CN108441146A - A kind of binder of silicon-carbon cathode material and preparation method thereof - Google Patents
A kind of binder of silicon-carbon cathode material and preparation method thereof Download PDFInfo
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- CN108441146A CN108441146A CN201810159382.0A CN201810159382A CN108441146A CN 108441146 A CN108441146 A CN 108441146A CN 201810159382 A CN201810159382 A CN 201810159382A CN 108441146 A CN108441146 A CN 108441146A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/12—N-Vinylcarbazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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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
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
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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
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/16—Homopolymers or copolymers of alkyl-substituted styrenes
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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
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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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
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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 kind of binders of silicon-carbon cathode material, the alkene for containing stiffening ring including side chain is copolymerized with containing the monomer of carboxyl or ester group, the polymer of formation, the present invention will contain the larger polyolefins monomer of stiffening ring steric hindrance containing side chain and prepare polymer by solution copolymerization with the monomer containing carboxyl and ester group, and the bonding agent as silicon carbon cathode material, the polymer bonding agent of preparation is when being bonded negative material, pendant reactive group carboxyl can be inhibited with silicon carbon cathode material active site strong bond, irreversible sliding phenomenon.Bonding agent takes into account rigidity and cementability simultaneously.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of binder of silicon-carbon cathode material, silicon-carbon electricity
The cathode pole piece in pond and preparation method thereof, silicon-carbon battery.
Background technology
Currently, the lithium ion battery produced and used mainly uses graphite negative electrodes material, but the embedding lithium capacity of theory of graphite
For 372mAh/g, graphite negative electrodes material, almost without room for promotion, has been unable to meet high energy density lithium ion on capacity
The growth requirement of battery；In addition, it is hidden to bring huge safety very close to the deposition potential of lithium to battery for its intercalation potential
Suffer from.Specific capacity when the completely embedding lithium of silicon forms Li22 Si5 alloys is up to 4200 mAh/g, is the negative material developed at present
In it is highest；The current potential of Li insertion extraction is moderate（Between 0~0.45 V), security performance is better than graphite negative electrodes material；And silicon
Content of the element in the earth's crust occupies second, derives from a wealth of sources, and is a kind of very promising lithium ion battery negative material.
But the Volumetric expansion during silicon Li insertion extraction is the principal element for limiting silicon materials and using.It is most of
Researcher is from the angle of material itself, by silicon materials nanosizing and Composite, so that its performance has been obtained a degree of
Take on a new look.These researchs are concentrated mainly on the microstructure of regulation activity material to optimize the performance of material, and only a small amount of research is reported
The road influence of binder and conductive agent to electrode performance, the results showed that：Electrode plates are a complicated unit, electrode material
Material, auxiliary material conductive agent, bonding agent and manufacture craft codetermine the final performance of pole piece, thus many extremely important
Performance, including cyclical stability and irreversible capacity for the first time are all strongly depend on the performance of binder, rather than just change
The structure and performance of material itself are with regard to attainable.
Thus, develop the research and development for being suitble to the binder of height ratio capacity silicium cathode material to become recent lithium battery auxiliary material
Emphasis.And recent studies have indicated that：Polymer with carboxyl（Such as polyacrylic acid（PAA））, sodium alginate（Alg）Compared to tradition
Binder such as Kynoar（PVDF）It is more suitable for making the binder of silicon based anode material.PAA is compared with PVDF, nothing
Set degree is high, and conformality in the electrolytic solution is good；- COOH the concentration of PAA unit masses compared with CMC is high, from poly-
From the point of view of closing the molecular structure that object bonds, PVDF, CMC, Alg and PAA belong to the polymer of straight-chain, after recycling for a long time,
Irreversible sliding easily occurs between active particle for the polymeric binder of this straight chain structure, causes active material and electrode
Electrical connectivity is lost between matrix, increases the irreversible specific capacity of electrode.
