CN115472834A - Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode - Google Patents

Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode Download PDF

Info

Publication number
CN115472834A
CN115472834A CN202110653757.0A CN202110653757A CN115472834A CN 115472834 A CN115472834 A CN 115472834A CN 202110653757 A CN202110653757 A CN 202110653757A CN 115472834 A CN115472834 A CN 115472834A
Authority
CN
China
Prior art keywords
negative electrode
polymer
binder
silicon
active material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110653757.0A
Other languages
Chinese (zh)
Inventor
李政杰
潘中来
张晓正
李仁贵
杜鸿昌
夏圣安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Yindile Materials Science And Technology Group Co ltd
Huawei Technologies Co Ltd
Original Assignee
Sichuan Yindile Materials Science And Technology Group Co ltd
Huawei Technologies Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Yindile Materials Science And Technology Group Co ltd, Huawei Technologies Co Ltd filed Critical Sichuan Yindile Materials Science And Technology Group Co ltd
Priority to CN202110653757.0A priority Critical patent/CN115472834A/en
Publication of CN115472834A publication Critical patent/CN115472834A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present application provides a polymer comprising a backbone and side chains. The main chain mainly comprises a water-soluble acrylonitrile copolymer, and the polymerized monomers of the acrylonitrile copolymer comprise acrylic monomers and acrylonitrile monomers. One end of the side chain is connected with the main chain, and the other end is connected with the organic silicon group
Figure DDA0003112925180000011
X 1 、X 2 And X 3 Each independently selected from one of C1-C4 alkyl, hydroxyl, halogen atom and C1-C4 alkoxy, and X 1 、X 2 And X 3 Not simultaneously being alkyl. The chain atom number of the side chain is more than or equal to 3. The application also provides a binder, a negative electrode and a secondary battery comprising the polymer, application of the polymer and preparation of the negative electrodeA method. The main chain of the polymer has high mechanical strength, can maintain the stability of an electrode microscopic skeleton structure, and the side chain can be telescopic while realizing multi-dimensional bonding of silicon particles, so that the volume and stress change of the silicon particles in the charging and discharging processes can be buffered.

