CN110204646A - A kind of self-repair type conducting polymer and the preparation method and application thereof - Google Patents
A kind of self-repair type conducting polymer and the preparation method and application thereof Download PDFInfo
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 self-repair type conducting polymers and the preparation method and application thereof.The self-repair type conducting polymer is obtained by the radical copolymerization of vinyl monomer, and the vinyl monomer includes the second comonomer that can form the first monomer and intermolecular energy formation Quadrupolar hydrogen bond of conductive network.Self-repair type is creatively introduced into conducting polymer by the present invention, the long-term charge-discharge performance and high rate performance that the conducting polymer being prepared significantly improves the silicium cathode of lithium ion battery are (after charge and discharge cycles 200 are enclosed under 0.2C multiplying power, relative to control sample, 37.4%) de- lithium specific capacity improves at least.Moreover, the self-repair type conducting polymer being prepared using the present invention, can replace the binder and conductive agent in conventional lithium ion battery silicium cathode, and then simplify silicium cathode preparation process, conducive to the large-scale production of silicium cathode.
Description
Technical field
The invention belongs to lithium ion battery silicon negative electrode binder fields, and in particular to a kind of self-repair type conducting polymer and
Preparation method and application.
Background technique
Lithium ion battery is applied to portable electronic product, electric tool and power supply on vehicle etc. more and more.
But (Acs the problems such as electric car is in, and lithium ion battery still has energy density and low long-term cycle life
Applied Materials&Interfaces,2018,10(2):1672-1677).Lithium ion battery is by cathode, diaphragm, anode
It forming with electrolyte, the lithium ion battery of high-energy density, silicium cathode material are one of research emphasis in order to obtain, this is because
Theoretical specific capacity (372mAh/g) of the theoretical specific capacity (4200mAh/g) of silicium cathode than current most popular graphite cathode
High an order of magnitude.In addition, also there is low (the about 0.4V vs Li/Li of discharge potential with the lithium ion battery that silicon makees cathode+), it is former
Expect natural abundance height and advantages of environment protection (Chemical Society Reviews, 2018,47 (6): 2145-2164).
Traditional silicium cathode is made of active material (silicon), conductive agent (such as acetylene black and Super-P) and binder.?
Great variety (300%) can occur for embedding lithium/de- lithium process, the volume of silicon, this can make between silicon and conductive agent and collector mutually
Separation, destroys the conductive path of silicium cathode, and the specific capacity rapid decay and cyclical stability for eventually leading to battery are deteriorated
(Chemical Society Reviews,2018,47(6):2145-2164).Moreover, the enormousness variation of silicon can also destroy
Silicon face formed solid-electrolyte interface film (solid electrolyte interface, SEI film), cause silicon face with
The direct contact of electrolyte, and then lead to the lasting consumption of electrolyte and being continuously generated and destroying for SEI film, SEI film thickness is not
It is disconnected to increase, eventually lead to reduction and the lithium ion transport impedance of the coulombic efficiency of electrode increase (Nano Letters, 2012,
12(6):3315-3321)。
The type of optimization binder is to cope with one of the main method of these disadvantages of silicium cathode, in order to ensure poorly conductive
Silicon particle between electric conductivity, conductive agent is indispensable component in traditional silicium cathode.But do not have electro-chemical activity
Conductive agent and binder can all reduce battery energy density (Energy Environmental Science, 2015,8
(5):1538-1543).And the interaction between conductive agent and silicon is weaker, and in charge and discharge process, the violent volume of silicon becomes
Change is easy to make silicon and conductive agent to separate, and leads to the destruction of silicium cathode conductive path, and then reduces the capacity of silicium cathode and forthright again
Energy (Nano Energy, 2017,36:206-212).
In order to solve this problem, researchers, which develop not only, has good electric conductivity but also has good cementitiousness
Conductive adhesive.This conductive adhesive can keep effective conductive contact and picture between silicon to pass as conductive agent
The binder of system slows down the decaying of capacity of negative plates like that and extends service life (the Journal Of Power of lithium ion battery
Sources,2018,379:26-32).The dosage of silicium cathode conductive adhesive of good performance is less than conductive in traditional silicium cathode
The sum of agent and the dosage of binder increase activity substance content in cathode, and then are conducive to the raising of battery energy density
(Advanced Energy Materials,2018,8(11):1702314).Furthermore conductive adhesive can simplify when preparing cathode
Process.
