CN108598364A - A kind of lithium ion battery flexible electrical pole piece and preparation method thereof with coat - Google Patents
A kind of lithium ion battery flexible electrical pole piece and preparation method thereof with coat Download PDFInfo
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- CN108598364A CN108598364A CN201810413513.3A CN201810413513A CN108598364A CN 108598364 A CN108598364 A CN 108598364A CN 201810413513 A CN201810413513 A CN 201810413513A CN 108598364 A CN108598364 A CN 108598364A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 lithium ion battery flexible electrical pole piece and preparation method thereof with coat.The lithium ion battery flexible electrical pole piece includes pole piece matrix and is at least coated in the coat of pole piece matrix side, which includes following raw material：Kynoar, coumarone indene resin, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, hydroxylated cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, butyl acetate cellulose, carbon nanotube, graphene oxide, polyaniline, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, surface conditioning agent；The electrode slice is by preparing base-material, a modified base material, then coat slurry is coated on at least side of pole piece matrix, is obtained after dry by coat slurry.Lithium ion battery flexible electrical pole piece of the present invention has excellent toughness.
Description
Technical field
The invention belongs to electrochemical material preparing technical fields, and in particular to a kind of lithium ion battery with coat is soft
Property electrode slice and preparation method thereof.
Background technology
As people are for various frivolous, the demand of flexibility/foldable electronic, for development of small-scale, light and have
Have high-energy density, power density and with bending stability flexible serondary lithium battery more stringent requirements are proposed.Flexible electrical
Pole is one of the key factor of high-performance flexible secondary cell development.The positive electrode of current commodity serondary lithium battery stores up lithium machine
Reason is insertion reaction mechanism, and electron number is shifted in electrochemical process and is respectively less than an electronics, therefore uses these electrode materials
The mass-energy density metric density for being assembled into serondary lithium battery is generally below 200Wh/kg, and performance has reached or managed close to material
By the limit of capacity, therefore positive electrode has become the bottleneck that serondary lithium battery performance further increases.Serondary lithium battery assembles
Technique is coated in metal collector after mixing electrode material, conductive agent and binder, because metal collector density is big, and
Capacity is not contributed, thus greatly reduces the energy density of lithium battery.Simultaneously because metal surface smoother, makes gold
The adhesion strength for belonging to collector and active material is insufficient, causes active material and collector interface bond strength relatively low, in charge and discharge
It can be detached from electric process, the internal resistance of cell is made to be continuously increased, reduce cycle life.It usually will be curved for flexible electronic battery
It is used under the conditions of folding, active material is easier the break-off for occurring with metal collector.Therefore R and D high power capacity, length
The positive electrode without metal collector of cycle life, high active substance content is the important research direction in the field.
A kind of Chinese patent application document " flexible electrical pole piece and preparation method thereof with coat（Application publication number：
CN107611341A）" disclose a kind of flexible electrical pole piece with coat, including pole piece matrix and at least it is coated in pole piece base
The coat of piece side, pole piece matrix include corpus fibrosum, active material and conductive agent one, and corpus fibrosum is that nanofiber or racemosus are brilliant
Fiber, active material and conductive agent one are dispersed in corpus fibrosum, and active material is anode material for lithium-ion batteries or cathode material
Material；Coat includes the mixed slurry of binder two, surfactant and conductive agent two, two N doping three-dimensional grapheme of conductive agent
Tiny balloon.The electrode slice is acted on self by the self-supporting of corpus fibrosum so that active material is evenly dispersed inside it, has
Certain flexibility, while one layer of coat slurry is coated on pole piece matrix, scattered nitrogen-doped graphene hollow ball was both protected
The reticular structure of original carbon has been stayed, and has increased the contact area with solvent, has substantially increased the contact surface for reacting with it substance
Product, the electric conductivity of coat has good promotion, to improve the electrical property of lithium battery.
Chinese patent application document " a kind of preparation method and flexible electrode of flexible electrode（Application publication number：
CN104078248A）" disclose a kind of preparation method of flexible electrode and its flexible electrode of preparation, the preparation method of the application
Including：A, carbon nanotube and graphene oxide are made to evenly dispersed mixed dispersion liquid；B, it removes molten in mixed dispersion liquid
The film with three-dimensional conductive network is made in agent；C, the in-situ polymerization organic polymer conduction material in three-dimensional conductive network thin-film
Material, obtains ternary flexible compound film；D, the graphene oxide in ternary flexible compound film is restored, that is, obtains flexible electrode.It should
The preparation method of application makes carbon nanotube and graphene oxide form the film of three-dimensional conductive network, then in three dimensional network first
In-situ polymerization organic macromolecule conducting material in network；In three-dimensional conductive network, carbon nanotube is inserted between graphene sheet layer, not only
The spacing and specific surface area between graphene film are increased, and carbon nanotube can also make up graphene and be generated in oxidation process
Defect, be conducive to electron-transport, improve the specific capacitance of flexible electrode.
Invention content
The object of the present invention is to provide a kind of lithium ion battery flexible electrical pole piece and preparation method thereof with coat, with
It solves in a kind of Chinese patent application document " flexible electrical pole piece and preparation method thereof with coat（Application publication number：
CN107611341A）" and Patent Application Publication " a kind of preparation method and flexible electrode of flexible electrode（Application publication number：
CN104078248A）" disclosed on the basis of flexible electrical pole piece, how to optimize component, dosage, method etc., improve the flexible electrical
The problem of pole piece toughness.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of lithium ion battery flexible electrical pole piece with coat, including pole piece matrix and at least be coated in pole piece matrix side
Coat, the coat includes following raw material：Kynoar, coumarone indene resin, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, hydroxyl
Base cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, butyl acetate cellulose, carbon nanotube, graphene oxide, polyaniline,
Carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, surface conditioning agent；
The toughened and reinforced auxiliary agent, as unit of parts by weight, including following raw material：15-25 parts of butyl acrylate, potassium peroxydisulfate 4-
8 parts, mass fraction be 4-8% 3-9 parts of aluminum sulfate aqueous solution, mass percent be 4-6% 2-6 parts of hydrochloric acid solution, poly- isobutyl
4-9 parts of alkene, 3-5 parts of methacrylate, 2-6 parts of glass fibre, 1-5 parts of flax；
The toughening modifying filler, as unit of parts by weight, including following raw material：8-16 parts of carboxylic carbon nano-tube, nanometer two
4-8 parts of silica, 3-9 parts of tapioca starch, 2-5 parts of kaolin, 1-4 parts of carboxylic acrylonitrile butadiene rubber latex, 3-6 parts of polylactic acid, silane coupling agent
1-3 parts of KH-550,4-8 parts of polyvinyl alcohol, 3-9 parts of methyl methacrylate, 2-6 parts of ammonium persulfate, 1-5 parts of aluminium hydroxide；
The coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening
Modified filler, surface conditioning agent weight ratio be（18-36）：（8-12）：（4-6）：（2-5）：（3-6）：（1-3）：（10-20）：
（15-25）.
