymer to completely cover the surface of the nano silicon particles or silicon carbon negative electrode, can well cover an active material in the volume change process of lithium removal, reduces contact between the nano silicon particles and electrolyte, prevents continuous consumption of the electrolyte, and improves the stability of the negative electrode SEI film; meanwhile, the polyfluorene polymer and the derivative 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 charge and discharge process are truly maintained. In addition, the alginate radical in the alginate has low swelling rate, good shape retention, regular and uniform arrangement of carboxyl groups on a molecular chain and higher content, so that the internal resistance of a battery cell is minimized, the energy efficiency is maximized, and the alginate radical can form a stable SEI film through forming a hydrogen bond with the hydroxyl group on the surface of the nano silicon particle, has high polarity and stronger adhesive force, can effectively prevent the agglomeration and the falling-off of the nano silicon particle, and a proper amount of the alginate radical can also generate a synergistic effect with part of conductive polymer on the SEI film, so that the stability of the negative SEI film is further improved. Moreover, the use of the silane coupling agent can improve the binding force between the composite conductive adhesive and the nano silicon particles on one hand; on the other hand, the crosslinking of the conductive polymer and the alginate radical 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 anode material into an organic whole. In summary, the composite conductive adhesive prepared by the method has good conductivity, bonding performance and protection to the 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 used well under the condition of higher silicon content, the specific capacity of the negative electrode material is improved, the use of the conductive agent in the negative electrode of the lithium battery can be reduced or canceled, 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 the battery is increased, and meanwhile, the composite conductive adhesive protects the SEI film, and the first coulombic efficiency and the cycle performance of the battery are improved.
In a third aspect of the invention, the invention provides a negative electrode. According to an embodiment of the present invention, the negative electrode contains the above-described composite conductive binder or the composite conductive binder prepared by the above-described method. Thus, the negative electrode has high specific capacity, high first coulombic efficiency and excellent cycle performance. It should be noted that, the specific type of the active material and the current collector of the anode and the specific preparation method of the anode are all conventional technologies in the art, and meanwhile, the features and advantages described above for the composite conductive adhesive and the preparation method thereof are also applicable to the anode, and are not repeated here.
In a fourth aspect of the invention, the invention provides a battery. According to an embodiment of the present invention, the battery contains the above-described negative electrode. Thus, the battery has high specific capacity and 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 method of the battery are all conventional in the art, and the features and advantages described above for the negative electrode are also applicable to the battery, and are not repeated here.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) 100g of water and 200g of acetone are weighed, mixed and stirred uniformly, heated to 60 ℃, then 100g of conductive polymer polypyrene methacrylate is weighed, added into a mixed solvent consisting of water and acetone, and fully stirred uniformly to prepare the polypyrene methacrylate solution with the mass concentration of 25%.
(2) 200g of water and 100g of acetone are weighed, mixed and stirred uniformly, heated to 60 ℃, then 100g of potassium alginate is weighed, added into a mixed solvent consisting of water and acetone, and fully stirred uniformly to prepare a potassium alginate solution with the mass concentration of 25%.
(3) And then mixing the two solutions and stirring uniformly to obtain a mixed solution, and preserving the temperature at 60 ℃.
(4) 10g of water and 10g of acetone are weighed, mixed and stirred uniformly, heated to 40 ℃, then 5g of gamma- (2, 3-glycidoxy) propyl trimethoxy silane is weighed, added into a mixed solvent consisting of water and acetone, and fully stirred uniformly to prepare a silane coupling agent solution with the mass concentration of 20 percent.
(5) 8 drops of 0.2mol/L acetic acid solution are added into the silane coupling agent solution, hydrolysis is carried out for about 30 minutes under the stirring condition, so that gamma- (2, 3-glycidoxy) propyl trimethoxy silane is fully hydrolyzed, then a small amount of 0.2mol/L sodium hydroxide solution is added into the hydrolyzed silane coupling agent solution, the pH value is adjusted to 7, and the mixture solution is added into the mixture solution for uniform stirring, thus obtaining the composite conductive adhesive 1.
Example 2
(1) 150g of water and 250g of ethanol are weighed, mixed and stirred uniformly, heated to 50 ℃, then 150g of conductive polymer polypyrene methacrylate-co-methacrylic acid is weighed, added into a mixed solvent consisting of water and ethanol, and fully stirred uniformly to prepare a polypyrene methacrylate solution with the mass concentration of 27.3%.
(2) 150g of water and 100g of ethanol are weighed, mixed and stirred uniformly, heated to 50 ℃, then 70g of sodium alginate is weighed, added into a mixed solvent consisting of water and ethanol, and fully stirred uniformly to prepare an alginate solution with the mass concentration of 21.9%.
(3) And then mixing the two solutions and stirring uniformly to obtain a mixed solution, and preserving the temperature at 50 ℃.