It is another to there are 104953124 A of Chinese patent publication No. CN to disclose a kind of binder of silicon-carbon cathode material, silicon-carbon electricity
The cathode pole piece in pond and preparation method thereof, silicon-carbon battery, the binder of silicon-carbon cathode material include the polymer containing hydroxyl and
Polymer containing carboxyl.The cathode pole piece of silicon-carbon battery is dehydrated the characteristic for forming ester group using carboxyl and hydroxyl at high temperature,
Binder in pole piece is cross-linked into reticular structure, and there is good rigidity and caking property.Above-mentioned binder has been used to prepare
The stabilization specific capacity of cathode pole piece of silicon-carbon battery be more than 600mAh/g, first charge discharge efficiency is more than 75%, the silicon in silicon-carbon battery
Base active particle is evenly distributed in the three-dimensional network of binder, and the rigid structure of binder inhibits the variation of pole piece thickness.
Above-mentioned patent mixes polyacrylic acid and polymer with hydroxyl, in the manufacturing process of pole piece heating make polyphosphazene polymer
Esterification occurs between conjunction object, to obtain crosslinked three-dimensional network polymer binder.Cohesive force between silicium cathode
Mainly by three-dimensional network cross-linked structure, this kind of binder is although two kinds of performances of cohesive force and mechanical strength can be taken into account simultaneously.But
The performance of binder and crosslinked degree are esterified ability and are affected in by hydroxyl and carboxyl esterification reaction process, product
Consistency is difficult to determine.
Invention content
Problem to be solved by this invention is aiming at the above shortcomings existing in the prior art, to provide a kind of silicon-carbon cathode material
Binder of material and preparation method thereof, and utilize the cathode pole piece and silicon-carbon battery of the silicon-carbon battery of binder preparation.It is logical
Cross by acrylic monomers and side chain contain stiffening ring or the larger monomeric compound copolymerization of steric hindrance and on the main chain of polyolefin
It introduces, then can effectively stop active chain structure and be subjected to displacement, maintain the stabilization of electrode structure.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
A kind of binder of silicon-carbon cathode material, it is characterised in that：Including side chain contain the alkene of stiffening ring with containing carboxyl or
The monomer of ester group is copolymerized, the polymer of formation.
The side chain contains the alkene of stiffening ring and the molar ratio 1 of the monomer containing carboxyl or ester group:（1-10）.
The side chain contain stiffening ring alkene be nitrogen vinyl carbazole, methyl styrene, vinylnaphthalene, to benzene divinyl
One kind in naphthalene, vinyl pyrrole ketone.
Monomer containing carboxyl or ester group is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, third
One kind in olefin(e) acid ethyl ester, butyl acrylate.
A kind of preparation method of the binder of silicon-carbon cathode material, it is characterised in that：Side chain is contained to the Olefin of stiffening ring
It with the monomer b containing carboxyl or ester group under initiator effect, is added in solvent, polymerisation in solution occurs for heating, forms a-co-
B copolymer binders.
The initiator of the nitrogenous class of initiator, including：Azodiisobutyronitrile（AIBN), azobisisoheptonitrile (ABVN) or
Azobisisovaleronitrile.
The solvent is dimethylformamide（DMF）, dimethyl sub-maple（DMSO）And acetonitrile（AN）In one kind or
Several mixed solvents.
The heating temperature is 50~150 DEG C, and the heating time is 1~10 hour.