2015, Park etc. (Journal Of The American Chemical Society, 2015,137 (7):
2565-2571) side chain conductive adhesive is introduced into lithium ion battery silicium cathode for the first time.Researcher has synthesized two kinds and has contained pyrene
Poly- pyrene class the conductive adhesive PPy and PPyE of cyclic group.The conductive adhesive can act on conduction electricity by the π-π stacking of pyrene ring
Son.Compared with traditional main chain conducting polymer, the preparation process of the conductive adhesive is simpler and is conducive to further modified.?
Under the charge-discharge magnification of 0.1C, the mass ratio of silicon and binder is 2:1 and silicon load is 0.13-0.15mg/cm2PPy/Si and
PPyE/Si cathode, after the circle of charge and discharge cycles 180, taking off lithium specific capacity is respectively 2100mAh/g and 2300mAh/g.
But when being applied to Si cathode, in charge and discharge process, the poly- pyrene class for the pyrene ring for having a large amount of rigidity big is conductive
The conductive network of binder is easy to destroy because of the stress that the violent volume change by silicon generates.In order to solve this problem, it assigns
Giving conductive adhesive self-reparing capability is a kind of good solution.Wherein, urea groups pyrimidone (ureido-
Pyrimidinone, UPy) group can be formed with Quadrupolar hydrogen bond combine dimeric structure, self-repair type water-setting can be used to prepare
Glue (Chemical Communications, 2012,48 (74): 9302-9304).
Summary of the invention
In order to overcome the shortcomings of the prior art, the object of the present invention is to provide a kind of self-repair type conducting polymer and
Preparation method and application.
The purpose of the present invention is realized at least through one of following technical solution.
A kind of self-repair type conducting polymer, the macromolecule are obtained by the radical copolymerization of vinyl monomer
It arrives, the vinyl monomer includes the second list that can form the first monomer and intermolecular energy formation Quadrupolar hydrogen bond of conductive network
Body.
Further, first monomer has pyrene ring, and second comonomer has urea groups pyrimidone (UPy) structure.
Further, first monomer is selected from:
Further, the second comonomer is selected from:
Further, the vinyl monomer further includes acrylic acid, methacrylic acid, polyethylene glycol acrylate list first
Ether or polyethylene glycol methacrylate-styrene polymer monomethyl ether.
Further, the amount Zhan of the substance of first monomer, second comonomer and other vinyl monomers total monomer
The percentage of the amount of substance is respectively 70-98%, 2-30% and 0-10%.
The present invention also provides the preparation methods of the self-repair type conducting polymer, include the following steps:
(1) initiator and all vinyl monomers being dissolved in organic solvent, stirring carries out free radical copolymerization,
Obtain the solution of polymerizate；
(2) solution of the polymerizate after will drop to room temperature, is precipitated in precipitating reagent；Then it is filtered, after filtering
Obtained solid is dissolved in organic solvent, is then precipitated in identical precipitating reagent again, and dissolution-precipitation process is repeated；
(3) finally sediment is dried in vacuo, obtains the self-repair type conducting polymer.
Further, the step (1) is identical with organic solvent used in (2), and organic solvent be Isosorbide-5-Nitrae-dioxane,
N,N-dimethylformamide or dimethyl sulfoxide；The initiator is azodiisobutyronitrile, azobisisoheptonitrile or peroxidating two
Benzoyl, the amount of the substance of initiator are the 0.1-1% of the amount of all vinyl monomer total materials.
Further, in the step (1), the volume of the amount of the total material of all vinyl monomers and organic solvent it
Than for (0.1-1): 1mol/L；Radical copolymerization temperature is 60-80 DEG C, polymerization time 8-24h.
Further, in the step (2), precipitating reagent is ether, acetone or n-hexane；Repeat dissolution-precipitation process
Number is 1-3 times；In the step (3), vacuum drying temperature is 50-90 DEG C, and the vacuum drying time is 16-48h.