Further, the coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughening
Strengthening helping agent, toughening modifying filler, surface conditioning agent weight ratio be 27：10：5：3.5：4.5：2：15：20.
Further, the coat is as unit of parts by weight, including following raw material：20-40 parts of Kynoar, ancient horse
Grand resin 18-36 parts, 8-14 parts of polytetrafluoroethylene (PTFE), 3-6 parts of butadiene-styrene rubber, 2-5 parts of hydroxylated cellulose, 1-5 parts of acrylonitrile, fluoro
3-6 parts of alkyl methoxyl group ether alcohol, 8-12 parts of butyl acetate cellulose, 4-8 parts of carbon nanotube, 3-6 parts of graphene oxide, polyaniline
2-4 parts, 4-6 parts of carbon black, 2-5 parts of polyphosphoric acids aluminium, 3-6 parts of nano-graphite, auxiliary agent 1-3 parts toughened and reinforced, toughening modifying filler
10-20 parts, 15-25 parts of surface conditioning agent.
Further, the toughened and reinforced auxiliary agent is prepared by following technique：Butyl acrylate and potassium peroxydisulfate are mixed
Uniform, reaction 1-3h is closed, mass fraction is then added dropwise as the aluminum sulfate aqueous solution of 4-8%, is demulsified, filtering, in 45-55 after washing
Dry 5-7h, is cooled to room temperature, then calcines 2-5h at 820-920 DEG C in calcining furnace in DEG C vacuum drying oven, cooling, is put into
1-3h is impregnated in the hydrochloric acid solution that mass percent is 4-6%, filtering is taken out, and cleans drying with clear water, poly- isobutyl is added after crushing
Alkene, methacrylate, glass fibre and flax are uniformly mixed, and are warming up to 110-130 DEG C, 10-30min are kept the temperature, in 650-
850r/min rotating speeds stir 20-30min, are cooled to room temperature up to toughened and reinforced auxiliary agent.
Further, the toughening modifying filler is prepared by following technique：By carboxylic carbon nano-tube, nano-silica
SiClx, tapioca starch, kaolin and carboxylic acrylonitrile butadiene rubber latex are uniformly mixed, and 10-12h is stirred in 65-75 DEG C, be then added polylactic acid,
Silane resin acceptor kh-550, polyvinyl alcohol and methyl methacrylate are uniformly mixed, and are stirred under 5500-6500r/min rotating speeds
2-4h then heats to 90-100 DEG C, keeps the temperature 0.5-1.5h, and ammonium persulfate is then added and aluminium hydroxide is uniformly mixed, then
It after being cleaned with deionized water, filters, is placed in 45-55 DEG C of baking oven dry 1-4h, is cooled to room temperature to obtain toughening modifying filler.
Further, the surface conditioning agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, isophthalic
Diamines and 1,3 butylene glycol are by weight 1-3：2-6：1-5：4-6：0.5-1.5 is mixed.
The preparation method of the present invention also provides a kind of lithium ion battery flexible electrical pole piece with coat, including following step
Suddenly：
S1：By Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber heating melting after obtain liquid sizing material, by hydroxylated cellulose,
Acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding cross 20-40 mesh sieve, so
After be added in liquid sizing material, continue heating stirring, be cooled to room temperature to obtain base-material；
S2：Coumarone indene resin, butyl acetate cellulose, carbon black and polyphosphoric acids aluminium are added after the base-material that S1 is obtained is heated up, receives
Meter Shi Mo is uniformly mixed, and is stirred after continuing heating, is cooled to room temperature to obtain a modified base material；
S3：Toughened and reinforced auxiliary agent, toughening modifying filler and surface conditioning agent is added after modified base material is heated up to be uniformly mixed,
It is stirred after continuing heating, is cooled to room temperature to obtain coat slurry；
S4, at least side that the coat slurry that S3 is obtained is coated on to pole piece matrix obtain the lithium with coat after dry
Ion battery flexible electrical pole piece.
Further, in S1, after Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are warming up to 120-150 DEG C of melting
Liquid sizing material is obtained, by hydroxylated cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyphenyl
Amine mixed grinding crosses 20-40 mesh sieve, is then added in liquid sizing material, is continuously heating to 140-160 DEG C in 650-850r/min
Rotating speed stirs 2-3h, is cooled to room temperature to obtain base-material.
Further, it is fine that coumarone indene resin, butyl acetate are added in S2, after the base-material that S1 is obtained is warming up to 90-110 DEG C
Dimension element, carbon black and polyphosphoric acids aluminium, nano-graphite are uniformly mixed, in 1500-2500r/min after being continuously heating to 120-130 DEG C
20-40min is stirred, is cooled to room temperature to obtain a modified base material.
Further, in S3, toughened and reinforced auxiliary agent is added after a modified base material is warming up to 110-120 DEG C, toughening changes
Property filler and surface conditioning agent be uniformly mixed, after being continuously heating to 130-150 DEG C in 850-1050r/min rotating speeds stir 30-
50min is cooled to room temperature to obtain coat slurry.
The invention has the advantages that：
（1）By embodiment 1-3 and the data of comparative example 10 and comparative example 11 as it can be seen that having coat made from embodiment 1-3
The toughness of lithium ion battery flexible electrical pole piece be significantly higher than the toughness of electrode slice made from comparative example 10 and comparative example 11；Together
When by the data of embodiment 1-3 as it can be seen that embodiment 1 be optimum embodiment, by embodiment 1 and the data of comparative example 1-9 as it can be seen that Gu
The grand resin of horse, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, table
Surface treatment agent plays synergistic effect in preparing the lithium ion battery flexible electrical pole piece with coat, and collaboration improves the electricity
The toughness properties of pole piece.
