CN107437600A - A kind of lithium ion battery active membrane of skeleton and gel-type vehicle integration and preparation method thereof - Google Patents
A kind of lithium ion battery active membrane of skeleton and gel-type vehicle integration and preparation method thereof Download PDFInfo
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- CN107437600A CN107437600A CN201610418968.5A CN201610418968A CN107437600A CN 107437600 A CN107437600 A CN 107437600A CN 201610418968 A CN201610418968 A CN 201610418968A CN 107437600 A CN107437600 A CN 107437600A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A kind of lithium ion battery active membrane of skeleton and gel-type vehicle integration of the present invention and preparation method thereof, skeleton is perforated membrane made from second composition by the line style of vinyl, pectination or hyperbranched amphipathic nature polyalcohol of hydrophilic chain end using linear polymer PVDF or PVDF HFP as first composition；The aperture of film is 0.05 1.0um, and film thickness is 20 80um；The formula composition of gel-type vehicle includes：Monomer or oligomer, thermal initiator and solvent containing unsaturated double-bond.The phase inversion that film-forming process of the present invention uses, obtains membrane porosity height, and effectively controllable in the relative broad range of aperture, pore-size distribution is narrow, preferably strengthens water retainability；The controllability of the membrane structure of the present invention is good, and production is reproducible；The wetability of electrolyte is improved, reduces inside battery electrode and membrane electrical resistance；The present invention improves battery temperature tolerance, battery is also unlikely to that blast and burning occurs in higher temperature, is especially suitable for being used in power lithium-ion battery.
Description
Technical field
The present invention relates to lithium ion battery separator Material Field, more particularly to gel electrolyte activity in electrokinetic cell every
Film and preparation method thereof.
Background technology
Lithium ion battery is new rechargeable battery, with use at present alkali/manganese cell, lead/sour battery and
The batteries such as nickel/hydrogen are compared, and lithium ion battery has open-circuit voltage height, specific capacity is high, have extended cycle life, security is good, to environment
Friendly, the advantages that self-discharge rate is low, memory-less effect.In liquid lithium ion battery, as important component, it leads barrier film
It is to separate the positive and negative electrode of battery to act on, and prevents the two poles of the earth from directly contacting and short circuit occurs, and its microcellular structure keeps necessary electricity
Solution liquid, forms the passage of ion movement and realizing makes the freely through function of ion.Though liquid electrolyte commercially obtains
Very ten-strike, but to solve the urgent needs of electronic device microminaturization, it is necessary to walk to develop the way of application polymer electrolyte
Footpath, that is, develop polymer Li-ion battery.
Polymer Li-ion battery is the lithium ion battery of new generation to emerge for 1999, in this battery, due to electrolysis
Matter is solid, can be processed into film, can use plastic-aluminum packaging film encapsulation again, therefore polymer Li-ion battery is than liquids in general lithium
Ion battery has many advantages, such as no liquid leakage, battery security height, specific energy density height, flexible shapes, can be made into thickness
The battery of degree less than 1mm etc..Polymer dielectric is divided into all solid state electrolyte and gel electrolyte, and liquid is added in gel electrolyte
Body plasticizer, and be not adding liquid plasticizer in all solid state electrolyte.