The present invention also provides the self-repair type conducting polymers to manufacture the application in lithium ion battery silicium cathode,
It can be used as the conductive adhesive of lithium ion battery silicium cathode.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) self-repair type, is creatively introduced by the preparation method of self-repair type conducting polymer provided by the invention
In conducting polymer, i.e., the second comonomer of Quadrupolar hydrogen bond is formed by introducing intermolecular energy, in being basically unchanged for electric conductivity
In the case of, it improves the cementitiousness of poly- pyrene conductive adhesive and assigns conductive adhesive self-reparing capability, substantially increase lithium
Ion battery silicium cathode is in the cycle performance and high rate performance (charge and discharge cycles 200 under 0.2C multiplying power under long-term charge and discharge cycles
After circle, relative to control sample, 37.4%) de- lithium specific capacity is improved at least；
(2) by changing the type of the first monomer, second comonomer and other vinyl monomers, different type can be obtained
Self-repair type conducting polymer, i.e. self-repair type conductive adhesive, and then greatly expand the type of conductive adhesive, with suitable
Answer the requirement to binder under different use conditions；
(3) traditional silicium cathode is made of silicon, conductive agent and binder, self-repair type conducting polymer energy provided by the invention
Instead of the conductive agent and binder of traditional silicium cathode, and the mass content (≤33.3wt%) of conductive adhesive is than traditional silicium cathode
Conductive agent and binder gross mass content (40wt%) it is small, also allow for the quality of silicon in the silicium cathode using conductive adhesive
The mass fraction of the silicon of score ratio tradition silicium cathode is big, and the ratio increase of active material is conducive to improve the energy density of battery.
In addition, the component of silicium cathode becomes two (silicon and conductive adhesives) from three (silicon, conductive agent and binder), without increasing volume
External equipment, this can simplify silicium cathode preparation process and the large-scale production conducive to silicium cathode.
Specific embodiment
Specific implementation of the invention is described further below in conjunction with example, but implementation and protection of the invention is not limited to
This.
Lithium ion battery described in following embodiments refers to fastening lithium ionic cell, the electrochemistry number mentioned in embodiment
According to being all data that button type lithium ion half-cell (being lithium piece to electrode) measures.The buckle type lithium-ion half-cell is in charge and discharge
The voltage range of circulation is 0.01-1.00V.In silicium cathode the partial size of silicon be 100-5000nm, self-repair type conducting polymer and
The mass ratio 1:(2-9 of silicon), the load of the silicon in silicium cathode is 0.2-2mg/cm2。
The conductive adhesive that all control samples use in the present invention is all containing only the poly- methyl-prop that can form conductive network
Olefin(e) acid pyrene methyl esters, but the pole piece that the corresponding control sample of different experiments sample uses may be different, because to guarantee to test sample and control
The mass ratio of the load of the partial size, silicon of the silicon of sample and silicon and conductive agent is all identical.
Embodiment 1
The preparation of first monomer: 0.06mol 1- pyrene methanol is dissolved in the tetrahydro furan of 130mL handled through dry and distillation
In muttering, 0.10mol anhydrous pyridine and 0.09mol anhydrous triethylamine is added；After acquired solution is cooled to 0 DEG C, 0.09mol is added dropwise
Methacrylic chloride, time for adding 25min；After dripping off, ice bath is removed, 8h is stirred with the revolving speed of 500rpm at 20 DEG C；It connects
48mL water and 320mL ether is added to system, be successively 5wt% with 100mL 1mol/L hydrochloric acid, 100mL concentration after liquid separation
Sodium bicarbonate solution and 100mL concentration be 25wt% brine It oil phase；It is spin-dried for ether, is recrystallized in methyl alcohol, most
It is dried in vacuo 32h at room temperature afterwards, obtainsIt is as the first monomer；
The preparation of second comonomer: by 0.04mol 2- amino-4-hydroxy -6- methylpyrimidine be added to 67.5mL through dry and
In the dimethyl sulfoxide for distilling processing, 15min is dissolved under conditions of temperature is 150 DEG C, revolving speed is 550rpm.It is dropped after dissolution
Temperature is restored after reaction system to room temperature, 0.04mol isocyanatoethyl is added at room temperature, then in room temperature
Lower stirring 2h.Then it is filtered, and is precipitated 3 times with acetone washing.Finally, being dried in vacuo 32h at room temperature, obtainIt is as second comonomer.