Description

Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode
Technical Field
The present application relates to a polymer, a binder including the polymer, a negative electrode including the polymer, a secondary battery including the polymer, an application of the polymer as the binder, and a method of preparing the negative electrode.
Background
At present, secondary batteries are widely used in mobile phones, notebook computers, portable electronic mobile devices, and mobile terminals such as unmanned aerial vehicles and electric vehicles. The secondary battery includes a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a lithium sulfur battery, and the like. As a secondary battery, a lithium ion battery generally employs lithium cobaltate/ternary/lithium iron phosphate as a positive electrode material and graphite as a negative electrode material. However, as the demand of the market for the energy density of the lithium ion battery is increased, the research and development of the high-capacity lithium ion battery material are more and more urgent. For the negative electrode material of the lithium ion battery, the silicon material has extremely high theoretical specific lithium storage capacity (up to 4200 mAh/g), abundant storage capacity and low cost, and becomes one of the most studied and most potential high-capacity negative electrode materials at present. However, when silicon is used as the most typical alloy negative electrode material and is alloyed with lithium, the silicon expands by over 300% in volume, and mechanical stress caused by large volume change easily pulverizes the silicon itself, so that the electrochemical activity of silicon particles is inactivated; meanwhile, the volume change of silicon also causes the damage of an electrode structure, the rapid attenuation of the battery capacity and the rapid deterioration of the cycle performance. Current strategies to address silicon anode expansion may be developed from binder design, and thus, binder design is increasingly being focused and studied. The binder is used as a key part of the electrode structure, provides an interconnected structure and mechanical strength for the electrode, maintains electron/ion transfer in the battery cycle process, and plays a crucial role in the overall electrochemical performance. Meanwhile, the adhesive is one of solutions for electrode expansion, and the volume expansion of silicon in the circulation process is restrained by adopting the adhesive with single or composite characteristics such as high elastic modulus, high adhesiveness, self-healing property, soft-hard block copolymer and the like.
Disclosure of Invention
A first aspect of an embodiment of the present application provides a polymer comprising:
a backbone consisting essentially of a water-soluble acrylonitrile copolymer having polymerized monomers including acrylic and acrylonitrile-based monomers;
a side chain having one end connected to the main chain and the other end connected to a silicone group
Figure BDA0003112925160000011
X 1 、X 2 And X 3 Each independently selected from the group consisting of C1-C4 alkyl, hydroxy, halogen, C1-C4 alkoxy, and X 1 、X 2 And X 3 Not being alkyl at the same time;
the chain atom number of the side chain is more than or equal to 3, and the chain atom number is the total number of non-hydrogen atoms in the non-branched chain of the side chain.
According to the polymer, a side chain is introduced into a main chain structure of a water-soluble acrylonitrile copolymer, and an organic silicon group connected with the side chain can form strong interaction with silicon particles with silicon hydroxyl on the surface, so that multidimensional bonding of the silicon particles is realized. In addition, the main chain comprising the acrylonitrile copolymer has high mechanical strength, can maintain the stability of the electrode microscopic skeleton structure, and the side chain is telescopic, so that the huge volume change and stress change of silicon particles in the charging and discharging processes can be effectively buffered.
In the embodiment of the application, the weight percentage of nitrile groups contained in the polymer is 4-30%; the weight percentage of the silicon element in the polymer is 0.01-5%.
In an embodiment of the present application, the polymer comprises 20% to 29% by weight of nitrile groups in the polymer.
In the embodiment of the application, the weight percentage of the silicon element in the polymer is 0.1-1%.
In an embodiment of the present invention, the acrylic monomer includes at least one of acrylic acid, an acrylate salt, methacrylic acid, and a methacrylate salt, and the acrylate salt and the methacrylate salt are at least one of a sodium salt, a potassium salt, a lithium salt, a rubidium salt, and a cesium salt, respectively.
In an embodiment of the present application, the acrylonitrile-based monomer includes at least one of acrylonitrile and methacrylonitrile.
In the embodiment of the present application, the polymerized monomers of the acrylonitrile copolymer further include acrylamide monomers or epoxy group-containing vinyl monomers.
The introduction of acrylamide monomers or epoxy group-containing olefin monomers can not only endow the copolymer with other functions, but also introduce amide groups or epoxy groups, thereby facilitating the grafting of the side chains.
In the embodiment of the present application, the acrylamide-based monomer is at least one of acrylamide, N-methacrylamide, N-ethylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, 2-methacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, and N-hydroxypropylacrylamide; the epoxy group-containing alkene monomer is at least one of glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether.
In the embodiment of the present application, the number of chain atoms of the side chain is not less than 5.
The side chain with the chain atom number more than or equal to 3 can better stretch and contract to adapt to the periodical huge volume change of the silicon particles in the charging and discharging process.
In the embodiments of the present application, the side chain has the structural formula
Figure BDA0003112925160000021
Figure BDA0003112925160000022
Figure BDA0003112925160000023
At least one of; wherein two ends of the main chain of the structural formula of the side chain are respectively connected with the main chain of the polymer and Si of the organosilicon group.
In a second aspect of embodiments herein there is provided a binder comprising a polymer as described in the first aspect of embodiments herein.
The polymer is used as a binder, especially the binder is used as the binder of a silicon-based negative electrode of a battery, and as the organic silicon group connected with the side chain of the polymer can form strong interaction with silicon particles with silicon hydroxyl on the surface in the negative electrode, the multidimensional bonding of the silicon particles is realized, so that the binder has good adhesion; in addition, the side chain of the polymer is telescopic, so that the huge volume change of silicon particles can be inhibited to a certain extent in the circulating process of the battery, and the expansion of the pole piece is effectively inhibited.
In an embodiment of the present application, the binder is a binder of a negative electrode of a battery.
A third aspect of embodiments of the present application provides a use of a polymer as described in the first aspect of embodiments of the present application as a binder.
In a fourth aspect of the embodiments, there is provided a negative electrode of a battery, comprising a negative electrode active material and a binder, the binder comprising the polymer according to the first aspect of the embodiments.
The aqueous polymer has good adhesion when being used as the adhesive of the silicon-based negative electrode, and can inhibit huge volume change of silicon particles to a certain extent in the circulation process, thereby effectively inhibiting the expansion of a pole piece.
In an embodiment of the present application, the negative electrode active material includes a silicon-based material.
In an embodiment of the present application, the negative electrode includes a current collector and a negative electrode active material layer attached on the current collector, and the negative electrode active material layer includes the negative electrode active material and the binder.