The present invention also provides a kind of production methods of the cathode pole piece of silicon-carbon battery, include the following steps：
（1）There is the Olefin of stiffening ring with another monomer b containing carboxyl or ester group under initiator effect side chain, suitable
When solvent in, occur polymerisation in solution under heating state, form a-co- b copolymer binders；
（2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes leading
Electric agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
The present invention has the following advantages：
The present invention takes compared with 104953124 A of CN and is totally different from referred in above-mentioned file carry out two kinds of polymer
The method for being simply mixed or being esterified.But by side chain with stiffening ring or steric hindrance larger olefinic monomer and acrylic monomers
It carries out " solution copolymerization ", finally obtains a kind of new " random " or " block " copolymer.Remain on monomeric acrylic-
COOH has given full play to the rich carboxylic advantage of single polyacrylic acid PAA binders, that is,-the COOH being evenly distributed can be with work
There are sufficiently large binding force and enough binding sites in property silicon materials and copper current collector surface.Simultaneously because new copolymer exists
The groups such as the larger stiffening ring of steric hindrance are introduced in PAA side chains, can prevent binder with silicon particle in multiple cycle charging
Irreversible sliding phenomenon occurs, greatly maintains the stability of electrode structure.In order to effectively slow down the polymer of straight chain structure
Irreversible sliding occurs between binder and active particle, overcomes the inherent defect of rich carboxylic binder and it is kept to have
Side chain is contained the larger olefin monomer of the steric hindrances such as stiffening ring with the monomer containing carboxyl or ester group in solution by advantage, the present invention
Middle copolymerization obtains polymer, and for the binder of silicon carbon cathode material.The polymeric binder of preparation is bonding negative material
When, pendant reactive group carboxyl can be inhibited with silicon carbon cathode material active site secure bond, irreversible sliding phenomenon.It bonds
Agent takes into account rigidity and caking property simultaneously.
After tested：Used the present invention silicon-carbon cathode material binder prepare silicon-carbon battery, cathode pole piece it is steady
Determine specific capacity and be more than 600 mAh/g, first charge discharge efficiency is more than 75%, and the silicon-based active particle in silicon-carbon battery is evenly distributed on bonding
In the stiffening ring of agent, it is shown that the rigid structure of higher mechanical stretching performance, binder effectively inhibits the huge body of pole piece
Product variation.The raw materials used in the present invention is cheap and easy to get, preparation process is simple, flow is short, process is easy to control, industrialization easy to implement
Production.
Specific implementation mode
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment, the sides
Method is conventional method unless otherwise instructed, and the material can obtain unless otherwise instructed from open commercial sources.
Embodiment 1
The present embodiment provides a kind of production methods and cathode pole piece of the bonding agent of silicon carbon cathode material, include the following steps：
1）By nitrogen vinyl carbazole and acrylic acid（AA）And initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to equipped with solvent two
Methyl Asia amide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-co- b is total
Polymers binder, is cooled to room temperature, polymer solids level 5~50%, can be used for negative electrode binder directly or through dilution.
The structural formula of nitrogen vinyl carbazole and acrylic acid：
The structural formula of the polymeric binder of preparation：
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 760mAh/g, and first charge discharge efficiency 76%, it is 605mAh/g to stablize specific capacity,
575mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, 2.46 f/mm of its cementitiousness after tested, in general, 0.5 f/mm or more of bonding numerical value of binder is recognized
To be excellent.Reason is attributed to silicon-based active particle and is firmly fixed on the active site of binder, effectively prevents activity
The sliding of particle and binder main chain.The pole piece of silicium cathode cubical expansivity after charge and discharge 100 times is only 18%.Binder
Rigid structure inhibits the variation of pole piece volume.Silicon-based active particle in the pole piece volume in process of intercalation can still increase
Greatly, but increased volume is filled primarily in pole piece in the hole of original silicon-carbon cathode material.
Embodiment 2
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By methyl styrene and acrylic acid（AA）And initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to equipped with solvent two
Methyl Asia amide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-co- b is total
Polymers binder, is cooled to room temperature, polymer solids level 5 ~ 50%, can be used for negative electrode binder directly or through dilution.
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 675mAh/g, and first charge discharge efficiency 75%, it is 575mAh/g to stablize specific capacity,
542mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 2.05 f/mm of its cementitiousness.
Embodiment 3
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By vinyl pyrrole ketone and acrylic acid（AA）And initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to equipped with solvent
Dimethyl imide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-co-b
Copolymer binder is cooled to room temperature, polymer solids level 5~50%, can be used for negative electrode binder directly or through dilution.