Embodiment 2
(1) the first monomer and 0.2mmol embodiment obtained 0.01mmol azodiisobutyronitrile, 9.8mmol embodiment 1
1 obtained second comonomer is dissolved in 20mL n,N-Dimethylformamide, under conditions of temperature is 60 DEG C, revolving speed is 550rpm
Reaction for 24 hours, obtains the solution of polymerizate；The solution of polymerizate after will drop to room temperature, is precipitated in ether, is carried out
Filter；The solid obtained after filtering is dissolved in n,N-Dimethylformamide, is then precipitated in ether again, it is heavy to repeat dissolution-
It forms sediment 2 times.It is finally dried in vacuo for 24 hours under the conditions of 90 DEG C, obtains self-repair type conducting polymer.
(2) the self-repair type conducting polymer is added in N-methyl pyrrolidones, heating is stirred as conductive adhesive
It mixes, obtains clear solution；Clear solution and silicon are mixed, is then coated on collector, is dried, obtain pole piece；
Pole piece is assembled into lithium ion battery in glove box.Wherein, the partial size of silicon is 100nm, self-repair type conducting polymer and silicon
Mass ratio 1:2, the load of silicon are 0.24mg/cm2。
The battery is under the multiplying power of 0.2C after the circle of charge and discharge cycles 200, and taking off lithium specific capacity is 2570mAh/g, than control
Sample (1750mAh/g) is high by 46.9%.The battery is 820mAh/g in the averagely de- lithium specific capacity that 1C rate charge-discharge 5 encloses, and is
5.9 times of control sample (140mAh/g).
Embodiment 3
(1) the first monomer and 2mmol obtained (1) the step of 0.1mmol azodiisobutyronitrile, 7mmol embodiment 1 is real
It is sub- that the second comonomer and 1mmol polyethylene glycol methacrylate-styrene polymer monomethyl ether that the step of applying example 1 (2) obtains are dissolved in 10mL dimethyl
In sulfone, 8h is reacted under conditions of temperature is 80 DEG C, revolving speed is 800rpm, obtains the solution of polymerizate；After will drop to room temperature
Polymerizate solution, precipitate, be filtered in acetone；The solid obtained after filtering is dissolved in dimethyl sulfoxide, so
It precipitates, repeats dissolution-precipitating 3 times in acetone again afterwards.It finally is dried in vacuo 16h under the conditions of 50 DEG C, obtains self-repair type
Conducting polymer.
(2) the self-repair type conducting polymer is added in N-methyl pyrrolidones, heating is stirred as conductive adhesive
It mixes, obtains clear solution；Clear solution and silicon are mixed, is then coated on collector, is dried, obtain pole piece；
Pole piece is assembled into lithium ion battery in glove box.Wherein, the partial size of silicon is 5000nm, self-repair type conducting polymer and silicon
Mass ratio 1:5, the load of silicon are 1mg/cm2。
The battery is under the multiplying power of 0.2C after the circle of charge and discharge cycles 200, and taking off lithium specific capacity is 1910mAh/g, than control
Sample (1390mAh/g) is high by 37.4%.The battery is 630mAh/g in the averagely de- lithium specific capacity that 1C rate charge-discharge 5 encloses, and is
5.7 times of control sample (110mAh/g).
Embodiment 4
(1) the first monomer for obtaining (1) the step of 0.01mmol dibenzoyl peroxide, 9.8mmol embodiment 1 and
The second comonomer that the step of 0.2mmol embodiment 1 (2) obtains is dissolved in 20mL n,N-Dimethylformamide, is 60 in temperature
DEG C, revolving speed be 550rpm under conditions of react the solution for obtaining polymerizate for 24 hours；Polymerizate after will drop to room temperature it is molten
Liquid precipitates in ether, is filtered；The solid obtained after filtering is dissolved in n,N-Dimethylformamide, is then existed again
It precipitates, repeats dissolution-precipitating 1 time in ether.It is finally dried in vacuo for 24 hours under the conditions of 90 DEG C, obtains self-repair type conductive polymer
Son.