The gel electrolyte used at present mainly has following several preparation methods：First, by polymeric matrix（Or monomer）, lithium
Salt, plasticizer and solvent, additive, such as inorganic nano-particle are optionally added in addition（Al2O3, SiO2Or TiO2Deng）, match somebody with somebody
It is made casting film after appropriate solution, heating is volatilized dry solvent（Or crosslinking）It can obtain gel electrolyte membrane afterwards.Such as publication number
, will in CN101381429A invention, its ter-polymers is obtained by MMA, AN, vinyl acetate monomer emulsion polymerization
This polymer powder, which is dissolved in DMF, to be obtained gel and is coated with a glass, and gel is put into and triggers phase transfer in tank, is entered
One step is dried to obtain the gelatin polymer film of self-supporting, activates and produces GPE, and electrical conductivity is 3.48 × 10-3S/cm, lithium ion mobility
Number is 0.51；In Publication No. CN101409364A invention, pass through the n-BMA monomer and benzene of different proportion
The emulsion polymerization of vinyl monomer obtains copolymer, and under conditions of ultrasonic wave, a certain amount of nano-particle is dispersed in THF,
Polymer dissolving is entered to obtain required polymer film again.But the usual mechanical performance of gel electrolyte membrane made from this method is not
It is good；2nd, by polymeric matrix（Or monomer）, solvent, optionally add additive, such as inorganic nano-particle in addition（Al2O3,
SiO2Or TiO2Deng）, after being configured to appropriate solution, by the solution-cast on supporter（Such as non-woven fabrics, polyalkene diaphragm etc.）,
Heating treats that solvent volatilization is dry（Or crosslinking）Afterwards, compound barrier film is obtained, this barrier film is obtained to gel electricity after electrolyte activates
Xie Zhi.As Publication No. CN101070398A invention in, synthesizing methylmethacrylate-methacryloxypropyl first
Trimethoxysilane copolymer, after this copolymer is carried out into solgel reaction, directly coating solidifies on MIcroporous polyolefin film,
Activation can obtain gel electrolyte membrane, and electrical conductivity is 1.2 × 10-3S/cm.But coat is with supporting the affine of interlayer in the method
Property is not high, when long-term use be present the characteristics of cyclicity difference；3rd, by monomer（Such as acrylonitrile, methyl methacrylate or epoxy second
Alkane etc.）, after initiator, lithium salts and plasticizer be configured to solution, injection is equipped with the battery container of both positive and negative polarity, poly- by original position
The mode of conjunction prepares polymer battery.In Publication No. CN 1645662A invention, by two kinds of monomers in mass ratio 1：1-9 is mixed
Close, then be mixed and stirred for uniformly with thermal initiator, liquid electrolyte, formation gel polymer electrolyte precursor, by gel polymerisation
In thing electrolyte precursors injection semi-finished product battery, vacuumize, seal, semi-finished product battery is subjected to heat polymerization, gel is made
Electrolyte, room-temperature conductivity is more than 10-3cm-1, electrochemical window is in more than 4.8V, and technique is relatively simple, and monomeric character is：
The monomer includes ethylene glycol dimethacrylate, tetraethylene glycol dimethylacrylate, ten ethyleneglycol dimethacrylates
Ester, glycol diacrylate.As Publication No. CN 101475663A invention in, using acrylonitrile and polyethylene glycol diformazan
Base acrylate is monomer, and EC is plasticizer, and AIBN is initiator, and lithium perchlorate is lithium salts, and add ionic liquid 1- butyl-
3- methyl imidazolium tetrafluoroborates are triggered, the mode of in-situ polymerization prepares lithium battery, institute as electrolyte components using free radical
Gel electrolyte room-temperature conductivity processed is higher, there is good dimensional stability and mechanical mechanics property, avoids leakage, volatilization,
Improve security.The more difficult control of this method polymerization process, and unreacted monomer and excessive initiator can not remove；4th,
Using Bellcore technologies as representative, swellable polymer is selected（Such as PVDF or PVDF-HFP）For matrix material, conjunction is added
Suitable solvent and plasticizer are configured to mixed solution, and it is largely micro- that the method as extracting higher boiling plasticizer possesses gained barrier film
Pore structure, the microporous barrier is finally immersed into activation in liquid electrolyte and can obtain gel electrolyte.Such as US Patent
Mentioned PVDF/HFP copolymers, plasticizer, SiO in 5296318 and US Patent 5418091 first2Superfine powder, it is mixed in
In acetone, suitable slurry is prepared at 50 DEG C, polymer precursor film is first made after casting, then extracting is gone in organic solvent
Plasticizer, so as to generate the film with certain microcellular structure, then soak electrolyte activation and prepare gel electrolyte.This method needs
Substantial amounts of plasticizer is used, increases cost, and extracts poration process and is difficult to control.Therefore, grew up in the last few years
Immersion precipitation thinks that conversion method is a kind of ideal porous polymer membrane preparation method.