In a fifth aspect, embodiments of the present application provide a secondary battery comprising an anode, a cathode, an electrolyte, and a separator between the anode and the cathode, the anode comprising an anode active material and a binder, the binder comprising a polymer as described in the first aspect of the embodiments of the present application.
The aqueous polymer binder has good adhesion as the binder of the silicon-based negative electrode, can inhibit the huge volume change of silicon particles to a certain extent in the circulation process, effectively keeps the adhesion between the active material and the current collector, can effectively reduce the internal resistance of the negative electrode plate, inhibit the expansion of the electrode plate and effectively prolong the service life of the battery.
In an embodiment of the present application, the negative electrode active material includes a silicon-based material.
In an embodiment of the present application, the negative electrode includes a current collector and a negative electrode active material layer attached on the current collector, the negative electrode active material layer including the negative electrode active material and the binder.
A sixth aspect of the present embodiment provides a method for manufacturing a negative electrode of a battery, including:
mixing a negative electrode active material, a binder and a solvent to form a slurry, wherein the binder comprises the polymer according to the first aspect of the embodiment of the application;
and coating the slurry on a negative current collector and drying.
In an embodiment of the present application, the solvent is water.
In an embodiment of the present application, the negative electrode active material includes a silicon-based material.
In an embodiment of the present application, the negative electrode active material further includes graphite.
Drawings
Fig. 1 is a schematic diagram of a lithium ion battery.
FIG. 2 is a schematic representation of a polymer of an embodiment of the present application.
Description of the main elements
Lithium ion battery 100
Positive electrode 10
Negative electrode 30
Diaphragm 50
Detailed Description
The embodiments of the present application will be described below with reference to the drawings.
The secondary battery shown in fig. 1 may be a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a lithium sulfur battery, or the like, and the present application will be described by taking a lithium ion battery as an example. The lithium ion battery 100 mainly includes a positive electrode 10 containing a positive electrode material, a negative electrode 30 containing a negative electrode material, a separator 50, and an electrolytic solution (not shown, and usually filled in pores of the positive electrode, the negative electrode, and the separator). During charging, lithium ions are extracted from the crystal lattice of the positive electrode material and inserted into the crystal lattice of the negative electrode material after passing through the electrolyte, so that the negative electrode is rich in lithium and the positive electrode is poor in lithium. During discharging, lithium ions are extracted from the crystal lattice of the negative electrode material, pass through the electrolyte and are inserted into the crystal lattice of the positive electrode material, so that the positive electrode is rich in lithium, and the negative electrode is poor in lithium. The difference of the potentials of the positive and negative electrode materials relative to the metallic lithium during the insertion and extraction of lithium ions is the working voltage of the battery.
When the negative electrode is made of a silicon-based material, the silicon-based material can expand and contract in volume when lithium is inserted into and removed from the silicon, so that the adhesion failure is easily caused along with the circulation, the expansion of a negative electrode pole piece and the expansion of a battery cell are caused, and the potential safety hazard can be even caused in serious conditions.
The existing water-based binder taking acrylonitrile copolymer as a main chain structure has high bonding strength and excellent chemical and electrochemical properties, and has excellent comprehensive performance when being used as a binder of a graphite negative electrode material. However, when the silicon-based negative electrode is used, the rigid polymer chain cannot adapt to the periodic huge volume change of the silicon particles with the increasing cycle number, the bonding and constraint effects on the silicon particles are gradually deteriorated, the negative electrode plate is cracked or the active substance coating is stripped, and finally the battery fails.
Accordingly, the present application provides a binder that can be used in silicon-based anodes to meet the low cycle expansion and long cycle life use requirements of silicon-based anodes.
The binder includes a polymer, as shown in fig. 2, including a main chain and at least one side chain connecting the main chain. One end of each side chain is connected with the main chain, and the other end is connected with a organosilicon group
Figure BDA0003112925160000041
Wherein X 1 、X 2 And X 3 The alkyl groups may be the same or different from each other, and are each independently one selected from the group consisting of a C1-C4 alkyl group, a hydroxyl group, a halogen atom, and a C1-C4 alkoxy group; and X 1 、X 2 And X 3 Not both simultaneously being alkyl, i.e. X 1 、X 2 And X 3 At least one of them is one of hydroxyl, halogen atom and C1-C4 alkoxy.
The organosilicon group attached to the side chain can form a strong interaction with the silicon particle (with silicon hydroxyl on the surface), thereby realizing multi-dimensional bonding of the silicon particle. The strong interaction refers to the physical or chemical action such as strong hydrogen bonds, ionic bonds or covalent bonds formed between the silicon active particles.
The backbone mainly comprises a water-soluble acrylonitrile copolymer. The acrylonitrile copolymer is a water-based copolymer which can be uniformly dispersed in water and is formed by polymerizing a plurality of monomers. The polymerized monomers of the acrylonitrile copolymer include acrylic monomers and acrylonitrile monomers. The acrylic monomer comprises at least one of acrylic acid, acrylate, methacrylic acid and methacrylate, and the acrylonitrile monomer comprises at least one of acrylonitrile and methacrylonitrile. The acrylate and the methacrylate are each at least one of a sodium salt, a potassium salt, a lithium salt, a rubidium salt, and a cesium salt.
The polymerization monomer of the acrylonitrile copolymer can also comprise an acrylamide monomer or an epoxy group-containing alkene monomer. That is, the acrylonitrile copolymer includes at least the following species: the first is that the two polymerized monomers are acrylic monomers and acrylonitrile monomers respectively; and the second polymerization monomer is three, namely at least one of an acrylamide monomer and an epoxy group-containing alkene monomer, an acrylic monomer and a acrylonitrile monomer. The acrylamide monomer is at least one of acrylamide, N-methacrylamide, N-ethyl acrylamide, N-dimethyl acrylamide, N-diethyl acrylamide, 2-methacrylamide, N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide. The alkene monomer containing epoxy group can be at least one of glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether. The introduction of acrylamide monomers or epoxy group-containing alkene monomers can not only endow the copolymer with other functions, but also introduce amide groups or epoxy groups, thereby facilitating grafting of the side chains.
In the present application, the side chain may contain a chain segment structural unit having a flexible characteristic such as an alkane group, an alkoxy group, or the like. The side chains are grafted to the backbone by chemical bonds. The side chains can be extended or compressed, similar to springs, and buffer the huge volume change and stress change of the silicon particles in the charge and discharge processes.
The side chain may be straight or may contain a branch. The number of chain atoms of the side chain is more than or equal to 3, the number of chain atoms is the total number of non-hydrogen atoms in a main chain of the side chain, the number of non-hydrogen atoms in a branched chain is not included, namely the total number of non-hydrogen atoms in the non-branched chain of the side chain, and the number of atoms of the organosilicon group connected with the tail end is not included. Researches show that the chain segment with the chain atom number more than or equal to 3 can be well stretched to adapt to the periodical huge volume change of the silicon particles in the charging and discharging processes. The side chain does not contain silicon, and the end of the side chain is connected with the organosilicon group containing silicon.