(2) the self-repair type conducting polymer is added in N-methyl pyrrolidones, heating is stirred as conductive adhesive
It mixes, obtains clear solution；Clear solution and silicon are mixed, is then coated on collector, is dried, obtain pole piece；
Pole piece is assembled into lithium ion battery in glove box.Wherein, the partial size of silicon is 5000nm, self-repair type conducting polymer and silicon
Mass ratio 1:9, the load of silicon are 2mg/cm2。
The battery is under the multiplying power of 0.2C after the circle of charge and discharge cycles 200, and taking off lithium specific capacity is 1680mAh/g, than control
Sample (1170mAh/g) is high by 43.6%.The battery is 580mAh/g in the averagely de- lithium specific capacity that 1C rate charge-discharge 5 encloses, and is
5.8 times of control sample (100mAh/g).
Embodiment 5
(1) the first monomer for obtaining (1) the step of 0.01mmol azobisisoheptonitrile, 9.8mmol embodiment 1 and
The second comonomer that the step of 0.2mmol embodiment 1 (2) obtains is dissolved in 20mL n,N-Dimethylformamide, is 60 in temperature
DEG C, revolving speed be 550rpm under conditions of react the solution for obtaining polymerizate for 24 hours；Polymerizate after will drop to room temperature it is molten
Liquid precipitates in ether, is filtered；The solid obtained after filtering is dissolved in n,N-Dimethylformamide, is then existed again
It precipitates, repeats dissolution-precipitating 2 times in ether.It is finally dried in vacuo for 24 hours under the conditions of 90 DEG C, obtains self-repair type conductive polymer
Son.
(2) the self-repair type conducting polymer is added in N-methyl pyrrolidones, heating is stirred as conductive adhesive
It mixes, obtains clear solution；Clear solution and silicon are mixed, is then coated on collector, is dried, obtain pole piece；
Pole piece is assembled into lithium ion battery in glove box.Wherein, the partial size of silicon is 1000nm, self-repair type conducting polymer and silicon
Mass ratio 1:4, the load of silicon are 0.24mg/cm2。
The battery is under the multiplying power of 0.2C after the circle of charge and discharge cycles 200, and taking off lithium specific capacity is 2230mAh/g, than control
Sample (1540mAh/g) is high by 44.8%.The battery is 740mAh/g in the averagely de- lithium specific capacity that 1C rate charge-discharge 5 encloses, and is
5.7 times of control sample (130mAh/g).
Embodiment 6
(1) the first monomer and 2mmol for obtaining (1) the step of 0.1mmol dibenzoyl peroxide, 7mmol embodiment 1
The second comonomer and 1mmol polyethylene glycol acrylate monomethyl ether that the step of embodiment 1 (2) obtains are dissolved in 10mL dimethyl sulfoxide
In, 8h is reacted under conditions of temperature is 80 DEG C, revolving speed is 800rpm, obtains the solution of polymerizate；After will drop to room temperature
The solution of polymerizate, is precipitated in acetone, is filtered；The solid obtained after filtering is dissolved in dimethyl sulfoxide, then
It precipitates, repeats dissolution-precipitating 3 times in acetone again.It finally is dried in vacuo 16h under the conditions of 50 DEG C, self-repair type is obtained and leads
Electric macromolecule.
(2) the self-repair type conducting polymer is added in N-methyl pyrrolidones, heating is stirred as conductive adhesive
It mixes, obtains clear solution；Clear solution and silicon are mixed, is then coated on collector, is dried, obtain pole piece；
Pole piece is assembled into lithium ion battery in glove box.Wherein, the partial size of silicon is 1000nm, self-repair type conducting polymer and silicon
Mass ratio 1:5, the load of silicon are 1mg/cm2。
The battery is under the multiplying power of 0.2C after the circle of charge and discharge cycles 200, and taking off lithium specific capacity is 2170mAh/g, than control
Sample (1500mAh/g) is high by 44.7%.The battery is 710mAh/g in the averagely de- lithium specific capacity that 1C rate charge-discharge 5 encloses, and is
5.6 times of control sample (126mAh/g).
Embodiment 7
(1) the first monomer for obtaining (1) the step of 0.05mmol azobisisoheptonitrile, 8mmol embodiment 1 and
The second comonomer and 0.5mmol acrylic acid that the step of 1.5mmol embodiment 1 (2) obtains are dissolved in 20mL Isosorbide-5-Nitrae dioxane,
Temperature is 70 DEG C, revolving speed reacts the solution for obtaining polymerizate for 24 hours under conditions of being 400rpm；Polymerization after will drop to room temperature
The solution of product, is precipitated in n-hexane, is filtered；The solid obtained after filtering is dissolved in Isosorbide-5-Nitrae dioxane, then again
It is secondary to be precipitated in n-hexane, it repeats dissolution-precipitating 1 time.It finally is dried in vacuo 48h under the conditions of 70 DEG C, self-repair type is obtained and leads
Electric macromolecule.