（2）By the data of comparative example 12-14 as it can be seen that coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium,
Nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, surface conditioning agent weight ratio do not exist（18-36）：（8-12）：（4-
6）：（2-5）：（3-6）：（1-3）：（10-20）：（15-25）When in range, the corresponding numerical value of toughness of electrode slice obtained with
The numerical value of embodiment 1-3 is very different, and the numerical value of embodiment 1-3 is much smaller than, with the prior art（Comparative example 10 and comparative example 11）
Numerical value it is suitable.It is coumarone indene resin of the present invention, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced
As reinforcement system, embodiment 1-3 controls prepare the lithium ion with coat for auxiliary agent, toughening modifying filler, surface conditioning agent
By adding coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, increasing when cell flexible electrode slice
Tough strengthening helping agent, toughening modifying filler, surface conditioning agent weight ratio be（18-36）：（8-12）：（4-6）：（2-5）：（3-6）：
（1-3）：（10-20）：（15-25）, realize using the toughness that coumarone indene resin is excellent in reinforcement system, and in butyl acetate fibre
Element, carbon black, polyphosphoric acids aluminium, nano-graphite are tieed up as under toughened and reinforced filler effect, using coumarone indene resin as reinforcement system
For major ingredient, realize that less toughened and reinforced filler effect in coumarone indene resin, improves the toughness of coumarone indene resin, and on surface
Under the grafting effect of inorganic agent, the toughness strengthening action of toughened and reinforced auxiliary agent and toughening modifying filler is utilized, effectively increases
The toughness of the electrode slice, coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughening are mended as a result,
Strong auxiliary agent, toughening modifying filler, surface conditioning agent are applied to as reinforcement system in the preparation of the electrode slice, effectively increase this
The toughness of electrode slice.
（3）Coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, increasing
Tough modified filler and surface conditioning agent are as reinforcement system, and wherein coumarone indene resin is major ingredient, and assigning reinforcement system enhances toughness
Performance, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite as toughness enhance reinforced filling, can not only make
During the melt process of coumarone indene resin, the toughness of coumarone indene resin is improved, moreover it is possible to improve electric conductivity, add surface
Inorganic agent is realized the toughness reinforcement of toughened and reinforced auxiliary agent and toughening modifying filler applying to the electrode base as graft modification agent
In the base-material of body coat, the grafting of the hydroxyl in surface conditioning agent on toughened and reinforced auxiliary agent and toughening modifying filler surface is realized
It realizes under effect and is combined with base-material, effectively increase the toughness properties of electrode slice of the present invention.
（4）Toughened and reinforced auxiliary agent is improved is added dropwise aluminum sulfate aqueous solution after mixing by butyl acrylate and potassium peroxydisulfate,
Demulsification, filtering is dry after washing, is calcined after being cooled to room temperature, cooling, is put into hydrochloric acid solution and impregnates, and filtering is taken out, and clear water is used
Drying is cleaned, polyisobutene, methacrylate, glass fibre and flax are added after crushing and is uniformly mixed, heats up, heat preservation is stirred
It mixes, is cooled to room temperature to obtain the final product, using butyl acrylate, polyisobutene, methacrylate as grafted monomers, with potassium peroxydisulfate
The benefit to monomer toughness on glass fibre and Flax Grafting to monomer, will be realized after acid solution is handled for initiator
By force, and the preparation of coat is applied to, effectively increases the toughness of electrode slice.
（5）Toughening modifying filler is by by carboxylic carbon nano-tube, nano silicon dioxide, tapioca starch, kaolin and carboxyl
NBR latex is uniformly mixed, then polylactic acid, silane resin acceptor kh-550, polyvinyl alcohol and methyl methacrylate is added in stirring
Ester is uniformly mixed, and is stirred under rotating speed, and ammonium persulfate is added after heating and heat preservation and aluminium hydroxide is uniformly mixed, then uses deionization
After water cleaning, filter, be placed in baking oven dry, be cooled to room temperature to obtain, with carboxylic carbon nano-tube, nano silicon dioxide,
Tapioca starch, kaolin are toughened and reinforced filler, basic emulsion are grafted with polylactic acid and carboxylic acrylonitrile butadiene rubber latex, in film forming agent polyethylene
Under the action of alcohol, in the case where silane resin acceptor kh-550 is acted on as grafting, realizes toughened and reinforced filler and be grafted to basic emulsion
On, the reinforcement of toughness is realized, the preparation of the electrode slice surface coating layer of the present invention is applied to, further improves electrode slice
Toughness.
（6）Surface conditioning agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, m-phenylene diamine (MPD) and 1,3-
Butanediol is mixed in a certain ratio, and wherein azobisisoheptonitrile has promoted the grafting of filler and base-material to change as initiator
The progress of property, the electrode slice surface coating layer of polyvinyl butyral and polyetherimide as the further reinforcement of toughening auxiliary agent
Toughness, m-phenylene diamine (MPD) promoted the film forming of coat as curing agent, improves the efficiency of film forming, made with 1,3-BDO
For coupling agent, realizes and base-material is surface-treated, under the basis of reinforcement toughness, realize the modification to base-material surface, it is real
Show reinforcement system to be combined with base-material, improves the reinforcement to coat toughness.
（7）The preparation method of lithium ion battery flexible electrical pole piece of the present invention is simple, for the purpose of preparing coat slurry, leads to
Cross and base-material be modified twice, to base-material surface graft modification, combined with base-material using toughening modifying system, so as to get painting
Coating has excellent toughness, is coated on at least side of pole piece matrix, is obtained after dry, obtained electrode slice has excellent
Toughness, and preparation process is simple, preparation efficiency is high.
Specific implementation mode
For ease of more fully understanding the present invention, it is illustrated by the following examples, these examples belong to the protection of the present invention
Range, but do not limit the scope of the invention.
In embodiment, the lithium ion battery flexible electrical pole piece with coat, including pole piece matrix and at least apply
Overlay on the coat of pole piece matrix side, the coat, as unit of parts by weight, including following raw material：Kynoar 20-
40 parts, 18-36 parts of coumarone indene resin, 8-14 parts of polytetrafluoroethylene (PTFE), 3-6 parts of butadiene-styrene rubber, 2-5 parts of hydroxylated cellulose, acrylonitrile
1-5 parts, 3-6 parts of fluoro-alkyl methoxyl group ether alcohol, 8-12 parts of butyl acetate cellulose, 4-8 parts of carbon nanotube, graphene oxide 3-
6 parts, 2-4 parts of polyaniline, 4-6 parts of carbon black, 2-5 parts of polyphosphoric acids aluminium, 3-6 parts of nano-graphite, it is auxiliary agent 1-3 parts toughened and reinforced, increase
Tough modified filler 10-20 parts, 15-25 parts of surface conditioning agent.