Immersion precipitation phase inversion process is also referred to as the wet method in inversion of phases filming technology, during using method film,
Polymer solution is first cast to be extruded on reinforcing material or from spinning nozzle, is then immersed in non-solvent bath rapidly, with solvent
Continuous exchange with non-solvent and the liquid-liquid phase separation of polymer solution occurs, the inversion of phases solidification of split-phase system cement-based powder material
Effect, ultimately form the film of different structure form and performance.In addition, during immersion precipitation phase inversion process is film-made, addition
Some have the polymers compositions of preferable complexing power with lithium salts, are remarkably improved the chemical property of gained gel electrolyte,
Such as electrical conductivity or cycle performance.These conventional additive polymers are mostly line style, pectination or hyperbranched amphipathic polymer etc.,
Wherein hydrophobic segment（The alkane such as PE, PP segment or PTFE, PVDF, PPO, polysiloxanes etc. contain heteroatomic alkane segment or PS
Deng containing fragrant hydrocarbon segment）There is preferable compatibility with film matrix, can effectively reduce the crystallinity of film matrix, formed more without fixed
Shape region；Hydrophilic segment（PEO or PEG）It can be enriched with during inversion of phases to film or fenestra surface migration, these are on surface
The component of enrichment is beneficial to lithium ion mobility in itself, equivalent to the passage for stopping having supplied a lithium ion fast transferring, thus method system
The barrier film obtained can be referred to as " active porous barrier film ".It is pointed out that this kind " active porous barrier film " is more compared to traditional
Hole barrier film has higher pick up, protects the premium properties such as liquid rate and electrical conductivity, but its active component is mainly in film or fenestra table
The PEO or PEG chain segment of face enrichment, and after the soaking electrolyte activation of the film, flowing in duct also inevitably be present
Liquid electrolyte, this is still the potential safety hazard during battery use.
Therefore, some are had to the gel-type vehicle of preferable complexing power with lithium salts（Contain the units such as PEO, PAN, PMMA
Polymer）It is incorporated into the duct of " active porous barrier film ", passes through the double bond in gel-type vehicle and the PEO of fenestra surface enrichment
Or the mode of PEG chain segment end-vinyl heat cross-linking, by these gel-type vehicles and film strong bonded, prepare skeleton and gel-type vehicle
The lithium ion battery " active membrane " of integration, has been a good problem to study.
The content of the invention
In order to overcome above-mentioned deficiency of the prior art, the invention provides one kind to obtain membrane porosity height, and aperture is wider
In the range of effectively it is controllable, pore-size distribution is narrow, can preferably strengthen water retainability a kind of skeleton and gel-type vehicle integration
The preparation method of lithium ion battery active membrane.
The object of the present invention is achieved like this：
A kind of lithium ion battery active membrane of skeleton and gel-type vehicle integration, 1）Described active membrane, skeleton is with line style
Polymer P VDF or PVDF-HFP are first composition, using hydrophilic chain end as the line style of vinyl, pectination or hyperbranched amphipathic
Polymer is perforated membrane made from second composition；The aperture of film is 0.05-1.0um, film thickness 20-80um；Gel-type vehicle
Formula composition includes：Monomer or oligomer, thermal initiator and solvent containing unsaturated double-bond.
A kind of preparation method of the lithium ion battery active membrane of skeleton and gel-type vehicle integration, comprises the following steps：
1）It is 5~15% parents by linear polymer PVDF or PVDF-HFP that weight/mass percentage composition is 8~25%, weight/mass percentage composition
Water chain end is the amphipathic nature polyalcohol of vinyl, weight/mass percentage composition is 0.1~10% additive, weight/mass percentage composition are
60~85% solvent is mixed and made into casting solution at 45~60 DEG C；Preparation liquid is spread into thickness on stainless steel carrier or glass carrier
The liquid film for 80~200 microns is spent, and immerses in 0~60 DEG C of coagulating bath and is solidified into precursor backbone；
2）The monomer or oligomer that are 1~20% by the weight/mass percentage composition containing unsaturated double-bond, weight/mass percentage composition 0.01
The solvent that~3% thermal initiator and weight/mass percentage composition is 75~90% is configured to solution；By step 1）Obtained skeleton leaching
Bubble 0.5~2 h in the solution, is put into after taking-up in sealable glass mold, scrubbed in 50-75 DEG C of thermal polymerization 2~5 h
The lithium ion battery active membrane of skeleton and gel-type vehicle integration is can obtain after drying.
Described linear polymer is：Kynoar（PVDF）Or Kynoar-hexafluoropropylene copolymer（PVDF-
HFP）；Additive is：H2O or polyvinylpyrrolidone；Solvent is：N, N '-dimethyl formamide or N, N '-dimethyl acetyl
Amine.