(4) 10g of water and 10g of ethanol are weighed, mixed and stirred uniformly, heated to 40 ℃, then 3g of vinyltrimethoxysilane is weighed, added into a mixed solvent consisting of water and ethanol, and fully stirred uniformly to prepare a silane coupling agent solution with the mass concentration of 13 percent.
(5) Directly adding the just prepared silane coupling agent solution for modification into the mixed solution, fully mixing, uniformly stirring, and standing for 12 hours at the temperature of 50 ℃ to obtain the composite conductive adhesive 2.
Example 3
The same procedure as in example 1 was followed except that the polypyrene methacrylate in example 1 was replaced with polyfluorene-based polymer-co-fluorenone to prepare a composite conductive adhesive 3.
Example 4
The same procedure as in example 2 was followed except that the polypyrene methacrylate-co-methacrylic acid in example 2 was replaced with polyfluorene-based polymer-co-fluorenone-co-methylbenzoate, to prepare composite conductive adhesive 4.
Comparative example 1
(1) 100g of water and 200g of acetone are weighed, mixed and stirred uniformly, heated to 60 ℃, then 100g of conductive polymer polypyrene methacrylate is weighed, added into a mixed solvent consisting of water and acetone, and fully stirred uniformly to prepare the polypyrene methacrylate solution with the mass concentration of 25%.
(2) 200g of water and 100g of acetone are weighed, mixed and stirred uniformly, heated to 60 ℃, then 100g of potassium alginate is weighed, added into a mixed solvent consisting of water and acetone, and fully stirred uniformly to prepare a potassium alginate solution with the mass concentration of 25%.
(3) And then mixing the two solutions and stirring uniformly to obtain a mixed solution, regulating the pH value of the mixed solution to 8 by using sodium hydroxide, and modifying the mixed solution without using a silane coupling agent to obtain the comparative adhesive 1.
Comparative example 2
600g of water is weighed, heated to 60 ℃, 200g of sodium alginate is weighed again, added into hot water, fully stirred to prepare sodium alginate solution with the mass concentration of 25%, and the pH value of the composite conductive adhesive is adjusted to 6 by sodium hydroxide, so that the comparative adhesive 2 is obtained.
Comparative example 3
600g of water is weighed, heated to 60 ℃, then 150g of sodium carboxymethyl cellulose (CMC) and 50g of Styrene Butadiene Rubber (SBR) are weighed, and the weighed sodium carboxymethyl cellulose and the styrene butadiene rubber are added into hot water in sequence, and are fully stirred uniformly to obtain the comparative adhesive 3.
Comparative example 4
600g of water was weighed, heated to 60 ℃, then 200g of sodium carboxymethylcellulose (CMC) was weighed again, added to hot water, and stirred well enough to obtain comparative adhesive 4.
Performance testing and analysis
According to the silicon-based material: flake graphite: and (2) a binder: the mass ratio of asphalt is 4:12:1:3 (the binders of the above examples and comparative examples with equal solid content are respectively selected for the binders), under the same pressure, temperature and other parameter conditions, silicon-carbon anode materials are prepared, and then electrochemical performance tests (counter electrode: pure lithium sheet, electrolyte: xinzhou bang LBC-A28) and mechanical stripping experiments are respectively carried out, and the experimental and 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 mechanical peel test results of the negative electrodes prepared in examples and comparative examples
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 present invention. In this specification, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (8)

1. A composite conductive adhesive comprising: a conductive polymer, an alginate and a silane coupling agent, wherein the conductive polymer comprises at least one of a polypyrene methacrylate, a polypyrene methacrylate derivative, a polyfluorene-based polymer and a polyfluorene-based polymer derivative,
the mass ratio of the conductive polymer to the alginate is (1:3) - (6:1),
the silane coupling agent accounts for 0.1-10% of the total mass of the conductive polymer, the alginate and the silane coupling agent.
2. The composite conductive adhesive of claim 1, wherein the polypyrene methacrylate derivative comprises at least one of polypyrene methacrylate-co-methacrylic acid and polypyrene methacrylate-co-triethylene oxide methyl ether methacrylate;
optionally, the polyfluorene-based polymer derivative comprises at least one of polyfluorene-co-fluorenone and polyfluorene-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.
3. A method of preparing the composite conductive adhesive of claim 1 or 2, comprising:
(1) Mixing a conductive polymer, an alginate and a solvent to obtain a mixed solution;
(2) And mixing the silane coupling agent with the mixed solution for reaction so as to obtain the composite conductive adhesive.
4. A method according to claim 3, 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 conductive polymer in the conductive polymer solution is 10% to 50%;
optionally, in step (ii), the mass concentration of alginate in the alginate solution is 10% to 50%;
optionally, in step (2), the temperature of the mixing reaction is 20 to 80 ℃.
5. The method of claim 3 or 4, 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.
6. The method of claim 3 or 4, 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 so as to obtain the composite conductive adhesive.
7. A negative electrode comprising the composite conductive binder of claim 1 or 2 or prepared by the method of any one of claims 3 to 6.
8. A battery comprising the negative electrode of claim 7.
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