The toughened and reinforced auxiliary agent is prepared by following technique：By weight by 15-25 parts of butyl acrylates and 4-8 parts
Potassium peroxydisulfate is uniformly mixed, and reacts 1-3h, and the aluminum sulfate aqueous solution that 3-9 parts of mass fractions are 4-8%, demulsification, mistake is then added dropwise
Filter dries 5-7h in 45-55 DEG C of vacuum drying oven, is cooled to room temperature, is then forged at 820-920 DEG C in calcining furnace after washing
2-5h is burnt, it is cooling, it is put into the hydrochloric acid solution that 2-6 parts of mass percents are 4-6% and impregnates 1-3h, filtering is taken out, and is cleaned with clear water
It is equal that 4-9 parts of polyisobutene, 3-5 parts of methacrylates, 2-6 parts of glass fibres and 1-5 parts of flax mixing are added in drying after crushing
It is even, it is warming up to 110-130 DEG C, keeps the temperature 10-30min, 20-30min is stirred in 650-850r/min rotating speeds, is cooled to room temperature i.e.
Obtain toughened and reinforced auxiliary agent.
The toughening modifying filler is prepared by following technique：By weight by 8-16 parts of carboxylic carbon nano-tubes, 4-8
Part nano silicon dioxide, 3-9 parts of tapioca starch, 2-5 parts of kaolin and 1-4 parts of carboxylic acrylonitrile butadiene rubber latexes are uniformly mixed, and are stirred in 65-75 DEG C
10-12h is mixed, 3-6 parts of polylactic acid, 1-3 parts of silane resin acceptor kh-550s, 4-8 parts of polyvinyl alcohol and 3-9 parts of methyl-props are then added
E pioic acid methyl ester is uniformly mixed, and 2-4h is stirred under 5500-6500r/min rotating speeds, then heats to 90-100 DEG C, keeps the temperature 0.5-
1.5h, is then added 2-6 parts of ammonium persulfates and 1-5 parts of aluminium hydroxides are uniformly mixed, and after then being cleaned with deionized water, filters,
It is placed in 45-55 DEG C of baking oven dry 1-4h, is cooled to room temperature to obtain toughening modifying filler.
The surface conditioning agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, m-phenylene diamine (MPD) and 1,3-
Butanediol is by weight 1-3：2-6：1-5：4-6：0.5-1.5 is mixed.
The preparation method of the lithium ion battery flexible electrical pole piece with coat, includes the following steps：
S1：Liquid sizing material is obtained after Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are warming up to 120-150 DEG C of melting, it will
Hydroxylated cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding, mistake
20-40 mesh sieves, and is then added in liquid sizing material, is continuously heating to 140-160 DEG C and stirs 2-3h in 650-850r/min rotating speeds,
It is cooled to room temperature to obtain base-material；
S2：Coumarone indene resin, butyl acetate cellulose, carbon black and poly are added after the base-material that S1 is obtained is warming up to 90-110 DEG C
Aluminum phosphate, nano-graphite are uniformly mixed, and 20-40min is stirred in 1500-2500r/min after being continuously heating to 120-130 DEG C, cold
But a modified base material is obtained to room temperature；
S3：Toughened and reinforced auxiliary agent, toughening modifying filler and surface treatment are added after modified base material is warming up to 110-120 DEG C
Agent is uniformly mixed, and is stirred 30-50min in 850-1050r/min rotating speeds after being continuously heating to 130-150 DEG C, is cooled to room temperature
To coat slurry；
S4, at least side that the coat slurry that S3 is obtained is coated on to pole piece matrix obtain the lithium with coat after dry
Ion battery flexible electrical pole piece.
Embodiment 1
A kind of lithium ion battery flexible electrical pole piece with coat, including pole piece matrix and at least be coated in pole piece matrix side
Coat, the coat, as unit of parts by weight, including following raw material：30 parts of Kynoar, coumarone indene resin 27
Part, 11 parts of polytetrafluoroethylene (PTFE), 4.5 parts of butadiene-styrene rubber, 3.5 parts of hydroxylated cellulose, 3 parts of acrylonitrile, fluoro-alkyl methoxyl group ether alcohol
4.5 parts, 10 parts of butyl acetate cellulose, 6 parts of carbon nanotube, 4.5 parts of graphene oxide, 3 parts of polyaniline, 5 parts of carbon black, poly phosphorus
3.5 parts of sour aluminium, 4.5 parts of nano-graphite, 2 parts of toughened and reinforced auxiliary agent, 15 parts of toughening modifying filler, 20 parts of surface conditioning agent.
The toughened and reinforced auxiliary agent is prepared by following technique：By weight by 20 parts of butyl acrylates and 6 parts of over cures
Sour potassium is uniformly mixed, and reacts 2h, and the aluminum sulfate aqueous solution that 6 parts of mass fractions are 6% is then added dropwise, is demulsified, filtering, after washing
Dry 6h, is cooled to room temperature, then calcines 3.5h at 870 DEG C in calcining furnace in 50 DEG C of vacuum drying ovens, cooling, is put into 4 parts
Mass percent to impregnate 2h in 5% hydrochloric acid solution, take out by filtering, cleans drying with clear water, 6.5 parts of addition is poly- different after crushing
Butylene, 4 parts of methacrylates, 4 parts of glass fibres and 3 portions of flax are uniformly mixed, and are warming up to 120 DEG C, are kept the temperature 20min, in
750r/min rotating speeds stir 25min, are cooled to room temperature up to toughened and reinforced auxiliary agent.
The toughening modifying filler is prepared by following technique：12 parts of carboxylic carbon nano-tubes, 6 parts are received by weight
Rice silica, 6 parts of tapioca starch, 3.5 parts of kaolin and 2.5 parts of carboxylic acrylonitrile butadiene rubber latexes are uniformly mixed, and stir 11h in 70 DEG C, so
4.5 parts of polylactic acid, 2 parts of silane resin acceptor kh-550s, 6 parts of polyvinyl alcohol and 6 parts of methyl methacrylates are added afterwards to be uniformly mixed,
3h is stirred under 6000r/min rotating speeds, then heats to 95 DEG C, keeps the temperature 1h, 4 parts of ammonium persulfates and 3 parts of hydroxides are then added
Aluminium is uniformly mixed, and after then being cleaned with deionized water, is filtered, and is placed in 50 DEG C of baking oven dry 2.5h, is cooled to room temperature to obtain
Toughening modifying filler.
The surface conditioning agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, m-phenylene diamine (MPD) and 1,3-
Butanediol is by weight 2：4：3：5：1 mixes.