When the side chain is a straight chain, the number of the chain atoms is the total number of atoms such as C, O, N, S and the like in the side chain. When the side chain contains a branched chain, the number of the chain atoms is C, O and N in the main chain of the side chainTotal number of atoms, S, etc. For example, when the side chain has the formula
Figure BDA0003112925160000051
The number of chain atoms is 6, wherein both ends of the main chain of the structural formula are respectively connected with the main chain of the polymer and Si of the organosilicon group.
In some embodiments, the number of chain atoms of the side chain is ≧ 5. In some embodiments, the side chain has from 5 to 50 chain atoms. In other embodiments, the side chain has from 5 to 20 chain atoms. In other embodiments, the number of chain atoms of the side chain is from 5 to 15.
The polymer contains nitrile groups (-CN), and the weight percentage of the nitrile groups in the polymer is 4-30%. Preferably, the weight percentage of the nitrile groups in the polymer is 20-29%. The nitrile groups are mainly derived from the backbone. When the side chain does not contain nitrile groups, all the nitrile groups come from the main chain; when the side chains contain nitrile groups, the nitrile groups are mainly from the main chain and a minor part from the side chains.
The silicon element is from the organosilicon group connected with the side chain, and the weight percentage of the silicon element in the polymer is 0.01-5%. In some embodiments, the silicon is present in the polymer in an amount of 0.1 to 1% by weight.
The side chain can have the formula
Figure BDA0003112925160000052
Figure BDA0003112925160000053
Figure BDA0003112925160000061
Figure BDA0003112925160000062
At least one of; wherein both ends of the main chain of the structural formula of the side chain listed above are respectively connected to the main chain of the polymer and Si of the organosilicon group, in the present application, toThe Si at which terminal is connected to the backbone of the polymer and which terminal is connected to the silicone group is not particularly limited. For example, the left end of the main chain of the structural formula of the side chain is connected to the main chain of the polymer, and the right end is connected to Si of the organosilicon group; or the right end of the main chain of the structural formula of the side chain is connected with the main chain of the polymer, and the left end is connected with Si of the organosilicon group.
When X is present 1 、X 2 And X 3 Are each methoxy (CH) 3 O-), then the organosilicon radicals
Figure BDA0003112925160000063
The radical is
Figure BDA0003112925160000064
When X is present 1 And X 2 Are each methoxy, X 3 Is methyl (-CH) 3 ) Then the organosilicon group
Figure BDA0003112925160000065
The radical is
Figure BDA0003112925160000066
When X is present 1 、X 2 And X 3 Are each ethoxy (C) 2 H 5 O-), then the organosilicon group
Figure BDA0003112925160000067
The group is
Figure BDA0003112925160000068
When X is present 1 And X 2 Are each ethoxy, X 3 Is methyl (-CH) 3 ) Then the organosilicon group
Figure BDA0003112925160000069
The group is
Figure BDA00031129251600000610
The organosilicon group
Figure BDA00031129251600000611
The radical may be
Figure BDA00031129251600000612
Figure BDA0003112925160000071
At least one of (a).
According to the adhesive, the side chain is introduced into the main chain structure of the water-soluble acrylonitrile copolymer and is connected with the organic silicon group, and the organic silicon group can form strong interaction anchoring with silicon particles with silicon hydroxyl on the surface, so that multidimensional adhesion of the silicon particles can be realized. The rigid main chain of the polyacrylonitrile copolymer has high mechanical strength, can maintain the stability of the electrode microscopic skeleton structure, and the side chain is telescopic, so that huge volume change and stress change of silicon particles in the charging and discharging processes are buffered. Meanwhile, the acrylonitrile copolymer of the main chain of the polymer is used as a solid electrolyte component, and has good lithium ion conductivity. Therefore, the aqueous binder has good adhesion when being used as the binder of the silicon-based negative electrode, can inhibit huge volume change of silicon particles to a certain extent in the circulation process, effectively keeps adhesion between an active material and a current collector, can effectively reduce internal resistance of a pole piece, inhibits expansion of the pole piece, and prolongs the service life of a battery.
The application's water-soluble binder compares Styrene Butadiene Rubber (SBR) system steric hindrance and is little, works as simultaneously the polymerization monomer of acrylonitrile copolymer includes the acrylate monomer, just the acrylate monomer is the lithium salt, then contain the lithium acrylate fragment in the acrylonitrile copolymer, can helping hand lithium ion conduction, improve the fast-charging performance and the low temperature performance of system.
In the preparation process of the polymer, the proportion of the acrylic monomer and the acrylonitrile monomer can be conventional in the field, the water solubility of the acrylic monomer and the acrylonitrile monomer is only required to be ensured, the whole binder formed by the polymer is water-soluble, and the binder can be uniformly mixed when being added into aqueous negative electrode slurry. In some embodiments, the weight ratio of acrylic monomer to acrylic monomer is 1 (0.1 to 2.5). Preferably, the weight ratio of the acrylic monomer to the acrylonitrile monomer is 1 (0.8 to 2.0). In some embodiments, when the polymerized monomers of the acrylonitrile copolymer further include acrylamide monomers or epoxy group-containing vinyl monomers, the weight ratio of the acrylamide monomers or epoxy group-containing vinyl monomers, acrylic monomers and acrylonitrile monomers is (0.1-2.5): 1- (0.1-2.5), preferably (0.8-2.0): 1- (0.8-2.0).
The polymers of the present application can be prepared by conventional methods. For example, it can be formed by copolymerizing or grafting the monomer raw materials.
The application also provides a negative electrode of a battery, which comprises the negative electrode active material and the binder. The negative active material includes a silicon-based material. In some embodiments, the negative active material may further include graphite. The silicon-based material is a simple substance or a compound containing a silicon element, for example, the silicon-based material is selected from one or more of silicon carbon, silicon monoxide, silicon oxide, silicon-iron alloy, silicon nanowire, micron silicon, nano silicon, porous silicon and silicon-germanium alloy. It is to be understood that the polymer described herein is not limited to use as a binder for a negative electrode of a battery, but may also be used as a binder in other possible fields or products.
In some embodiments, the negative electrode includes a current collector and a negative active material layer attached on the current collector, the negative active material layer including a negative active material, a conductive agent, and the above-described binder. The negative active material includes a silicon-based material and graphite. The negative electrode may be formed using methods conventional in the art.
The application also provides a preparation method of the cathode, which comprises the following steps: mixing the binder, the negative electrode active material, and the solvent to form a slurry; and coating the slurry on a negative current collector, drying, compacting and the like. The solvent is water. The negative active material includes a silicon-based material, or contains both a silicon-based material and graphite. The negative current collector may be a copper foil. And a proper amount of conductive agent is also added into the slurry.