Described line style amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, have AB diblock structures,
ABA three blocks structure or the more block structures of ABAABB；Wherein hydrophobic segment be the alkane segment such as PE, PP or PTFE, PVDF,
PPO, polysiloxanes etc. contain fragrant hydrocarbon segment containing heteroatomic alkane segment or PS etc.；Hydrophilic segment is PEO or PEG；It is wherein close
Water segment accounts for the 20~60% of total polymer weight.
Described pectination amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, main chain are hydrophobic segment, are
The alkane such as PE, PP segment or PTFE, PVDF, PPO, polysiloxanes etc. contain fragrant hydrocarbon chain containing heteroatomic alkane segment or PS etc.
Section；Hydrophilic side chain is PEO or PEG；Wherein hydrophilic segment accounts for the 20~60% of total polymer weight.
Described hyperbranched amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, core are polyamide-amide, gathered
Amine -ester, polypropylene-imine, polyester or polyethers；Hydrophilic arm is PEO or PEG, and wherein hydrophilic segment accounts for the 20 of total polymer weight
~60%.
Described vinylated raw material is glycidyl fat or methyl propenoic acid glycidyl fat；
Described coupling agent is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene -1,6- diisocyanate
Or IPDI；
Described catalyst is dibutyl tin dilaurate；
The described monomer containing unsaturated double-bond or oligomer are：Small molecule monomer simultaneously containing EO, AN, MMA unit or
The low-molecular weight polymer of number-average molecular weight≤5000 simultaneously containing PEO, PAN, PMMA unit；
Described thermal initiator is dibenzoyl peroxide, azodiisobutyronitrile, di-isopropyl peroxydicarbonate or peroxidating
Two dicyclohexyl carbonates；
Described solvent be benzene,toluene,xylene, MEK, acetylacetone,2,4-pentanedione, tetrahydrofuran, dioxane, dimethyl sulfoxide (DMSO),
Ethyl acetate or/and butyl acetate.
Positive beneficial effect：The system of the lithium ion battery active membrane of skeleton and gel-type vehicle integration disclosed by the invention
Preparation Method, due to the phase inversion that film-forming process uses, membrane porosity height is obtained, effective controllable, aperture in the relative broad range of aperture
Narrowly distributing, it can preferably strengthen water retainability；The controllability of the membrane structure of the present invention is good, and production is reproducible；The present invention's
The introducing of amphipathic nature polyalcohol is effectively increased enrichment of the active component on film or fenestra surface, beneficial to the profit for improving electrolyte
It is moist, reduce inside battery electrode and membrane electrical resistance；The introducing of the amphipathic nature polyalcohol of the present invention is effectively increased activity
Component film or fenestra surface enrichment, beneficial to provide a lithium ion fast transferring passage；Present invention introduces gel base
Chemical bond be present between matter and film matrix, the stability of raising and gel-type vehicle beneficial to film-strength；The gel of the present invention
The introducing of matrix is effectively increased electrolyte absorption and gelling, and the electrolyte of liquid is converted into gel state, improves
Battery temperature tolerance, battery is also unlikely in higher temperature that blast and burning occurs, be especially suitable for in lithium ion power
Used in battery.
Brief description of the drawings
Fig. 1 is the lithium ion battery active membrane surface photo of the middle skeleton of embodiment 1 and gel-type vehicle integration；
Fig. 2 is the lithium ion battery active membrane cross-section photographs of the middle skeleton of embodiment 1 and gel-type vehicle integration；
Fig. 3 is by the septation assembled battery initial discharge capacity figure of embodiment 1；
Fig. 4 is the lithium ion battery active membrane surface photo of the middle skeleton of embodiment 2 and gel-type vehicle integration；
Fig. 5 is the lithium ion battery active membrane cross-section photographs of the middle skeleton of embodiment 2 and gel-type vehicle integration；
Fig. 6 is by the septation assembled battery initial discharge capacity figure of embodiment 2.
Embodiment
With reference to embodiment the present invention will be further described the present invention.