The preparation method of the lithium ion battery flexible electrical pole piece with coat, includes the following steps：
S1：Liquid sizing material is obtained after Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are warming up to 135 DEG C of meltings, by hydroxyl
Cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding cross 30 mesh
Sieve, is then added in liquid sizing material, is continuously heating to 150 DEG C and stirs 2.5h in 750r/min rotating speeds, is cooled to room temperature to obtain
Base-material；
S2：Coumarone indene resin, butyl acetate cellulose, carbon black and poly phosphorus are added after the base-material that S1 is obtained is warming up to 100 DEG C
Sour aluminium, nano-graphite are uniformly mixed, and are stirred 30min in 2000r/min after being continuously heating to 125 DEG C, are cooled to room temperature to obtain one
Secondary modified base material；
S3：Modified base material is warming up to after 115 DEG C and toughened and reinforced auxiliary agent, toughening modifying filler and surface conditioning agent is added mixes
It closes uniformly, stirs 40min in 950r/min rotating speeds after being continuously heating to 140 DEG C, be cooled to room temperature to obtain coat slurry；
S4, at least side that the coat slurry that S3 is obtained is coated on to pole piece matrix obtain the lithium with coat after dry
Ion battery flexible electrical pole piece.
Embodiment 2
A kind of lithium ion battery flexible electrical pole piece with coat, including pole piece matrix and at least be coated in pole piece matrix side
Coat, the coat, as unit of parts by weight, including following raw material：20 parts of Kynoar, coumarone indene resin 36
Part, 8 parts of polytetrafluoroethylene (PTFE), 6 parts of butadiene-styrene rubber, 2 parts of hydroxylated cellulose, 5 parts of acrylonitrile, 3 parts of fluoro-alkyl methoxyl group ether alcohol, vinegar
12 parts of acid butyl ester cellulose, 6 parts of graphene oxide, 2 parts of polyaniline, 6 parts of carbon black, 2 parts of polyphosphoric acids aluminium, is received 4 parts of carbon nanotube
6 parts of meter Shi Mo, 1 part of toughened and reinforced auxiliary agent, 20 parts of toughening modifying filler, 15 parts of surface conditioning agent.
The toughened and reinforced auxiliary agent is prepared by following technique：By weight by 15 parts of butyl acrylates and 8 parts of over cures
Sour potassium is uniformly mixed, and reacts 1h, and the aluminum sulfate aqueous solution that 9 parts of mass fractions are 4% is then added dropwise, is demulsified, filtering, after washing
Dry 5h, is cooled to room temperature, then calcines 2h at 920 DEG C in calcining furnace in 55 DEG C of vacuum drying ovens, cooling, is put into 6 parts of matter
Impregnate 3h in the hydrochloric acid solution that amount percentage is 4%, filtering is taken out, and drying is cleaned with clear water, be added after crushing 4 parts of polyisobutene,
5 parts of methacrylates, 2 parts of glass fibres and 5 portions of flax are uniformly mixed, and are warming up to 110 DEG C, 30min are kept the temperature, in 650r/min
Rotating speed stirs 30min, is cooled to room temperature up to toughened and reinforced auxiliary agent.
The toughening modifying filler is prepared by following technique：8 parts of carboxylic carbon nano-tubes, 8 parts are received by weight
Rice silica, 3 parts of tapioca starch, 5 parts of kaolin and 1 part of carboxylic acrylonitrile butadiene rubber latex are uniformly mixed, and are stirred 10h in 75 DEG C, are then added
Enter 6 parts of polylactic acid, 1 part of silane resin acceptor kh-550,8 parts of polyvinyl alcohol and 3 parts of methyl methacrylates to be uniformly mixed, in
2h is stirred under 6500r/min rotating speeds, then heats to 100 DEG C, keeps the temperature 0.5h, 6 parts of ammonium persulfates and 1 part of hydroxide is then added
Aluminium is uniformly mixed, and after then being cleaned with deionized water, is filtered, and is placed in 55 DEG C of baking oven dry 1h, is cooled to room temperature and is increased
Tough modified filler.
The surface conditioning agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, m-phenylene diamine (MPD) and 1,3-
Butanediol is by weight 1：6：1：6：0.5 mixes.
The preparation method of the lithium ion battery flexible electrical pole piece with coat, includes the following steps：
S1：Liquid sizing material is obtained after Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are warming up to 120 DEG C of meltings, by hydroxyl
Cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding cross 40 mesh
Sieve, is then added in liquid sizing material, is continuously heating to 140 DEG C and stirs 2h in 850r/min rotating speeds, is cooled to room temperature to obtain base
Material；
S2：Coumarone indene resin, butyl acetate cellulose, carbon black and polyphosphoric acids are added after the base-material that S1 is obtained is warming up to 90 DEG C
Aluminium, nano-graphite are uniformly mixed, and 40min is stirred in 1500r/min after being continuously heating to 130 DEG C, are cooled to room temperature to obtain primary
Modified base material；
S3：Modified base material is warming up to after 110 DEG C and toughened and reinforced auxiliary agent, toughening modifying filler and surface conditioning agent is added mixes
It closes uniformly, stirs 50min in 850r/min rotating speeds after being continuously heating to 150 DEG C, be cooled to room temperature to obtain coat slurry；
S4, at least side that the coat slurry that S3 is obtained is coated on to pole piece matrix obtain the lithium with coat after dry
Ion battery flexible electrical pole piece.
Embodiment 3
A kind of lithium ion battery flexible electrical pole piece with coat, including pole piece matrix and at least be coated in pole piece matrix side
Coat, the coat, as unit of parts by weight, including following raw material：40 parts of Kynoar, coumarone indene resin 18
Part, 14 parts of polytetrafluoroethylene (PTFE), 3 parts of butadiene-styrene rubber, 5 parts of hydroxylated cellulose, 1 part of acrylonitrile, 6 parts of fluoro-alkyl methoxyl group ether alcohol,
8 parts of butyl acetate cellulose, 8 parts of carbon nanotube, 3 parts of graphene oxide, 4 parts of polyaniline, 4 parts of carbon black, 5 parts of polyphosphoric acids aluminium,
3 parts of nano-graphite, 3 parts of toughened and reinforced auxiliary agent, 10 parts of toughening modifying filler, 25 parts of surface conditioning agent.
The toughened and reinforced auxiliary agent is prepared by following technique：By weight by 25 parts of butyl acrylates and 4 parts of over cures
Sour potassium is uniformly mixed, and reacts 3h, and the aluminum sulfate aqueous solution that 3 parts of mass fractions are 8% is then added dropwise, is demulsified, filtering, after washing
Dry 7h, is cooled to room temperature, then calcines 5h at 820 DEG C in calcining furnace in 45 DEG C of vacuum drying ovens, cooling, is put into 2 parts of matter
Impregnate 1h in the hydrochloric acid solution that amount percentage is 6%, filtering is taken out, and drying is cleaned with clear water, be added after crushing 9 parts of polyisobutene,
3 parts of methacrylates, 6 parts of glass fibres and 1 portion of flax are uniformly mixed, and are warming up to 130 DEG C, 10min are kept the temperature, in 850r/min
Rotating speed stirs 20min, is cooled to room temperature up to toughened and reinforced auxiliary agent.