The application also provides a lithium ion battery which comprises a negative electrode, a positive electrode and electrolyte. The positive electrode and the electrolyte may be used as commonly used in the art. Preferably, the lithium ion battery further comprises a diaphragm positioned between the negative electrode and the positive electrode, the diaphragm can effectively prevent the positive electrode and the negative electrode from contacting to cause internal short circuit, and can also prevent molecules with larger volume from passing through and only allow charged ions with small volume to pass through, so that the concentration difference near the positive electrode and the negative electrode is improved, the diffusion of ions is facilitated, and the storage efficiency of the battery is improved. The separator is a battery separator commonly used in the field. The negative electrode is the negative plate. It is to be understood that the binder is not limited to application to lithium ion battery systems, but may also be applied to other secondary battery systems, such as sodium ion batteries, potassium ion batteries, magnesium ion batteries, lithium sulfur batteries, and the like.
The application also provides a battery pack which comprises a plurality of lithium ion batteries. The battery pack may include a battery module composed of a plurality of lithium ion batteries. Several lithium ion batteries may be connected in series or in parallel.
The technical solution of the embodiments of the present application is further described below by specific examples.
The parts of each raw material in examples 1 to 14 and comparative examples 1 to 4 below are parts by weight.
Example 1
Example 1 a silicon-based negative electrode binder was prepared using sodium acrylate, acrylonitrile and 3- (acryloxy) propyltrimethoxysilane copolymerized in an aqueous phase.
The preparation method comprises the following steps: adding 40 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, and reacting acrylic acid with the sodium hydroxide to generate sodium acrylate; then 58 parts of acrylonitrile and 2 parts of 3- (acryloxy) propyl trimethoxy silane are added; introducing nitrogen to drive oxygen for 30min; heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the transparent silicon-based negative electrode binder.
Example 2
Example 2 a silicon-based negative electrode binder was prepared using the copolymerization of sodium methacrylate, acrylonitrile and 3- (methacryloyloxy) propyltrimethoxysilane in an aqueous phase.
The preparation method comprises the following steps: adding 45 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to be 7-8, and then adding 53 parts of acrylonitrile and 2 parts of 3- (methacryloyloxy) propyl trimethoxy silane; introducing nitrogen to drive oxygen for 30min; heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the transparent silicon-based negative electrode binder.
Example 3
Example 3 a silicon-based negative electrode binder was prepared using sodium methacrylate, acrylonitrile and 3- (methacryloyloxy) propylmethyldimethoxysilane copolymerized in an aqueous phase.
The preparation method comprises the following steps: adding 40 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to be 7-8, and then adding 57 parts of acrylonitrile and 3 parts of 3- (methacryloyloxy) propyl methyldimethoxysilane; introducing nitrogen to drive oxygen for 30min; and heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the transparent silicon-based negative electrode binder.
Example 4
Example 4 a silicon-based negative electrode binder was prepared by copolymerizing sodium methacrylate, acrylamide and acrylonitrile in an aqueous phase and then adding 3-glycidoxypropyltriethoxysilane.
The preparation method comprises the following steps: adding 35 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, then adding 52 parts of acrylonitrile and 10 parts of acrylamide, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, adding 3 parts of 3-glycidyl ether oxypropyltriethoxysilane after 9 hours of polymerization reaction, and continuing stirring and reacting for 2 hours to obtain the silicon-based negative electrode binder.
Example 5
Example 5 a silicon-based negative electrode binder was prepared by copolymerizing sodium acrylate, acrylamide and acrylonitrile in an aqueous phase followed by the addition of 3-glycidoxypropylmethyldimethoxysilane.
The preparation method comprises the following steps: adding 30 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring for dissolving, adjusting the rotating speed to 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, adding 55 parts of acrylonitrile and 10 parts of acrylamide, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, adding 0.05 part of ammonium persulfate to initiate reaction, adding 5 parts of 3-glycidyl ether oxypropyl methyldimethoxysilane after 9 hours of polymerization reaction, and continuously stirring for reacting for 2 hours to obtain the silicon-based negative electrode binder.
Example 6
Example 6 a silicon-based negative electrode binder was prepared by copolymerizing sodium methacrylate, acrylamide and acrylonitrile in an aqueous phase, followed by the addition of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
The preparation method comprises the following steps: adding 35 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, then adding 52 parts of acrylonitrile and 10 parts of acrylamide, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, adding 3 parts of 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane after 9 hours of polymerization reaction, and continuously stirring and reacting for 2 hours to obtain the silicon-based negative electrode binder.
Example 7
Example 7 a silicon-based negative electrode binder was prepared by copolymerizing sodium acrylate, acrylonitrile, and glycidyl methacrylate in an aqueous phase, followed by the addition of 3-aminopropyltriethoxysilane.
The preparation method comprises the following steps: adding 30 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, adding 55 parts of acrylonitrile and 10 parts of glycidyl methacrylate, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, adding 0.05 part of potassium persulfate to initiate reaction, adding 5 parts of 3-aminopropyltriethoxysilane after 9 hours of polymerization reaction, and continuously stirring and reacting for 2 hours to obtain the silicon-based negative electrode binder.
Example 8
Example 8 a silicon-based negative electrode binder was prepared by copolymerizing sodium acrylate, acrylonitrile and glycidyl methacrylate in an aqueous phase followed by the addition of 3-aminopropylmethyldiethoxysilane.
The preparation method comprises the following steps: adding 35 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, then adding 52 parts of acrylonitrile and 8 parts of glycidyl methacrylate, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, then adding 0.05 part of potassium persulfate to initiate reaction, adding 5 parts of 3-aminopropylmethyldiethoxysilane after polymerization reaction for 9 hours, and continuously stirring and reacting for 2 hours to obtain the silicon-based cathode binder.
Example 9
Example 9 a silicon-based negative electrode binder was prepared by copolymerizing sodium methacrylate, acrylonitrile and allyl glycidyl ether in an aqueous phase followed by the addition of 3-divinyltriaminopropylmethyldimethoxysilane.
The preparation method comprises the following steps: adding 40 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring for dissolving, adjusting the rotating speed to 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, adding 48 parts of acrylonitrile and 8 parts of allyl glycidyl ether, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, adding 0.05 part of potassium persulfate to initiate reaction, adding 4 parts of 3-diethylenetriaminopropylmethyldimethoxysilane after the polymerization reaction is carried out for 9h, and continuously stirring for reacting for 2h to obtain the silicon-based cathode binder.
Example 10
Example 10 a silicon-based negative electrode binder was prepared using lithium acrylate, acrylonitrile, and 3- (acryloxy) propyltrimethoxysilane copolymerized in an aqueous phase.
The preparation method comprises the following steps: adding 40 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding lithium hydroxide to adjust the pH value to be 7-8, and reacting acrylic acid with the lithium hydroxide to generate lithium acrylate; then 58 parts of acrylonitrile and 2 parts of 3- (acryloxy) propyl trimethoxy silane are added; introducing nitrogen to drive oxygen for 30min; and heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the transparent silicon-based negative electrode binder.
Example 11
Example 11 a silicon-based negative electrode binder was prepared by copolymerizing lithium acrylate, acrylamide and acrylonitrile in an aqueous phase followed by the addition of 3-glycidoxypropylmethyldimethoxysilane.