(2) the self-repair type conducting polymer is added in N-methyl pyrrolidones, heating is stirred as conductive adhesive
It mixes, obtains clear solution；Clear solution and silicon are mixed, is then coated on collector, is dried, obtain pole piece；
Pole piece is assembled into lithium ion battery in glove box.Wherein, the partial size of silicon is 5000nm, self-repair type conducting polymer and silicon
Mass ratio 1:9, the load of silicon are 2mg/cm2。
The battery is under the multiplying power of 0.2C after the circle of charge and discharge cycles 200, and taking off lithium specific capacity is 2160mAh/g, than control
Sample (1470mAh/g) is high by 46.9%.The battery is 690mAh/g in the averagely de- lithium specific capacity that 1C rate charge-discharge 5 encloses, and is
5.8 times of control sample (120mAh/g).
Above embodiments are only preferrred embodiment of the present invention, for explaining only the invention, are not intended to limit the present invention, this
Field technical staff should belong to guarantor of the invention without departing from change made under spirit of the invention, replacement, modification etc.
Protect range.
Claims (10)
1. a kind of self-repair type conducting polymer, which is characterized in that the self-repair type conducting polymer is by vinyl-based
The radical copolymerization of monomer obtains, and the vinyl monomer includes the first monomer and intermolecular energy that can form conductive network
Form the second comonomer of Quadrupolar hydrogen bond.
2. self-repair type conducting polymer according to claim 1, which is characterized in that first monomer has pyrene ring,
Second comonomer has urea groups pyrimidone structure.
3. self-repair type conducting polymer according to claim 1, which is characterized in that the second comonomer isFirst monomer is
4. self-repair type conducting polymer according to claim 1, which is characterized in that the vinyl monomer further includes
Acrylic acid, methacrylic acid, polyethylene glycol acrylate monomethyl ether or polyethylene glycol methacrylate-styrene polymer monomethyl ether.
5. self-repair type conducting polymer according to claim 4, which is characterized in that first monomer, second comonomer
With the amount Zhan of the substance of other vinyl monomers the percentage of the amount of total monomeric substance be respectively 70-98%, 2-30% and
0-10%.
6. the preparation method of any one of the claim 1-5 self-repair type conducting polymer, which is characterized in that including walking as follows
It is rapid:
(1) initiator and all vinyl monomers are dissolved in organic solvent, stirring carries out free radical copolymerization, obtains
The solution of polymerizate；
(2) solution of the polymerizate after will drop to room temperature, is precipitated in precipitating reagent；Then it is filtered, will be obtained after filtering
Solid be dissolved in organic solvent, then precipitated in identical precipitating reagent again, repeat dissolution-precipitation process；
(3) finally sediment is dried in vacuo, obtains the self-repair type conducting polymer.
7. preparation method according to claim 6, which is characterized in that organic solvent phase used in the step (1) and (2)
Together, and organic solvent is Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide or dimethyl sulfoxide；The initiator is that azo two is different
Butyronitrile, azobisisoheptonitrile or dibenzoyl peroxide, the amount of the substance of initiator are all vinyl monomer total materials
The 0.1-1% of amount.
8. preparation method according to claim 6, which is characterized in that in the step (1), all vinyl monomers
The ratio between amount and the volume of organic solvent of total material are (0.1-1): 1mol/L；Radical copolymerization temperature is 60-80 DEG C, polymerization
Time is 8-24h.
9. radical copolymerization step according to claim 6, which is characterized in that in the step (2), precipitating reagent is second
Ether, acetone or n-hexane；Repeating dissolution-precipitation process number is 1-3 times；In the step (3), vacuum drying temperature is
50-90 DEG C, the vacuum drying time is 16-48h.
10. application of any one of the claim 1-5 self-repair type conducting polymer in manufacture lithium ion battery silicium cathode,
It is characterized in that, conductive adhesive of the self-repair type conducting polymer as lithium ion battery silicium cathode.
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