The toughening modifying filler is prepared by following technique：16 parts of carboxylic carbon nano-tubes, 4 parts are received by weight
Rice silica, 9 parts of tapioca starch, 2 parts of kaolin and 4 parts of carboxylic acrylonitrile butadiene rubber latexes are uniformly mixed, and are stirred 12h in 65 DEG C, are then added
Enter 3 parts of polylactic acid, 3 parts of silane resin acceptor kh-550s, 4 parts of polyvinyl alcohol and 9 parts of methyl methacrylates to be uniformly mixed, in
4h is stirred under 5500r/min rotating speeds, then heats to 90 DEG C, keeps the temperature 1.5h, 2 parts of ammonium persulfates and 5 parts of hydroxides are then added
Aluminium is uniformly mixed, and after then being cleaned with deionized water, is filtered, and is placed in 45 DEG C of baking oven dry 4h, is cooled to room temperature and is increased
Tough modified filler.
The surface conditioning agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, m-phenylene diamine (MPD) and 1,3-
Butanediol is by weight 3：2：5：4：1.5 mixing.
The preparation method of the lithium ion battery flexible electrical pole piece with coat, includes the following steps：
S1：Liquid sizing material is obtained after Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are warming up to 150 DEG C of meltings, by hydroxyl
Cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding cross 20 mesh
Sieve, is then added in liquid sizing material, is continuously heating to 160 DEG C and stirs 3h in 650r/min rotating speeds, is cooled to room temperature to obtain base
Material；
S2：Coumarone indene resin, butyl acetate cellulose, carbon black and polyphosphoric acids are added after the base-material that S1 is obtained is warming up to 90 DEG C
Aluminium, nano-graphite are uniformly mixed, and 40min is stirred in 1500r/min after being continuously heating to 130 DEG C, are cooled to room temperature to obtain primary
Modified base material；
S3：Modified base material is warming up to after 110 DEG C and toughened and reinforced auxiliary agent, toughening modifying filler and surface conditioning agent is added mixes
It closes uniformly, stirs 50min in 850r/min rotating speeds after being continuously heating to 150 DEG C, be cooled to room temperature to obtain coat slurry；
S4, at least side that the coat slurry that S3 is obtained is coated on to pole piece matrix obtain the lithium with coat after dry
Ion battery flexible electrical pole piece.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack coumarone indene resin in the raw material of pole piece, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced help
Agent, toughening modifying filler, surface conditioning agent.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack coumarone indene resin in the raw material of pole piece.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack butyl acetate cellulose in the raw material of pole piece.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack carbon black in the raw material of pole piece.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack polyphosphoric acids aluminium in the raw material of pole piece.
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack nano-graphite in the raw material of pole piece.
Comparative example 7
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack toughened and reinforced auxiliary agent in the raw material of pole piece.
Comparative example 8
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack toughening modifying filler in the raw material of pole piece.
Comparative example 9
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Lack surface conditioning agent in the raw material of pole piece.
Comparative example 10
Using a kind of Chinese patent application document " flexible electrical pole piece and preparation method thereof with coat（Application publication number：
CN107611341A）" in method described in specific embodiment 1-4 prepare flexible electrical pole piece.
Comparative example 11
Using Chinese patent application document " a kind of preparation method and flexible electrode of flexible electrode（Application publication number：
CN104078248A）" in method described in specific embodiment 1 prepare flexible electrical pole piece.
Comparative example 12
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Coumarone indene resin is 17 parts in the raw material of pole piece, butyl acetate cellulose is 13 parts, carbon black is 2 parts, polyphosphoric acids aluminium is 6 parts,
Nano-graphite is 2 parts, toughened and reinforced auxiliary agent is 4 parts, toughening modifying filler is 8 parts, surface conditioning agent is 26 parts.
Comparative example 13
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Coumarone indene resin is 38 parts in the raw material of pole piece, butyl acetate cellulose is 7 parts, carbon black is 8 parts, polyphosphoric acids aluminium is 1 part, receives
Meter Shi Mo is 7 parts, toughened and reinforced auxiliary agent is 0.6 part, toughening modifying filler is 7 parts, surface conditioning agent is 28 parts.
Comparative example 14
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing the lithium ion battery flexible electrical with coat
Coumarone indene resin is 16 parts in the raw material of pole piece, butyl acetate cellulose is 13 parts, carbon black is 3 parts, polyphosphoric acids aluminium is 1 part,
Nano-graphite is 7 parts, toughened and reinforced auxiliary agent is 0.8 part, toughening modifying filler is 22 parts, surface conditioning agent is 13 parts.
The test of the performances such as toughness is carried out to product made from embodiment 1-3 and comparative example 1-14, the results are shown in table below.
| Experimental project | Elongation % | Tensile strength Mpa |
| Embodiment 1 | 696 | 25.8 |
| Embodiment 2 | 694 | 23.9 |
| Embodiment 3 | 693 | 24.2 |
| Comparative example 1 | 367 | 16.8 |
| Comparative example 2 | 674 | 23.1 |
| Comparative example 3 | 681 | 22.6 |
| Comparative example 4 | 688 | 21.3 |
| Comparative example 5 | 680 | 23.4 |
| Comparative example 6 | 691 | 22.5 |
| Comparative example 7 | 689 | 22.9 |
| Comparative example 8 | 690 | 21.8 |
| Comparative example 9 | 692 | 22.0 |
| Comparative example 10 | 106-119 | 8.1-8.6 |
| Comparative example 11 | 189-204 | 7.4-8.0 |
| Comparative example 12 | 224 | 8.7 |
| Comparative example 13 | 222 | 9.2 |
| Comparative example 14 | 219 | 9.3 |
As seen from the above table：（1）By embodiment 1-3 and the data of comparative example 10 and comparative example 11 as it can be seen that embodiment 1-3 systems
The toughness of the lithium ion battery flexible electrical pole piece with coat obtained is significantly higher than made from comparative example 10 and comparative example 11
The toughness of electrode slice；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
（2）By embodiment 1 and the data of comparative example 1-9 as it can be seen that coumarone indene resin, butyl acetate cellulose, carbon black, poly
Aluminum phosphate, nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, surface conditioning agent are preparing the lithium ion with coat
Synergistic effect is played in cell flexible electrode slice, collaboration improves the toughness properties of the electrode slice；This is：Coumarone indene resin,
Butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler and surface conditioning agent
As reinforcement system, wherein coumarone indene resin is major ingredient, assigns the performance of reinforcement system enhancing toughness, butyl acetate cellulose,
Carbon black, polyphosphoric acids aluminium, nano-graphite enhance reinforced filling as toughness, can not only act at the melting of coumarone indene resin
During reason, improve the toughness of coumarone indene resin, moreover it is possible to improve electric conductivity, addition surface conditioning agent as graft modification agent,
Realization applies to the toughness reinforcement of toughened and reinforced auxiliary agent and toughening modifying filler in the base-material of the electrode matrix coat, realizes
Toughened and reinforced auxiliary agent and the hydroxyl on toughening modifying filler surface realize and base-material knot under the grafting effect of surface conditioning agent
It closes, effectively increases the toughness properties of electrode slice of the present invention.
Wherein, toughened and reinforced auxiliary agent improves that aluminum sulfate is added dropwise in butyl acrylate and potassium peroxydisulfate after mixing is water-soluble
Liquid is demulsified, and filtering is dry after washing, is calcined after being cooled to room temperature, cooling, is put into hydrochloric acid solution and impregnates, and filtering is taken out, and uses
Clear water cleans drying, and polyisobutene, methacrylate, glass fibre and flax are added after crushing and is uniformly mixed, heats up, protects
Temperature, stirring, is cooled to room temperature to obtain the final product, using butyl acrylate, polyisobutene, methacrylate as grafted monomers, with mistake
Potassium sulfate is initiator, tough to monomer by glass fibre and Flax Grafting to monomer, realizing after acid solution is handled
The reinforcement of property, and the preparation of coat is applied to, effectively increase the toughness of electrode slice.
Wherein, toughening modifying filler is by by carboxylic carbon nano-tube, nano silicon dioxide, tapioca starch, kaolin and carboxylic
Base NBR latex is uniformly mixed, then polylactic acid, silane resin acceptor kh-550, polyvinyl alcohol and methacrylic acid is added in stirring
Methyl esters is uniformly mixed, and is stirred under rotating speed, and ammonium persulfate and aluminium hydroxide are added after heating and heat preservation and is uniformly mixed, then spend from
It after sub- water cleaning, filters, is placed in drying in baking oven, is cooled to room temperature to obtain, with carboxylic carbon nano-tube, nanometer titanium dioxide
Silicon, tapioca starch, kaolin are toughened and reinforced filler, and basic emulsion is grafted with polylactic acid and carboxylic acrylonitrile butadiene rubber latex, poly- in film forming agent
Under the action of vinyl alcohol, in the case where silane resin acceptor kh-550 is acted on as grafting, realizes toughened and reinforced filler and be grafted to basis
In lotion, the reinforcement of toughness is realized, the preparation of the electrode slice surface coating layer of the present invention is applied to, further improves electrode
The toughness of piece.
（3）By the data of comparative example 12-14 as it can be seen that coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium,
Nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, surface conditioning agent weight ratio do not exist（18-36）：（8-12）：（4-
6）：（2-5）：（3-6）：（1-3）：（10-20）：（15-25）When in range, the corresponding numerical value of toughness of electrode slice obtained with
The numerical value of embodiment 1-3 is very different, and the numerical value of embodiment 1-3 is much smaller than, with the prior art（Comparative example 10 and comparative example 11）
Numerical value it is suitable.It is coumarone indene resin of the present invention, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced
As reinforcement system, embodiment 1-3 controls prepare the lithium ion with coat for auxiliary agent, toughening modifying filler, surface conditioning agent
By adding coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, increasing when cell flexible electrode slice
Tough strengthening helping agent, toughening modifying filler, surface conditioning agent weight ratio be（18-36）：（8-12）：（4-6）：（2-5）：（3-6）：
（1-3）：（10-20）：（15-25）, realize using the toughness that coumarone indene resin is excellent in reinforcement system, and in butyl acetate fibre
Element, carbon black, polyphosphoric acids aluminium, nano-graphite are tieed up as under toughened and reinforced filler effect, using coumarone indene resin as reinforcement system
For major ingredient, realize that less toughened and reinforced filler effect in coumarone indene resin, improves the toughness of coumarone indene resin, and on surface
Under the grafting effect of inorganic agent, the toughness strengthening action of toughened and reinforced auxiliary agent and toughening modifying filler is utilized, effectively increases
The toughness of the electrode slice, coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughening are mended as a result,
Strong auxiliary agent, toughening modifying filler, surface conditioning agent are applied to as reinforcement system in the preparation of the electrode slice, effectively increase this
The toughness of electrode slice.
The above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
Claims (10)
1. a kind of lithium ion battery flexible electrical pole piece with coat, including pole piece matrix and at least it is coated in pole piece matrix one
The coat of side, which is characterized in that the coat includes following raw material：Kynoar, coumarone indene resin, polytetrafluoroethyl-ne
Alkene, butadiene-styrene rubber, hydroxylated cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, butyl acetate cellulose, carbon nanotube, oxidation
Graphene, polyaniline, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening modifying filler, surface conditioning agent；
The toughened and reinforced auxiliary agent, as unit of parts by weight, including following raw material：15-25 parts of butyl acrylate, potassium peroxydisulfate 4-
8 parts, mass fraction be 4-8% 3-9 parts of aluminum sulfate aqueous solution, mass percent be 4-6% 2-6 parts of hydrochloric acid solution, poly- isobutyl
4-9 parts of alkene, 3-5 parts of methacrylate, 2-6 parts of glass fibre, 1-5 parts of flax；
The toughening modifying filler, as unit of parts by weight, including following raw material：8-16 parts of carboxylic carbon nano-tube, nanometer two
4-8 parts of silica, 3-9 parts of tapioca starch, 2-5 parts of kaolin, 1-4 parts of carboxylic acrylonitrile butadiene rubber latex, 3-6 parts of polylactic acid, silane coupling agent
1-3 parts of KH-550,4-8 parts of polyvinyl alcohol, 3-9 parts of methyl methacrylate, 2-6 parts of ammonium persulfate, 1-5 parts of aluminium hydroxide；
The coumarone indene resin, butyl acetate cellulose, carbon black, polyphosphoric acids aluminium, nano-graphite, toughened and reinforced auxiliary agent, toughening
Modified filler, surface conditioning agent weight ratio be（18-36）：（8-12）：（4-6）：（2-5）：（3-6）：（1-3）：（10-20）：
（15-25）.
2. the lithium ion battery flexible electrical pole piece according to claim 1 with coat, which is characterized in that the weight
Amount is than being 27：10：5：3.5：4.5：2：15：20.
3. the lithium ion battery flexible electrical pole piece according to claim 1 with coat, which is characterized in that the coating
Layer is as unit of parts by weight, including following raw material：20-40 parts of Kynoar, 18-36 parts of coumarone indene resin, polytetrafluoroethylene (PTFE)
8-14 parts, 3-6 parts of butadiene-styrene rubber, 2-5 parts of hydroxylated cellulose, 1-5 parts of acrylonitrile, 3-6 parts of fluoro-alkyl methoxyl group ether alcohol, acetic acid
8-12 parts of cellulose butyrate, 4-8 parts of carbon nanotube, 3-6 parts of graphene oxide, 2-4 parts of polyaniline, 4-6 parts of carbon black, polyphosphoric acids
2-5 parts of aluminium, 3-6 parts of nano-graphite, auxiliary agent 1-3 parts toughened and reinforced, 10-20 parts of toughening modifying filler, surface conditioning agent 15-25
Part.
4. the lithium ion battery flexible electrical pole piece according to claim 1 with coat, which is characterized in that the toughening
Strengthening helping agent is prepared by following technique：Butyl acrylate and potassium peroxydisulfate are uniformly mixed, 1-3h is reacted, matter is then added dropwise
Measure the aluminum sulfate aqueous solution that score is 4-8%, be demulsified, filtering, after washing in 45-55 DEG C of vacuum drying oven dry 5-7h, be cooled to
Then room temperature calcines 2-5h in calcining furnace at 820-920 DEG C, cooling, is put into the hydrochloric acid solution that mass percent is 4-6%
Middle immersion 1-3h, filtering take out, with clear water clean drying, after crushing be added polyisobutene, methacrylate, glass fibre and
Flax is uniformly mixed, and is warming up to 110-130 DEG C, keeps the temperature 10-30min, and 20-30min is stirred in 650-850r/min rotating speeds, cooling
To room temperature up to toughened and reinforced auxiliary agent.
5. the lithium ion battery flexible electrical pole piece according to claim 1 with coat, which is characterized in that the toughening
Modified filler is prepared by following technique：By carboxylic carbon nano-tube, nano silicon dioxide, tapioca starch, kaolin and carboxyl
NBR latex is uniformly mixed, and stirs 10-12h in 65-75 DEG C, polylactic acid, silane resin acceptor kh-550, polyvinyl alcohol is then added
It is uniformly mixed with methyl methacrylate, 2-4h is stirred under 5500-6500r/min rotating speeds, then heat to 90-100 DEG C, protected
Warm 0.5-1.5h, is then added ammonium persulfate and aluminium hydroxide is uniformly mixed, and after then being cleaned with deionized water, filters, is placed in
Dry 1-4h, is cooled to room temperature to obtain toughening modifying filler in 45-55 DEG C of baking oven.
6. the lithium ion battery flexible electrical pole piece according to claim 1 with coat, which is characterized in that the surface
Inorganic agent is by azobisisoheptonitrile, polyvinyl butyral, polyetherimide, m-phenylene diamine (MPD) and 1,3 butylene glycol by weight 1-
3：2-6：1-5：4-6：0.5-1.5 is mixed.
7. a kind of preparation side according to lithium ion battery flexible electrical pole piece of the claim 1-6 any one of them with coat
Method, which is characterized in that include the following steps：
S1：By Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber heating melting after obtain liquid sizing material, by hydroxylated cellulose,
Acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding cross 20-40 mesh sieve, so
After be added in liquid sizing material, continue heating stirring, be cooled to room temperature to obtain base-material；
S2：Coumarone indene resin, butyl acetate cellulose, carbon black and polyphosphoric acids aluminium are added after the base-material that S1 is obtained is heated up, receives
Meter Shi Mo is uniformly mixed, and is stirred after continuing heating, is cooled to room temperature to obtain a modified base material；
S3：Toughened and reinforced auxiliary agent, toughening modifying filler and surface conditioning agent is added after modified base material is heated up to be uniformly mixed,
It is stirred after continuing heating, is cooled to room temperature to obtain coat slurry；
S4, at least side that the coat slurry that S3 is obtained is coated on to pole piece matrix obtain the lithium with coat after dry
Ion battery flexible electrical pole piece.
8. the preparation method of the lithium ion battery flexible electrical pole piece according to claim 7 with coat, feature exist
In, in S1, liquid sizing material is obtained after Kynoar, polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are warming up to 120-150 DEG C of melting, it will
Hydroxylated cellulose, acrylonitrile, fluoro-alkyl methoxyl group ether alcohol, carbon nanotube, graphene oxide and polyaniline mixed grinding, mistake
20-40 mesh sieves, and is then added in liquid sizing material, is continuously heating to 140-160 DEG C and stirs 2-3h in 650-850r/min rotating speeds,
It is cooled to room temperature to obtain base-material.
9. the preparation method of the lithium ion battery flexible electrical pole piece according to claim 7 with coat, feature exist
In in S2, coumarone indene resin, butyl acetate cellulose, carbon black and more are added after the base-material that S1 is obtained is warming up to 90-110 DEG C
Poly aluminium phosphate, nano-graphite are uniformly mixed, and 20-40min is stirred in 1500-2500r/min after being continuously heating to 120-130 DEG C,
It is cooled to room temperature to obtain a modified base material.
10. the preparation method of the lithium ion battery flexible electrical pole piece according to claim 7 with coat, feature exist
In in S3, being added after a modified base material is warming up to 110-120 DEG C at toughened and reinforced auxiliary agent, toughening modifying filler and surface
It manages agent to be uniformly mixed, stirs 30-50min in 850-1050r/min rotating speeds after being continuously heating to 130-150 DEG C, be cooled to room temperature
Obtain coat slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810413513.3A CN108598364A (en) | 2018-05-03 | 2018-05-03 | A kind of lithium ion battery flexible electrical pole piece and preparation method thereof with coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN109768281A (en) * | 2018-12-21 | 2019-05-17 | 上海力信能源科技有限责任公司 | A kind of cathode composite mortar and preparation method thereof, lithium battery cathode pole piece |
| CN113097489A (en) * | 2021-04-01 | 2021-07-09 | 辽宁奥亿达新材料有限公司 | Lithium ion battery carbon negative electrode liquid phase coating material, preparation and coating method |
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| CN109768281A (en) * | 2018-12-21 | 2019-05-17 | 上海力信能源科技有限责任公司 | A kind of cathode composite mortar and preparation method thereof, lithium battery cathode pole piece |
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Application publication date: 20180928 |