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 720mAh/g, and first charge discharge efficiency 78%, it is 635mAh/g to stablize specific capacity,
585mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 2.76 f/mm of its cementitiousness.
Embodiment 4
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By vinyl naphthalene and acrylic acid（AA）And initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to equipped with solvent diformazan
Base Asia amide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-co- b is copolymerized
Object binder, is cooled to room temperature, polymer solids level 5~50%, can be used for negative electrode binder directly or through dilution.
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 705mAh/g, and first charge discharge efficiency 73%, it is 618mAh/g to stablize specific capacity,
545mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 2.12 f/mm of its cementitiousness.
Embodiment 5
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）It will be to benzene divinyl and acrylic acid（AA）With initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to equipped with solvent
Dimethyl imide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-co-b
Copolymer binder is cooled to room temperature, polymer solids level 5~50%, can be used for negative electrode binder directly or through dilution.
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 665mAh/g, and first charge discharge efficiency 73%, it is 602mAh/g to stablize specific capacity,
534mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 2.36 f/mm of its cementitiousness.
Embodiment 6
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By glycidyl methacrylate（GMA）With acrylic acid（AA）And initiator azodiisobutyronitrile（AIBN）Mixing,
It is added dropwise to and solvent dimethyl imide is housed（DMF）Four-hole bottle in, being 80 DEG C~150 DEG C in temperature, that solution occur is poly-
It closes, forms a-co- b copolymer binders, are cooled to room temperature, polymer solids level 5~50%, can be directly or through diluting for bearing
Pole binder.
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 675mAh/g, and first charge discharge efficiency 75%, it is 642mAh/g to stablize specific capacity,
554mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 2.58 f/mm of its cementitiousness.
Embodiment 7
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By vinyl pyrrolidone and dodecenylsuccinic acid and initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to dress
There is solvent dimethyl imide（DMF）Four-hole bottle in, in the case that temperature be 50 DEG C~150 DEG C polymerisation in solution occurs, formed
a-co- b copolymer binders, are cooled to room temperature, polymer solids level 5~50%, can be bonded directly or through dilution for cathode
Agent.
2）It is coated on negative current collector after silicon-carbon cathode material and auxiliary material are mixed, it is dry, wherein the auxiliary material includes conduction
Agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 620mAh/g, and first charge discharge efficiency 72%, it is 575mAh/g to stablize specific capacity,
555mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 2.08 f/mm of its cementitiousness.
Embodiment 8
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By nitrogen vinyl carbazole and dodecenylsuccinic acid and initiator azodiisobutyronitrile（AIBN）Mixing, is added dropwise to and is equipped with
Solvent dimethyl imide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-co- b copolymer binders, are cooled to room temperature, polymer solids level 5~50%, can be used for negative electrode binder directly or through dilution.
2）Will silicon-carbon cathode material and auxiliary material mix after be coated on negative current collector, it is dry, wherein the auxiliary material includes
Conductive agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 585mAh/g, and first charge discharge efficiency 71%, it is 550mAh/g to stablize specific capacity,
542mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 1.95 f/mm of its cementitiousness.
Embodiment 9
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By nitrogen vinyl carbazole and dodecenylsuccinic acid and initiator azodiisobutyronitrile（AIBN it) mixes, is added dropwise to and is equipped with
Solvent dimethyl imide（DMF）Four-hole bottle in, be 50 DEG C~150 DEG C in temperature and occur polymerisation in solution, form a-
Co-b copolymer binders, are cooled to room temperature, polymer solids level 5~50%, can be used for negative electrode binder directly or through dilution.
2）Will silicon-carbon cathode material and auxiliary material mix after be coated on negative current collector, it is dry, wherein the auxiliary material includes
Conductive agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 573mAh/g, and first charge discharge efficiency 71%, it is 550mAh/g to stablize specific capacity,
538mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 1.86 f/mm of its cementitiousness.
Embodiment 10
The present embodiment provides a kind of production methods and cathode pole piece of the binder of silicon carbon cathode material, include the following steps：
1）By glycidyl methacrylate（GMA）With dodecenylsuccinic acid and initiator azodiisobutyronitrile（AIBN）It is mixed
It closes, is added dropwise to equipped with solvent dimethyl imide（DMF）Four-hole bottle in, in the case that temperature be 80 DEG C~150 DEG C occur it is molten
Liquid polymerize, and forms a-co-b copolymer binders, is cooled to room temperature, polymer solids level 5~50%, can be used directly or through dilution
In negative electrode binder.
2）Will silicon-carbon cathode material and auxiliary material mix after be coated on negative current collector, it is dry, wherein the auxiliary material includes
Conductive agent and above step（1）The binder of preparation obtains the cathode pole piece of silicon-carbon battery.
3）It is to electrode, polyalkene diaphragm and to include organic mixed solvent with lithium piece using the cathode in step 2（ EC
（Ethyl carbonate ester）+DMC（Dimethyl carbonate））Electrolyte LiPF6（A concentration of 1mol/L, in the gloves full of argon gas
It is assembled into 2032 button cells in case, cycle is implemented with different multiplying powers and multiplying power is tested.
The present embodiment has carried out charge-discharge performance test to the composite cathode material for lithium ion cell of preparation, specific
Performance parameter is as follows：First discharge specific capacity has reached 565mAh/g, and first charge discharge efficiency 70%, it is 556mAh/g to stablize specific capacity,
526mAh/g is stilled remain in after 100 cycles.
This experiment is also tested the cementitiousness of binder, using peel test fixing device, implements to electrode
90 degree of peel tests, after tested 1.75 f/mm of its cementitiousness.
Above embodiment properties critical data is summarized as follows table：
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary embodiment party that uses
Formula, however the present invention is not limited thereto.For those skilled in the art, in the spirit for not departing from the present invention
In the case of essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Claims (8)
1. a kind of binder of silicon-carbon cathode material, it is characterised in that：The alkene that contains stiffening ring including side chain and contain carboxyl
Or the monomer copolymerization of ester group, the polymer of formation.
2. a kind of binder of silicon-carbon cathode material according to claim 1, it is characterised in that：The side chain contains rigidity
The molar ratio 1 of the alkene of ring and the monomer containing carboxyl or ester group:（1-10）.
3. a kind of binder of silicon-carbon cathode material according to claim 1, it is characterised in that：The side chain contains just
Property ring alkene be nitrogen vinyl carbazole, methyl styrene, vinylnaphthalene, to one kind in benzene divinyl naphthalene, vinyl pyrrole ketone.
4. a kind of binder of silicon-carbon cathode material according to claim 1, it is characterised in that：Containing carboxyl or ester group
Monomer is one in acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate
Kind.
5. a kind of preparation method of the binder of silicon-carbon cathode material, it is characterised in that：By side chain contain the Olefin of stiffening ring with
Monomer b containing carboxyl or ester group is added under initiator effect in solvent, and polymerisation in solution occurs for heating, forms a-co-b
Copolymer binder.
6. a kind of preparation method of the binder of silicon-carbon cathode material according to claim 5, it is characterised in that：It is described to draw
The initiator of the nitrogenous class of agent is sent out, including：Azodiisobutyronitrile（AIBN）, azobisisoheptonitrile（ABVN）Or azobisisovaleronitrile.
7. a kind of preparation method of the binder of silicon-carbon cathode material according to claim 5, it is characterised in that：Described
Solvent is dimethylformamide（DMF）, dimethyl sub-maple（DMSO）And acetonitrile（AN）One or more of mixed solvent.
8. a kind of preparation method of the binder of silicon-carbon cathode material according to claim 5, it is characterised in that：It is described to add
Hot temperature is 50~150 DEG C, and the heating time is 1~10 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110429253A (en) * | 2019-07-29 | 2019-11-08 | 武汉理工大学 | Nitrogen doped silicon carbon compound cathode materials based on silsesquioxane and preparation method thereof |
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Application publication date: 20180824 |