A kind of lithium ion battery active membrane of skeleton and gel-type vehicle integration, 1）Described active membrane, skeleton with
Linear polymer PVDF or PVDF-HFP are first composition, using hydrophilic chain end as the line style of vinyl, pectination or hyperbranched two
Parent's property polymer is perforated membrane made from second composition；The aperture of film is 0.05-1.0um, film thickness 20-80um；Gel base
The formula composition of matter includes：Monomer or oligomer, thermal initiator and solvent containing unsaturated double-bond.
A kind of preparation method of the lithium ion battery active membrane of skeleton and gel-type vehicle integration, comprises the following steps：
1）It is 5~15% parents by linear polymer PVDF or PVDF-HFP that weight/mass percentage composition is 8~25%, weight/mass percentage composition
Water chain end is the amphipathic nature polyalcohol of vinyl, weight/mass percentage composition is 0.1~10% additive, weight/mass percentage composition are
60~85% solvent is mixed and made into casting solution at 45~60 DEG C；Preparation liquid is spread into thickness on stainless steel carrier or glass carrier
The liquid film for 80~200 microns is spent, and immerses in 0~60 DEG C of coagulating bath and is solidified into precursor backbone；
2）The monomer or oligomer that are 1~20% by the weight/mass percentage composition containing unsaturated double-bond, weight/mass percentage composition 0.01
The solvent that~3% thermal initiator and weight/mass percentage composition is 75~90% is configured to solution；By step 1）Obtained skeleton leaching
Bubble 0.5~2 h in the solution, is put into after taking-up in sealable glass mold, scrubbed in 50-75 DEG C of thermal polymerization 2~5 h
The lithium ion battery active membrane of skeleton and gel-type vehicle integration is can obtain after drying.
Described linear polymer is：Kynoar（PVDF）Or Kynoar-hexafluoropropylene copolymer（PVDF-
HFP）；Additive is：H2O or polyvinylpyrrolidone；Solvent is：N, N '-dimethyl formamide or N, N '-dimethyl acetyl
Amine.
Described line style amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, have AB diblock structures,
ABA three blocks structure or the more block structures of ABAABB；Wherein hydrophobic segment be the alkane segment such as PE, PP or PTFE, PVDF,
PPO, polysiloxanes etc. contain fragrant hydrocarbon segment containing heteroatomic alkane segment or PS etc.；Hydrophilic segment is PEO or PEG；It is wherein close
Water segment accounts for the 20~60% of total polymer weight.
Described pectination amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, main chain are hydrophobic segment, are
The alkane such as PE, PP segment or PTFE, PVDF, PPO, polysiloxanes etc. contain fragrant hydrocarbon chain containing heteroatomic alkane segment or PS etc.
Section；Hydrophilic side chain is PEO or PEG；Wherein hydrophilic segment accounts for the 20~60% of total polymer weight.
Described hyperbranched amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, core are polyamide-amide, gathered
Amine -ester, polypropylene-imine, polyester or polyethers；Hydrophilic arm is PEO or PEG, and wherein hydrophilic segment accounts for the 20 of total polymer weight
~60%.
Described vinylated raw material is glycidyl fat or methyl propenoic acid glycidyl fat；
Described coupling agent is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene -1,6- diisocyanate
Or IPDI；
Described catalyst is dibutyl tin dilaurate；
The described monomer containing unsaturated double-bond or oligomer are：Small molecule monomer simultaneously containing EO, AN, MMA unit or
The low-molecular weight polymer of number-average molecular weight≤5000 simultaneously containing PEO, PAN, PMMA unit；
Described thermal initiator is dibenzoyl peroxide, azodiisobutyronitrile, di-isopropyl peroxydicarbonate or peroxidating
Two dicyclohexyl carbonates；
Described solvent be benzene,toluene,xylene, MEK, acetylacetone,2,4-pentanedione, tetrahydrofuran, dioxane, dimethyl sulfoxide (DMSO),
Ethyl acetate or/and butyl acetate.