The preparation method comprises the following steps: adding 30 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring for dissolving, adjusting the rotating speed to 300r/min, adding lithium hydroxide to adjust the pH value to 7-8, adding 55 parts of acrylonitrile and 10 parts of acrylamide, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, adding 0.05 part of ammonium persulfate to initiate reaction, adding 5 parts of 3-glycidyl ether oxypropyl methyldimethoxysilane after 9 hours of polymerization reaction, and continuously stirring for reacting for 2 hours to obtain the silicon-based negative electrode binder.
Example 12
Example 12 a silicon-based negative electrode binder was prepared by copolymerizing lithium acrylate, acrylonitrile, and glycidyl methacrylate in an aqueous phase, followed by the addition of 3-aminopropyltriethoxysilane.
The preparation method comprises the following steps: adding 30 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding lithium hydroxide to adjust the pH value to 7-8, adding 55 parts of acrylonitrile and 10 parts of glycidyl methacrylate, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, adding 0.05 part of potassium persulfate to initiate reaction, adding 5 parts of 3-aminopropyltriethoxysilane after 9 hours of polymerization reaction, and continuously stirring and reacting for 2 hours to obtain the silicon-based negative electrode binder.
Example 13
Example 13 a silicon-based negative electrode binder was prepared using the copolymerization of lithium methacrylate, acrylonitrile, and 3- (methacryloyloxy) propyltrimethoxysilane in an aqueous phase.
The preparation method comprises the following steps: adding 45 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding lithium hydroxide to adjust the pH value to be 7-8, and then adding 53 parts of acrylonitrile and 2 parts of 3- (methacryloyloxy) propyl trimethoxy silane; introducing nitrogen to drive oxygen for 30min; heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the transparent silicon-based negative electrode binder.
Example 14
Example 14 a silicon-based negative electrode binder was prepared by copolymerizing lithium methacrylate, acrylonitrile, and allyl glycidyl ether in an aqueous phase followed by the addition of 3-divinyltriaminopropylmethyldimethoxysilane.
The preparation method comprises the following steps: adding 40 parts of methacrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding lithium hydroxide to adjust the pH value to 7-8, adding 48 parts of acrylonitrile and 8 parts of allyl glycidyl ether, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, adding 0.05 part of potassium persulfate to initiate reaction, adding 4 parts of 3-diethylenetriaminopropyl methyldimethoxysilane after polymerization reaction is carried out for 9 hours, and continuously stirring and reacting for 2 hours to obtain the silicon-based cathode binder.
Comparative example 1
Comparative example 1 a silicon-based negative electrode binder was prepared by copolymerizing sodium acrylate, acrylonitrile and vinyltrimethoxysilane in an aqueous phase.
The preparation method comprises the following steps: adding 40 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, and then adding 58 parts of acrylonitrile and 2 parts of vinyl trimethoxy silane; introducing nitrogen to drive oxygen for 30min; heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the silicon-based negative electrode binder.
Comparative example 2
Comparative example 2 a silicon-based negative electrode binder was prepared by copolymerizing sodium acrylate and acrylonitrile in an aqueous phase, and then adding 3- (acryloxy) propyltrimethoxysilane for blending.
The preparation method comprises the following steps: adding 40 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding sodium hydroxide to adjust the pH value to 7-8, adding 58 parts of acrylonitrile, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, stopping the reaction after the polymerization reaction lasts for 9 hours, adding 2 parts of 3- (acryloyloxy) propyl trimethoxy silane, and continuously and uniformly stirring to obtain the silicon-based negative electrode binder.
Comparative example 3
Comparative example 3 a silicon-based negative electrode binder was prepared by copolymerizing lithium acrylate, acrylonitrile and vinyltrimethoxysilane in an aqueous phase.
The preparation method comprises the following steps: adding 40 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding lithium hydroxide to adjust the pH value to 7-8, and then adding 58 parts of acrylonitrile and 2 parts of vinyl trimethoxy silane; introducing nitrogen to drive oxygen for 30min; heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, and reacting for 9 hours to obtain the silicon-based negative electrode binder.
Comparative example 4
Comparative example 4 a silicon-based negative electrode binder was prepared by copolymerizing lithium acrylate and acrylonitrile in an aqueous phase, and then adding 3- (acryloxy) propyltrimethoxysilane for blending.
The preparation method comprises the following steps: adding 40 parts of acrylic acid and 566 parts of distilled water into a reaction container, stirring and dissolving at the rotating speed of 300r/min, adding lithium hydroxide to adjust the pH value to 7-8, adding 58 parts of acrylonitrile, introducing nitrogen to drive oxygen for 30min, heating to 70 ℃, then adding 0.05 part of ammonium persulfate to initiate reaction, stopping the reaction after 9 hours of polymerization reaction, adding 2 parts of 3- (acryloyloxy) propyl trimethoxy silane, and continuously stirring uniformly to obtain the silicon-based negative electrode binder.
The silicon cathode lithium ion battery is prepared by the following method:
mixing 0.95 weight part of negative electrode active material compounded by silicon monoxide and graphite, 0.02 weight part of conductive agent (carbon black, SP) and 0.03 weight part of silicon-based negative electrode binder (the mass parts are calculated by the solid content after complete drying) prepared in the above examples and comparative examples by taking water as a solvent, stirring and grinding to prepare negative electrode slurry, adjusting the solid content of the slurry to be 50%, uniformly coating the slurry on a copper foil, and then drying, compacting and punching to prepare a negative electrode piece; carrying out vacuum drying on the obtained negative pole piece at 100 +/-5 ℃ for 24 hours, then placing the negative pole piece in a glove box in a dry argon atmosphere, and assembling the button cell by taking a metal lithium piece as a counter electrode; the diaphragm is a polyolefin microporous film, and the electrolyte is commercially available electrolyte for a silicon-based negative lithium ion battery.
The silicon negative electrode lithium ion batteries prepared by using the binders in the above examples 1 to 14 are sequentially numbered as A1 to A14, and the silicon negative electrode lithium ion batteries prepared by using the binders in the comparative examples 1 to 4 are sequentially numbered as C1 to C4. The prepared silicon cathode lithium ion battery is subjected to charge and discharge tests at 25 ℃, and the performance of the battery is shown in the table.
Figure BDA0003112925160000111
Figure BDA0003112925160000121
As can be seen from the above table, the lithium ion batteries with silicon cathodes prepared by using the binders described in examples 1 to 14 have good cycle performance, and the capacity retention rates after 50 times of charge and discharge reach 90% or more, which is obviously better than the cycle performance of the lithium ion batteries with silicon cathodes prepared by using the binders described in comparative examples 1 to 4. The silane coupling agents added in the comparative examples 2 and 4 are not grafted to the main chain of the binding agent through chemical bonds to form side chains, the silane coupling agents selected in the comparative examples 1 and 3 do not contain side chains after being copolymerized with main chain monomers, and the flexibility of the side chains is insufficient, so that the binding agent in the comparative examples cannot effectively stabilize the stability of an electrode structure in the charging and discharging processes of the silicon cathode lithium ion battery, and the difference in cycle performance is caused.
It should be noted that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present application, and all should be covered by the scope of the present application; the embodiments and features of the embodiments of the present application may be combined with each other without conflict. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (23)