Embodiment 1
1）It is that 5% hydrophilic chain end is the two of vinyl by polymer P VDF that weight/mass percentage composition is 20%, weight/mass percentage composition
Solvent N, the N- dimethyl that additive PEG 2000 that parent's property polymer, weight/mass percentage composition are 2%, weight/mass percentage composition are 73%
Acetamide is mixed and made into casting solution at 60 DEG C；It is 30 microns that preparation liquid is spread into thickness on stainless steel carrier or glass carrier
Liquid film, and immerse in 40 DEG C of coagulating bath and be solidified into precursor backbone；
2）By monomer divinyl-BDO ether（Weight/mass percentage composition is 10%）, thermal initiator azodiisobutyronitrile（Matter
It is 0.02% to measure percentage composition）And solvent acetone（Weight/mass percentage composition is 90%）It is configured to solution；By step（1）Obtained bone
Frame soaks 1 h in the solution, is put into after taking-up in sealable glass mold, in 65 DEG C of h of thermal polymerization 5, is after scrubbed drying
Can obtain skeleton and gel-type vehicle integration lithium ion battery active membrane, as shown in Figure 1, Figure 2 and Figure 3.
Embodiment 2
1）It is that 8% hydrophilic chain end is vinyl by polymer P VDF-HFP that weight/mass percentage composition is 20%, weight/mass percentage composition
Amphipathic nature polyalcohol, weight/mass percentage composition be 2% additive PVP, weight/mass percentage composition be 70% it is molten
Agent N,N-dimethylformamide is mixed and made into casting solution at 70 DEG C；Preparation liquid is spread on stainless steel carrier or glass carrier
Thickness is 40 microns of liquid film, and immerses in 30 DEG C of coagulating bath and be solidified into precursor backbone；
2）By monomers methyl methacrylate（Weight/mass percentage composition is 8%）, thermal initiator azodiisobutyronitrile（Quality percentage contains
Measure as 0.02%）And solvent acetone（Weight/mass percentage composition is 92%）It is configured to solution；By step（1）Obtained skeleton is immersed in
1 h in solution, it is put into after taking-up in sealable glass mold, in 65 DEG C of h of thermal polymerization 4, bone is can obtain after scrubbed drying
Frame and the lithium ion battery active membrane of gel-type vehicle integration, as shown in Figure 4, Figure 5 and Figure 6.
The preparation method of the lithium ion battery active membrane of skeleton and gel-type vehicle integration disclosed by the invention, due to system
The phase inversion that membrane process uses, membrane porosity height is obtained, effectively controllable in the relative broad range of aperture, pore-size distribution is narrow, can be compared with
Good enhancing water retainability；The controllability of the membrane structure of the present invention is good, and production is reproducible；The amphipathic nature polyalcohol of the present invention
Introducing is effectively increased enrichment of the active component on film or fenestra surface, beneficial to the wetability for improving electrolyte, reduces electricity
Pond internal electrode and membrane electrical resistance；The introducing of the amphipathic nature polyalcohol of the present invention is effectively increased active component in film or fenestra
The enrichment on surface, beneficial to the passage for providing a lithium ion fast transferring；Present invention introduces gel-type vehicle and film matrix between
Chemical bond be present, the stability of raising and gel-type vehicle beneficial to film-strength；The introducing of the gel-type vehicle of the present invention is effective
Add electrolyte absorb and gelling, the electrolyte of liquid is converted into gel state, battery temperature tolerance is improved, makes
Battery is also unlikely to that blast and burning occurs in higher temperature, is especially suitable for being used in power lithium-ion battery.
Above case study on implementation is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, in the field those of ordinary skill possessed knowledge, that is made within the spirit and principles in the present invention is any
Modification, equivalent substitute and improvement etc., it is regarded as the protection domain of the application.
Claims (10)
1. a kind of skeleton and the lithium ion battery active membrane of gel-type vehicle integration, it is characterised in that：Described active membrane,
Skeleton is using linear polymer PVDF or PVDF-HFP as first composition, using hydrophilic chain end as the line style of vinyl, pectination or super
Branched amphipathic nature polyalcohol is perforated membrane made from second composition；The aperture of film is 0.05-1.0um, film thickness 20-80um；
The formula composition of gel-type vehicle includes：Monomer or oligomer, thermal initiator and solvent containing unsaturated double-bond.
A kind of 2. preparation side of the lithium ion battery active membrane of skeleton and gel-type vehicle integration as claimed in claim 1
Method, it is characterised in that comprise the following steps：
1）It is 5~15% parents by linear polymer PVDF or PVDF-HFP that weight/mass percentage composition is 8~25%, weight/mass percentage composition
Water chain end is the addition that the line style, pectination or hyperbranched amphipathic nature polyalcohol, weight/mass percentage composition of vinyl are 0.1~10%
Agent, the solvent that weight/mass percentage composition is 60~85% are mixed and made into casting solution at 45~60 DEG C；By preparation liquid in stainless steel carrier or
The liquid film that thickness is 80~200 microns is spread on glass carrier, and immerses in 0~60 DEG C of coagulating bath and is solidified into precursor backbone；
2）The monomer or oligomer that are 1~20% by the weight/mass percentage composition containing unsaturated double-bond, weight/mass percentage composition 0.01
The solvent that~3% thermal initiator and weight/mass percentage composition is 75~90% is configured to solution；By step 1）Obtained skeleton leaching
Bubble 0.5~2 h in the solution, is put into after taking-up in sealable glass mold, scrubbed in 50-75 DEG C of thermal polymerization 2~5 h
The lithium ion battery active membrane of skeleton and gel-type vehicle integration is can obtain after drying.
3. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：Described linear polymer is：Kynoar（PVDF）Or Kynoar-hexafluoropropylene copolymer
（PVDF-HFP）；Additive is：H2O or polyvinylpyrrolidone；Solvent is：N, N '-dimethyl formamide or N, N '-dimethyl
Acetamide.
4. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：
Described line style amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, there is AB diblock structures, ABA tri-
Block structure or the more block structures of ABAABB；Wherein hydrophobic segment is the alkane segments such as PE, PP or PTFE, PVDF, PPO, gathered
Siloxanes etc. contains fragrant hydrocarbon segment containing heteroatomic alkane segment or PS etc.；Hydrophilic segment is PEO or PEG；Wherein hydrophilic segment
Account for the 20~60% of total polymer weight；
Described pectination amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, main chain are hydrophobic segment, are PE, PP
Containing heteroatomic alkane segment or PS etc. contain fragrant hydrocarbon segment Deng alkane segment or PTFE, PVDF, PPO, polysiloxanes etc.；It is hydrophilic
Side chain is PEO or PEG；Wherein hydrophilic segment accounts for the 20~60% of total polymer weight；
Described hyperbranched amphipathic nature polyalcohol is characterized as：Number-average molecular weight 5000 to 10 ten thousand, core be polyamide-amide, polyamine-
Ester, polypropylene-imine, polyester or polyethers；Hydrophilic arm is PEO or PEG, wherein hydrophilic segment account for total polymer weight 20~
60%。
5. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：Described vinylated raw material is glycidyl fat or methyl propenoic acid glycidyl fat.
6. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：Described coupling agent is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene -1,6-
Diisocyanate or IPDI.
7. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：Described catalyst is dibutyl tin dilaurate.
8. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：The described monomer containing unsaturated double-bond or oligomer are：Simultaneously containing the small of EO, AN, MMA unit
Molecule monomer or the low-molecular weight polymer of number-average molecular weight≤5000 simultaneously containing PEO, PAN, PMMA unit.
9. the preparation side of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：Described thermal initiator is dibenzoyl peroxide, azodiisobutyronitrile, dicetyl peroxydicarbonate diisopropyl
Ester or di-cyclohexylperoxy di-carbonate.
10. the preparation of a kind of skeleton according to claim 2 and the lithium ion battery active membrane of gel-type vehicle integration
Method, it is characterised in that：Described solvent be benzene,toluene,xylene, MEK, acetylacetone,2,4-pentanedione, tetrahydrofuran, dioxane,
Dimethyl sulfoxide (DMSO), ethyl acetate or/and butyl acetate.
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| CN109494409A (en) * | 2018-10-19 | 2019-03-19 | 安徽正熹标王新能源有限公司 | A kind of lithium battery preparation method |
| CN110212141A (en) * | 2019-06-18 | 2019-09-06 | 林雨露 | It is a kind of based on the lithium battery of polyethene microporous membrane new types of diaphragm material |
| CN111463478A (en) * | 2020-03-31 | 2020-07-28 | 珠海冠宇电池股份有限公司 | Solid-state battery comprising interface buffer layer and preparation method thereof |
| CN114649637A (en) * | 2022-03-22 | 2022-06-21 | 赣南师范大学 | Co-jet spinning lithium ion battery diaphragm and preparation method thereof |
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