1. A polymer, comprising:
a backbone consisting essentially of a water-soluble acrylonitrile copolymer having polymerized monomers including acrylic and acrylonitrile-based monomers;
a side chain having one end connected to the main chain and the other end connected to a silicone group
Figure FDA0003112925150000011
X 1 、X 2 And X 3 Each independently selected from one of C1-C4 alkyl, hydroxyl, halogen atom and C1-C4 alkoxy, and X 1 、X 2 And X 3 Not being alkyl at the same time;
the chain atom number of the side chain is more than or equal to 3, and the chain atom number is the total number of non-hydrogen atoms in the non-branched chain of the side chain.
2. The polymer of claim 1, wherein the polymer comprises from 4% to 30% by weight of nitrile groups in the polymer; the weight percentage of the silicon element in the polymer is 0.01-5%.
3. A polymer according to claim 1 or 2, characterized in that the polymer contains nitrile groups in a percentage of 20-29% by weight of the polymer.
4. The polymer according to any one of claims 1 to 3, wherein the percentage by weight of elemental silicon in the polymer is between 0.1% and 1%.
5. The polymer of any of claims 1-4, wherein the acrylic monomer comprises at least one of an acrylic acid salt, a methacrylic acid salt, and a methacrylic acid salt, the acrylic acid salt and the methacrylic acid salt each being at least one of a sodium salt, a potassium salt, a lithium salt, a rubidium salt, and a cesium salt.
6. The polymer of any one of claims 1 to 5, wherein the acrylonitrile-based monomer comprises at least one of acrylonitrile and methacrylonitrile.
7. The polymer according to any one of claims 1 to 6, wherein the polymerized monomers of the acrylonitrile copolymer further comprise acrylamide-based monomers or epoxy-containing olefinic monomers.
8. The polymer of claim 7, wherein the acrylamide-based monomer is at least one of acrylamide, N-methacrylamide, N-ethylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, 2-methacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, and N-hydroxypropylacrylamide; the epoxy group-containing alkene monomer is at least one of glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether.
9. The polymer according to any of claims 1 to 8, wherein the number of chain atoms of the side chain is 5 or more.
10. The polymer according to any one of claims 1 to 9,
the structural formula of the side chain is
Figure FDA0003112925150000012
Figure FDA0003112925150000013
Figure FDA0003112925150000021
Figure FDA0003112925150000022
At least one of; wherein, two ends of the main chain of the structural formula of the side chain are respectively connected with the main chain of the polymer and the Si of the organic silicon group.
11. A binder comprising the polymer of any one of claims 1 to 10.
12. The binder of claim 11, wherein the binder is a binder of a negative electrode of a battery.
13. Use of a polymer according to any one of claims 1 to 10 as a binder.
14. A negative electrode for a battery comprising a negative electrode active material and a binder, characterized in that the binder comprises the polymer of any one of claims 1 to 10.
15. The negative electrode for a battery according to claim 14, wherein the negative electrode active material comprises a silicon-based material.
16. The negative electrode of the battery according to claim 14, wherein the negative electrode comprises a current collector and a negative electrode active material layer attached to the current collector, and the negative electrode active material layer comprises the negative electrode active material and the binder.
17. A secondary battery comprising a negative electrode, a positive electrode, and an electrolyte, wherein the negative electrode comprises a negative electrode active material and a binder, and wherein the binder comprises the polymer according to any one of claims 1 to 10.
18. The secondary battery according to claim 17, wherein the negative electrode active material comprises a silicon-based material.
19. The secondary battery according to claim 17, wherein the negative electrode includes a current collector and a negative electrode active material layer attached to the current collector, the negative electrode active material layer including the negative electrode active material and the binder.
20. A method of making a negative electrode for a battery, comprising:
mixing a negative electrode active material, a binder, a solvent to form a slurry, the binder including the polymer of any one of claims 1 to 10;
and coating the slurry on a negative current collector and drying.
21. The method of manufacturing a negative electrode for a battery according to claim 20, wherein the solvent is water.
22. The method of preparing a negative electrode for a battery according to claim 20, wherein the negative electrode active material comprises a silicon-based material.
23. The method for manufacturing an anode of a battery according to claim 22, wherein the anode active material further includes graphite.
CN202110653757.0A 2021-06-11 2021-06-11 Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode Pending CN115472834A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110653757.0A CN115472834A (en) 2021-06-11 2021-06-11 Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110653757.0A CN115472834A (en) 2021-06-11 2021-06-11 Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode

Publications (1)

Publication Number Publication Date
CN115472834A true CN115472834A (en) 2022-12-13

Family

ID=84364832

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110653757.0A Pending CN115472834A (en) 2021-06-11 2021-06-11 Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode

Country Status (1)

Country Link
CN (1) CN115472834A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116217794A (en) * 2023-01-09 2023-06-06 万华化学集团电池科技有限公司 Solution type binder and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116217794A (en) * 2023-01-09 2023-06-06 万华化学集团电池科技有限公司 Solution type binder and preparation method and application thereof
CN116217794B (en) * 2023-01-09 2024-04-09 万华化学集团电池科技有限公司 Solution type binder and preparation method and application thereof

Similar Documents

Publication Publication Date Title
EP1629556B1 (en) Composite binder for an electrode with dispersants chemically bound
KR101615940B1 (en) Binder Composition for Secondary Battery, and Electrode Employed with the Same, and Lithium Secondary Battery
KR20190039993A (en) Acrylonitrile Copolymer Adhesives and Their Applications in Lithium Ion Batteries
CN111662418B (en) Lithiation functional polymer for lithium ion cell and its prepn and application
CN111635478B (en) Low-impedance binder and preparation method and application thereof
CN102959773A (en) Binder having excellent adhesion for secondary battery
KR101483504B1 (en) Electrode Material for Secondary Battery Providing Excellent Rate and Cycling Characteristics
CN102473923A (en) Binder having good adhesion for secondary battery
CN110010896B (en) Ion conductive cross-linking adhesive for lithium ion battery and preparation method thereof
CN111785968A (en) Silicon-based negative electrode binder of lithium ion battery and preparation method and application thereof
CN113024707A (en) Environment-friendly aqueous silicon-carbon negative electrode binder and preparation method and application thereof
CN114039097A (en) Lithium ion battery
CN114388795B (en) Silicon-carbon negative electrode binder of lithium ion battery and preparation method thereof
CN113851710B (en) Sodium ion difunctional gel polymer electrolyte, preparation method and application thereof
KR101640109B1 (en) Binder Composition for Secondary Battery Providing Improved Adhesion Strength, and Lithium Secondary Battery Comprising The Same
CN115472834A (en) Polymer, binder comprising polymer, negative electrode and preparation method of negative electrode
WO2016082657A1 (en) Lithium metal electrode, method for preparing same, and lithium rechargeable battery
KR101717209B1 (en) Binder Having Higher Performance and Lithium Secondary Battery Comprising the Same
KR20170076296A (en) Binder composition for secondary battery, electrode employed with the same, and lithium secondary battery comprising the same
CN111682262B (en) Three-dimensional cross-linked network gel polymer electrolyte membrane and preparation method and application thereof
CN110492101B (en) Lithium ion battery cathode binder and preparation method and application thereof
CN113025235A (en) Lithium ion battery binder and preparation method and application thereof
CN116515032A (en) High-toughness water-based binder, preparation method and application thereof, lithium ion battery negative electrode slurry and lithium ion battery negative electrode
CN115911391A (en) Adhesive for lithium ion battery, preparation method and application thereof
CN114122398B (en) Integrated conductive adhesive and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination