CN105529495A - Polymer film and preparation method thereof, gel electrolyte and polymer battery - Google Patents

Polymer film and preparation method thereof, gel electrolyte and polymer battery Download PDF

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CN105529495A
CN105529495A CN201410709371.7A CN201410709371A CN105529495A CN 105529495 A CN105529495 A CN 105529495A CN 201410709371 A CN201410709371 A CN 201410709371A CN 105529495 A CN105529495 A CN 105529495A
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polymer
emulsion
polymer film
transition temperature
inorganic particle
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金丽娜
宋威
单军
吴金祥
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BYD Co Ltd
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BYD Co Ltd
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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 provides a polymer film to overcome the problem that a gel polymer electrolyte is relatively low in ionic conductivity in the prior art. The polymer film comprises a first polymer matrix, second polymer particles and inorganic particles, wherein the second polymer particles and the inorganic particles are distributed in the first polymer matrix; the glass-transition temperature of the first polymer matrix is lower than 40 DEG C; the glass-transition temperature of the second polymer particles is higher than 40 DEG C; the glass-transition temperature of the polymer film is 30-60 DEG C; and the air permeability is 150-600sec/100mL. Meanwhile, the invention further discloses a preparation method of the polymer film and a gel electrolyte and a polymer battery comprising the polymer film. The gel electrolyte prepared by the polymer film provided by the invention has excellent ionic conducting properties.

Description

A kind of polymer film and preparation method thereof, gel electrolyte and polymer battery
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of polymer film and preparation method thereof, and adopt gel electrolyte and the polymer battery of this polymer film.
Background technology
Polymer Li-ion battery is the high-energy-density secondary cell system of new generation grown up on liquid lithium ionic cell basis.The general structure of polymer Li-ion battery comprises positive pole, negative pole and the polymer dielectric between positive pole and negative pole.Positive pole comprises plus plate current-collecting body and positive active material, and negative pole comprises negative current collector and negative electrode active material, and described positive active material and negative electrode active material are oppositely arranged, and are contained in battery case together with polymer dielectric.
Compared with conventional liquid lithium ion battery, polymer Li-ion battery has following obvious advantage: 1, adopt polymer dielectric to replace liquid electrolyte solution, effectively can avoid the electrolyte leakage problem that liquid state batteries may exist, the reliability of battery is higher; 2, adopt lightweight soft plastic material to be shell, compared to the liquid state batteries adopting metal shell, can effectively reduce battery case quality on the one hand, improve the quality efficiency of battery, make polymer Li-ion battery have higher specific energy; On the other hand, can effectively reduce because of the internal hematocrit of metal shell tire out not inresponsive, blast under abuse conditions, the probability of the unsafe acts such as burning, make polymer Li-ion battery have better security performance; 3, configuration design flexibly, convenient, can be used for that development is ultra-thin, overlarge area and various Special-shaped battery.
Polymeric matrix conventional in gel polymer electrolyte (GPE) mainly contains the copolymer p (VDF – HFP) etc. of polyethylene glycol oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), Kynoar (PVDF) and Pian Fu Yi Xi – hexafluoropropylene.The ionic conductivity of PEO system GPE 25 DEG C time can reach 10 -3the S/cm order of magnitude.But mechanical property is poor, this mainly by PEO in the electrolytic solution part solvable caused by.It is high that PAN system GPE has conductivity at room temperature, reaches as high as 10 -2s/cm, good flame resistance, oxidation Decomposition voltage advantages of higher; But due to PAN chain containing strong polar group-CN, with metal lithium electrode poor compatibility, serious with lithium electrode interface passivation phenomenon, and PAN crystallinity is strong, and when temperature raises, electrolyte can be separated out.Have a carbonyl side base in MMA unit in PMMA, can produce stronger interaction with the oxygen in carbonates plasticizer, therefore good with compatibility of electrolyte, conductivity at room temperature is high by (10 -3s/cm).PMMA system GPE and metal lithium electrode interface impedance low, interface stability is better.But its mechanical strength is low, impact uses.-CF in PVDF 2be very strong electron withdraw group, therefore, PVDF system GPE has fabulous electrochemical stability.And its dielectric constant high (ε=8.4), contribute to dissociating and the raising of carrier concentration of lithium salts.But its symmetrical configuration, regular, degree of crystallinity is high, is unfavorable for ionic conduction.And (PVDF-HFP) copolymer is for PVDF, degree of crystallinity reduces, and pick up improves.Ionic conductivity can reach 10 -3s/cm.But because the C-F interface in Li and PVDF based polyalcohol can react, form LiF, therefore PVDF base polymer electrolyte is to lithium chemically unstable.Introduced as can be seen from above: often kind of a polymer has its advantage and defect.
The PVDF system Soft Roll polymer Li-ion battery of current industrialization has the advantages such as hardness is high, good cycle, high-temperature storage performance are good.PVDF perforated membrane adopts the pore-creating of Solvent evaporation precipitation phase separation method, be dissolved in organic solvent-acetone by polymer, inorganic oxide particle, and add a certain amount of pore creating material DMC (dimethyl carbonate), in dry process, acetone first volatilizees, volatilize after DMC, after DMC vapors away, leave hole.But, use a large amount of acetone as solvent in said process, easy blast on fire, dangerous.And the cost of raw material high (230 yuan/kg).
Exist in prior art and will be widely used in leather finish, fiber treatment, plastics, the water system self-crosslinking pure-acrylic emulsion (acrylic acid esters co-polymer) in the fields such as anticorrosion, antirust, woodenware, the decoration of exterior wall of metal uses for reference polymer Li-ion battery field, abandoned the use of a large amount of organic solvent, the greenization achieving polymer Li-ion battery is produced.This matrix is used for polymer Li-ion battery tool pick up high, the thermally-stabilised advantage such as good.But found by great many of experiments, described polymer film is the dense film of atresia, and gas permeability is bad, and pick up too high (750wt%), easily cause inside battery both positive and negative polarity to lack electrolyte; And the ionic conductivity of described GPE is on the low side.When being applied to lithium ion soft-package battery, the adhesiveness of anticathode is not high enough (fine to the adhesiveness of positive pole), easily causes battery hardness inadequate, and battery is produced, and polarization is large, cycle performance and the not high enough problem of high rate performance.
Summary of the invention
Technical problem to be solved by this invention is for gel polymer electrolyte ionic conductivity of the prior art problem on the low side, provides a kind of polymer film.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme:
A kind of polymer film is provided, comprises the first polymeric matrix and the second polymer beads of being distributed in described first polymeric matrix and inorganic particle; The glass transition temperature of described first polymeric matrix is less than 40 DEG C, and the glass transition temperature of described second polymer beads is more than 40 DEG C; The glass transition temperature of described polymer film is 30-60 DEG C, and air permeability is 150-600sec/100mL.
Meanwhile, present invention also offers the preparation method of above-mentioned polymer film, comprise the steps:
S1, by the first polymer emulsion and the second polymer emulsion mixing, obtain mixed emulsion; The glass transition temperature of described mixed emulsion is 30-60 DEG C; The glass transition temperature of described first polymer emulsion is less than 40 DEG C, and the glass transition temperature of described second polymer emulsion is more than 40 DEG C;
S2, described mixed emulsion to be mixed with the dispersion liquid containing inorganic particle, obtain coating liquid; In described coating liquid, the total solid content of mixed emulsion and the mass ratio of inorganic particle are: 1:10-10:1.
S3, apply described coating liquid, form liquid film, after solidification, obtain described polymer film; The temperature of described solidification is greater than the glass transition temperature of described first polymer emulsion, is less than the glass transition temperature of described second polymer emulsion.
In addition, present invention also offers a kind of gel electrolyte, the electrolyte comprising foregoing polymer film and be adsorbed in described polymer film.
Further, present invention also offers a kind of polymer battery, comprise positive pole, negative pole, barrier film and foregoing gel electrolyte, described gel electrolyte is between described positive pole and negative pole.
In polymer film provided by the invention, utilize the second polymer beads and inorganic particle mutually to pile up and carry out pore-creating, second polymer beads and inorganic particle can be effectively bonded as one by the first polymeric matrix simultaneously formed by the first polymer emulsion of lower glass transition temperatures, form the polymer film that glass transition temperature is 30-60 DEG C, this polymer film has excellent permeability.The gel electrolyte prepared by this polymer film has excellent ionic conductivity.
Meanwhile, polymer film provided by the invention has excellent high voltage performance.
Accompanying drawing explanation
Fig. 1 is the SEM picture that polymer film Ma2 that the embodiment of the present invention 2 prepares amplifies 10000 times;
Fig. 2 is the Soft Roll SL435573 type LiCoO that the embodiment of the present invention 2 prepares 2the dissection photo of/Graphite polymer battery;
The linear scan curve chart of the gel electrolyte Li/Pt battery that Fig. 3 adopts the polymer film Ma2 of the embodiment of the present invention 2 to prepare;
The Soft Roll SL435573 type LiCoO that Fig. 4 embodiment of the present invention 2 and comparative example 3 prepare 2discharge capacity in/Graphite polymer battery 1C cyclic process is with the variation relation curve chart of cycle-index.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Polymer film provided by the invention comprises the first polymeric matrix and the second polymer beads of being distributed in described first polymeric matrix and inorganic particle; The glass transition temperature of described first polymeric matrix is less than 40 DEG C, and the glass transition temperature of described second polymer beads is more than 40 DEG C; The glass transition temperature of described polymer film is 30-60 DEG C, and air permeability is 150-600sec/100mL.
In the present invention, under preferable case, the glass transition temperature of described first polymeric matrix is more than-70 DEG C and is less than 40 DEG C, and the glass transition temperature of described second polymer beads is 40-70 DEG C.
According to the present invention, above-mentioned first polymeric matrix is obtained by self-crossing emulsion solidification, and in the first polymeric matrix, strand is that three-dimensional network is interconnected.Concrete, the first polymeric matrix described above be selected from the copolymer of acrylate copolymer, copolymer in cinnamic acrylic ester, vinyl chloride-acrylate copolymer, AN-AE, polyurethane, vinylacetate-ethylene one or more.
For above-mentioned second polymer beads, in the present invention, preferably adopt acrylate copolymer particle.Have more excellent ionic conductivity after being prepared into gel electrolyte for making polymer film, under preferable case, the average grain diameter of described second polymer beads is 0.1-1.0 μm.
In the present invention, above-mentioned first polymeric matrix and the second polymer beads can adopt same class polymer, understandable, when the first polymeric matrix and the second polymer beads are same class polymer, as previously mentioned, the glass transition temperature of the first polymeric matrix only need selected is less than 40 DEG C, and the glass transition temperature of the second polymer beads is more than 40 DEG C.
According to the present invention, for above-mentioned inorganic particle, specifically can adopt the various inorganic particles that this area is conventional, such as, described inorganic particle is selected from Al 2o 3, SiO 2, SnO 2, ZrO 2, TiO 2, SiC, Si 3n 4, CaO, MgO, ZnO, BaTiO 3, LiAlO 2, BaSO 4in one or more.For better matching with the second polymer beads, make polymer film have excellent gas permeability, be beneficial to the ionic conductivity improving gel electrolyte, the average grain diameter of described inorganic particle is 0.01-10 μm.
The present inventor before making the present invention, found by great many of experiments, form gel electrolyte after the fine and close swelling electrolyte of self-crosslinking polyacrylates film and in for polymer battery time, with the adhesive property just having excellence, but it is poor with the adhesive property of negative pole, cause battery hardness inadequate, and polarization is large, cycle performance and high rate performance bad.Further, the pick up of above-mentioned polymer film is too high, easily causes inside battery both positive and negative polarity to lack electrolyte.To this, according to the present invention, under preferable case, also containing auxiliary polyalcohol in described polymer film, described auxiliary polyalcohol choosing is containing the acrylate of polystyrene copolymerization unit, containing the acrylate of polybutadiene copolymer unit, containing one or more in the acrylate of polyacrylonitrile copolymerization units by above-mentioned auxiliary polyalcohol, the adhesive property with negative pole can be improved on the one hand, on the other hand, the imbibition ability of polymer film can be reduced, be beneficial to the both positive and negative polarity and electrolyte good contact that keep inside battery, ensure the cycle performance of battery, and ensure that in cyclic process, positive/negative plate is indeformable.
Be understandable that, when the first polymeric matrix and the second polymer beads adopt different materials, its glass transition temperature may be different, and the first corresponding polymeric matrix and the relative amount of the second polymer beads also can there are differences.In the present invention, the relative amount of the first polymeric matrix and the second polymer beads need ensure that the glass transition temperature of polymer film is in 30-60 DEG C, meanwhile, the relative amount of the first polymeric matrix, the second polymer beads and inorganic particle need ensure that the air permeability of the polymer film obtained is 150-600sec/100mL.When meeting above-mentioned performance, the relative amount of the first polymeric matrix, the second polymer beads and inorganic particle can change in a big way.
In the present invention, under preferable case, the gross mass of the first polymeric matrix and the second polymer beads and the mass ratio of inorganic particle are: 1:10-10:1.As previously mentioned, when also containing auxiliary polyalcohol in polymer film, the gross mass of the first polymeric matrix, the second polymer beads, auxiliary polyalcohol and the mass ratio of inorganic particle are: 1:10-10:1.Meanwhile, in described polymer film, the volume fraction of described second polymer beads is 40-90vol%.
As previously mentioned, when in polymer film simultaneously containing auxiliary polyalcohol, during pick up for reducing polymer film, for ensureing the chemical property of the battery finally prepared, under preferable case, the addition of auxiliary polyalcohol is as the criterion for 40-380wt% to make the pick up of described polymer film.
According to the present invention, in described polymer film, dispersant can also be contained.Above-mentioned dispersant is water-soluble polymer dispersant.Comprise ionic (polyelectrolyte) and nonionic two class.Ionic dispersant used is polycarboxylic acid dispersant, its by (as acrylic acid, the maleic anhydride etc.) homopolymerization of carboxylic vinyl monomer or with other monomer copolymerizations, the esterification of rear alkali neutralized alcohol obtains.Specifically comprise: polyacrylic acid (PAA), polymine (PEI), softex kw (CTAB), polyamide, polyacrylamide (PAM), acrylic acid-acrylic ester analog copolymer, the copolymer [P (AA/AM)] of acrylic acid-acrylamide, the copolymer of ammonium acrylate-esters of acrylic acid, styrene-maleic anhydride copolymer (SMA), Styrene-acrylic copolymer, acrylic acid-maleic anhydride copolymer, maleic anhydride-acrylamide copolymer etc.
Non-ionic dispersing agent used comprises polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), AEO (JFC) etc.The weight average molecular weight of described polymer is 100-500000g/mol, preferred 1000-100000g/mol.
The content of above-mentioned dispersant can change in a big way, and such as, the content of dispersant is the 0.05-10wt% of inorganic particle quality, and preferred 0.1-6wt%, more excellent selects 0.1-2wt%.
Meanwhile, in the present invention, in described polymer film, surfactant can also be contained.Above-mentioned surfactant can be lauryl sodium sulfate (SDS), the neopelex (SDBS) of anionic, dioctyl succinate disulfonate acid, sodium glycocholate, sodium sulfate of polyethenoxy ether of fatty alcohol (AES), aliphatic alcohol polyethenoxy ammonium sulfate (AESA).Or above-mentioned surfactant also can be the AEO (as AEO9), APES (as OP-10), NPE (as TX-10), alkyl, polyether etc. of nonionic.In the present invention, the content of described surfactant can change in a big way, and such as, the content of surfactant is the 0.05-10wt% of inorganic particle quality, and preferred 0.1-5wt%, more excellent selects 0.1-2wt%.
In addition, thickener can also be contained in described polymer film.Described thickener can be thickener conventional in prior art, such as, comprise synthesis high score subclass PAA, PEO, PVA, PVP, PAM, acrylic acid-acrylic ester class copolymer emulsion, polyurethane thickener and cellulose family methylcellulose, sodium carboxymethylcellulose (CMC), hydroxyethylcellulose, hydroxypropyl methylcellulose etc.Under preferable case, the weight average molecular weight of described thickener is 1000-2000000g/mol, is more preferably 100000-1000000g/mol.The content of described thickener can change in a big way, and such as, the addition of thickener is the 0.05-10wt% of inorganic particle quality, and preferred 0.1-5wt%, more excellent selects 0.1-2wt%.
Meanwhile, present invention also offers the preparation method of above-mentioned polymer film, comprise the steps:
S1, by the first polymer emulsion and the second polymer emulsion mixing, obtain mixed emulsion; The glass transition temperature of described mixed emulsion is 30-60 DEG C; The glass transition temperature of described first polymer emulsion is less than 40 DEG C, and the glass transition temperature of described second polymer emulsion is more than 40 DEG C;
S2, described mixed emulsion to be mixed with the dispersion liquid containing inorganic particle, obtain coating liquid; In described coating liquid, the total solid content of mixed emulsion and the mass ratio of inorganic particle are: 1:10-10:1.
S3, apply described coating liquid, form liquid film, after solidification, obtain described polymer film; The temperature of described solidification is greater than the glass transition temperature of described first polymer emulsion, is less than the glass transition temperature of described second polymer emulsion.
According to the present invention, the latex particle in the first polymer emulsion is used for after the drying, softening transform occurs, the latex particle in the second polymer emulsion and inorganic particle is bonded as one.Concrete, in the present invention, the glass transition temperature of described first polymer emulsion is less than 40 DEG C, under preferable case, and the glass transition temperature of the first polymer emulsion is more than-70 DEG C and is less than 40 DEG C.
In the present invention, above-mentioned first polymer emulsion be selected from self-crosslinking pure-acrylic emulsion (acrylate copolymer), self-crosslinking styrene-acrylic copolymer emulsion (styrene and acrylate copolymer), self-crosslinking chlorine acrylic emulsion (vinyl chloride and acrylate copolymer), self-crosslinking acrylonitrile compolymer emulsion (acrylonitrile and acrylate copolymer), self-crosslinkable polyurethane emulsion, EVA emulsion (ethene and vinyl acetate co-polymer) one or more.The above-mentioned various emulsion of glass transition temperature in aforementioned range is commonly known in the art, and such as, self-crosslinking pure-acrylic emulsion can be P1005 (T g=-18 DEG C) or P1020 (T g=38 DEG C); Self-crosslinking acrylonitrile compolymer emulsion can be P850 (T g=-15 DEG C) and A1030 (T g=28 DEG C); Self-crosslinking styrene-acrylic copolymer emulsion can be A202 (T g=-20 DEG C), S601 (T g=30 DEG C), S606 (T g=40 DEG C), A206 (T g=-20 DEG C), A400 (T g=-8 DEG C) or A402 (T g=-8 DEG C); Self-crosslinking chlorine acrylic emulsion can be C056 (T g=10 DEG C) (above emulsion is all from Shanghai Ai Gao Chemical Co., Ltd.).Usually, the glass transition temperature T of commercially available self-crosslinking EVA emulsion gfor-3 ~ 7 DEG C.And the T of commercially available self-crosslinkable polyurethane emulsion gbe generally-62 DEG C.
The first polymer emulsion adopted in the present invention is self-crossing emulsion, and the polymer segment in follow-up dry solidification process in emulsion after polymerization can occur, thus forms three-dimensional network-like structure, is beneficial to the thermal stability and mechanical performance that improve gained film.
Latex particle in above-mentioned second polymer emulsion still keeps its shape after the drying, for inorganic particle acting in conjunction, formed hole, give polymer film with the permeability of excellence, be beneficial to raising ionic conductivity.In the present invention, the glass transition temperature of described second polymer emulsion is more than 40 DEG C.Under preferable case, the glass transition temperature of described second polymer emulsion is 40-70 DEG C.
Glass transition temperature is that second polymer emulsion of 40-70 DEG C can be selected from self-crosslinking pure-acrylic emulsion (acrylic acid esters co-polymer) of the prior art.It should be noted that the second polymer emulsion can adopt the emulsion identical with the first polymer emulsion kind, but the glass transition temperature of the two is different, such as, the second polymer emulsion can adopt self-crosslinking pure-acrylic emulsion P1040 (T g=60 DEG C, Shanghai Ai Gao Chemical Co., Ltd.).
For above-mentioned second polymer emulsion, under preferable case, the average grain diameter of latex particle is wherein 0.1-1.0 μm.
According to the present invention, in above-mentioned steps S1, when the first polymer emulsion mixes with the second polymer emulsion, the relative amount of the two need ensure that the glass transition temperature of the mixed emulsion obtained is 30-60 DEG C.The glass transition temperature of above-mentioned mixed emulsion is used for the vitrification point of the polymer of film forming and obtains by theory calculate, circular is known in those skilled in the art, is not described in detail in the present invention.
Under preferable case, in described mixed emulsion, the addition of described second polymer emulsion is as the criterion for 40-90vol% to make the volume fraction of the second polymer beads in the polymer film for preparing.
In the present invention, by adopting above-mentioned second polymer emulsion and the first polymer emulsion and inorganic particle acting in conjunction, effectively can improve the permeability of the polymer film prepared, greatly improving its ionic conductivity.Simultaneously, due to the existence of the latex particle of the high glass-transition temperature in the second polymer emulsion, and that the cause problem of polymer film adhesive property extreme difference excessive due to inorganic particle amount can be avoided, and that the cause problem of permeability difference excessive due to the first polymer emulsion amount can be avoided simultaneously.
In the present invention, for improve the polymer film for preparing make gel electrolyte after with the adhesive property of both positive and negative polarity (mainly negative pole) and the absorbent improving polymer film, under preferable case, in described step S1, comprise auxiliary polyalcohol emulsion to mix with the first polymer emulsion, the second polymer emulsion and jointly mix, obtain described mixed emulsion.
Described auxiliary polyalcohol emulsion be selected from the acrylic acid ester emulsion containing polystyrene copolymerization unit, the acrylic acid ester emulsion containing polybutadiene copolymer unit, containing one or more in the acrylic acid ester emulsion of polyacrylonitrile copolymerization units.What above-mentioned auxiliary polyalcohol emulsion can ensure the gel electrolyte that formed by this polymer film and both positive and negative polarity on the one hand has effective adhesive, and can be reduced in suitable scope by the pick up of polymer film, guarantee both positive and negative polarity fully can contact with electrolyte simultaneously.
According to the present invention, for above-mentioned mixed emulsion, under preferable case, except meet aforesaid first polymer emulsion mix with the second polymer emulsion time, the two relative amount need ensure that the glass transition temperature of the mixed emulsion obtained is 30-60 DEG C, the addition of described second polymer emulsion with outside the condition making the volume fraction of the second polymer beads in the polymer film for preparing and be as the criterion for 40-90vol%, the addition of described auxiliary polyalcohol emulsion is as the criterion for 40-380wt% to make the pick up of the polymer film prepared.
Those skilled in the art can according to selected different material, adjusts the first polymer emulsion, relative amount between the second polymer emulsion and auxiliary polyalcohol emulsion, to meet above-mentioned requirements.Understandable, due to the nature difference between each material, when adopting different material, first polymer emulsion, relative amount between the second polymer emulsion and auxiliary polyalcohol emulsion can be different, and are that those skilled in the art grasped by the relation with contents between the above-mentioned three kinds of materials of adjustment to meet aforesaid condition.
According to the present invention, need to provide the dispersion liquid containing inorganic particle simultaneously.Concrete, also comprise before described step S2 and first dispersant solution being mixed with inorganic particle, obtain the dispersion liquid containing inorganic particle.
Described dispersant is water-soluble polymer dispersant, specifically comprises ionic (polyelectrolyte) and nonionic two class.
Ionic dispersant used is polycarboxylic acid dispersant, its by (as acrylic acid, the maleic anhydride etc.) homopolymerization of carboxylic vinyl monomer or with other monomer copolymerizations, the esterification of rear alkali neutralized alcohol obtains.Comprise: polyacrylic acid (PAA), polymine (PEI), softex kw (CTAB), polyamide, polyacrylamide (PAM), acrylic acid-acrylic ester analog copolymer, the copolymer [P (AA/AM)] of acrylic acid-acrylamide, the copolymer of ammonium acrylate-esters of acrylic acid, styrene-maleic anhydride copolymer (SMA), Styrene-acrylic copolymer, acrylic acid-maleic anhydride copolymer, maleic anhydride-acrylamide copolymer etc.
Described non-ionic dispersing agent comprises polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), AEO (JFC) etc.The weight average molecular weight of described polymer is 100-500000g/mol, preferred 1000-100000g/mol.
In the present invention, in described dispersant solution, the concentration of dispersant is 0.01%-10wt%, and preferred 0.05%-5wt%, more excellent selects 0.1%-2wt%.
When adopted ionic dispersant is anionic polymer (as PAM); dispersant solution is adjusted to pH=8-9; anionic polymer can be made to dissociate completely, thus inorganic particle is effectively protected, inorganic particle is stably dispersed in aqueous phase.
When adopted ionic dispersant is that cation type polymer is (as PEI; CTAB) time, dispersant solution is adjusted to pH=4-5, cation type polymer can be made to dissociate well; thus inorganic particle is effectively protected, make it stably be dispersed in aqueous phase.When adopted dispersant is non-ionic polyalcohol dispersant, do not regulate the pH value of solution.
As known in the art, by hydrochloric acid (HCl) or ammoniacal liquor (NH 3h 2o) pH value of dispersant solution is regulated.
For above-mentioned inorganic particle, be not particularly limited in the present invention, can adopt various inorganic particle well known in the art, such as described inorganic particle is selected from Al 2o 3, SiO 2, SnO 2, ZrO 2, TiO 2, SiC, Si 3n 4, CaO, MgO, ZnO, BaTiO 3, LiAlO 2, BaSO 4in one or more.For better coordinating with the latex particle in aforesaid second polymer emulsion, to form loose structure, the average grain diameter of described inorganic particle is 0.01-10 μm.
In the present invention, the addition of described dispersant is the 0.05-10wt% of described inorganic particle quality, is preferably 0.1-6wt%, is more preferably 0.1-2wt%.
According to the present invention, after dispersant solution is mixed with inorganic particle, preferably stirring at low speed 1-30min under 50-1000rpm rotating speed, then under 1100-8000rpm rotating speed high-speed stirred 1-30min.After above-mentioned first stirring at low speed-high-speed stirred, inorganic particle can be made evenly stable dispersion.
In the present invention, when described dispersant solution be pH value is the anionic dispersing agent solution of 8-9, also comprises in described step S1 and the pH value of described mixed emulsion is adjusted to 8-9.Similar, when the cationic dispersing agent solution of described dispersant solution to be pH value be 4-5, also comprise in described step S1 and the pH value of described mixed emulsion is adjusted to 4-5.And when dispersant solution is non-ionic polyalcohol dispersant, without the need to regulating the pH value of mixed emulsion in described step S1.
According to the present invention, provide above-mentioned mixed emulsion and containing inorganic particle dispersion liquid after, described mixed emulsion is mixed with the dispersion liquid containing inorganic particle, obtains coating liquid.
During mixing, in described coating liquid, the total solid content of mixed emulsion and the mass ratio of inorganic particle are: 1:10-10:1.
Under preferable case, in described step S2, comprise and surfactant and/or thickener and mixed emulsion, dispersion liquid containing inorganic particle are mixed.
Described surfactant is lauryl sodium sulfate (SDS), the neopelex (SDBS) of anionic, dioctyl succinate disulfonate acid, sodium glycocholate, sodium sulfate of polyethenoxy ether of fatty alcohol (AES), aliphatic alcohol polyethenoxy ammonium sulfate (AESA).The AEO (as AEO9) of nonionic, APES (as OP-10), NPE (as TX-10), alkyl, polyether etc.The addition of described surfactant is the 0.05-10wt% of described inorganic particle addition, is preferably 0.1-5wt%, is more preferably 0.1-2wt%.
Described thickener comprises synthesis high score subclass PAA, PEO, PVA, PVP, PAM, acrylic acid-acrylic ester class copolymer emulsion, polyurethane thickener and cellulose family methylcellulose, sodium carboxymethylcellulose (CMC), hydroxyethylcellulose, hydroxypropyl methylcellulose etc.The weight average molecular weight of described thickener is 1000-2000000g/mol, and more excellent selects 100000-1000000g/mol.The addition of described thickener is the 0.05-10wt% of described inorganic particle addition, is preferably 0.1-5wt%, is more preferably 0.1-2wt%.
In described step S2, after above-mentioned surfactant and/or thickener and mixed emulsion, dispersion liquid containing inorganic particle being mixed, be also included in high-speed stirred 1-30min under 1100-8000rpm rotating speed, then under 50-1000rpm rotating speed stirring at low speed 1-30min.By above-mentioned stir process, each particle in the coating liquid obtained can be made evenly stable dispersion.
According to the present invention, as described in step S3, also comprise coating described coating liquid, formed liquid film, through solidification after obtain described polymer film; The temperature of described solidification is greater than the glass transition temperature of described first polymer emulsion, is less than the glass transition temperature of described second polymer emulsion.
Such as, coating liquid is applied on lithium ion battery general barrier film side, the general barrier film both sides of lithium ion battery, lithium ion battery positive plate, negative electrode for lithium ion battery sheet and PTFE plate with certain thickness, after drying, forms polymer film E1, E2, E3, E4 and E5.
In the preparation method of above-mentioned polymer film provided by the invention, adopt comprise the first polymer emulsion of lower glass transition temperatures, high glass-transition temperature the second polymer emulsion, containing or the mixed emulsion of auxiliary polyalcohol emulsion that do not contain, suitably reduce the pick up of the polymer film obtained, improve the viscosity of anticathode, improve the hardness of battery, play partly pore-creating effect simultaneously.Meanwhile, by above-mentioned mixed emulsion with containing inorganic particle dispersion liquid with the use of, prepare coating liquid.
After dry solidification, the latex particle of the second polymer emulsion coordinates pore-creating with inorganic particle, gives the permeability of polymer film excellence, is beneficial to raising ionic conductivity, and can overcome that battery polarization is large, the problem of circulation and high rate performance difference.
In coating liquid, there is the first latex particle of the first polymer emulsion, the second latex particle of the second polymer emulsion, because the first latex particle glass transition temperature is low, in follow-up dry solidification process, there is softening or deformation in the first latex particle.Because the second latex particle glass transition temperature is high, in follow-up dry solidification process, the second latex particle still keeps original shape.
In the process of air drying, moisture volatilizees gradually, and the second latex particle still keeps its shape after air drying, thus forms hole between the second latex particle and inorganic particle.And softening or deformation occur the first latex particle, the second latex particle and inorganic particle are combined as a whole, the hole between filling second latex particle and inorganic particle can be avoided simultaneously to a certain extent, thus ensure that polymer film has excellent permeability.Meanwhile, the polymer film prepared by said method has excellent high voltage performance.
Meanwhile, present invention also offers a kind of gel electrolyte, the electrolyte comprising foregoing polymer film and be adsorbed in described polymer film.
The method adopting polymer film to prepare gel electrolyte is known, such as, can adopt polymer film Electolyte-absorptive and swelling, can obtain gel electrolyte.Concrete, after aforesaid polymer film E5 is cut into suitable size, at 25 DEG C after vacuumize 10-30h, transfer to rapidly in glove box (water and oxygen content be less than 3ppm).Polymer film is soaked in the electrolytic solution after 24h, gel electrolyte F5 can be obtained.
Meanwhile, present invention also offers a kind of polymer battery, comprise positive pole, negative pole, barrier film and gel electrolyte as above, described gel electrolyte is between described positive pole and negative pole.
The preparation method of above-mentioned polymer battery is known in the field, such as, is specifically as follows:
In drying shed, separate based lithium-ion battery positive plate and negative plate (takeup type or stacked) with aforesaid polymer film E1, the coat side wherein on polymer film E1, towards positive pole, adds electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, is designated as F1 (P).
In drying shed, separate based lithium-ion battery positive plate and negative plate (takeup type or stacked) with polymer film E1, the coat side wherein on polymer film E1, towards negative pole, adds electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, is designated as F1 (N).
In drying shed, separate based lithium-ion battery positive plate and negative plate (takeup type or stacked) with polymer film E2, add electrolyte, seal into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, is designated as F2.
In drying shed, separate the polymer film E3 and negative plate (takeup type or stacked) that comprise positive pole with the general barrier film of lithium ion battery, add electrolyte, seal into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, is designated as F3 (P).
In drying shed, separate positive plate with the general barrier film of lithium ion battery and comprise the polymer film E4 (takeup type or stacked) of negative pole, adding electrolyte, seal into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, is designated as F4 (N).
According to the present invention, the general barrier film of described lithium ion battery comprises PP barrier film, PE barrier film and PE/PP/PE tri-layers of barrier film etc.
Described positive plate is by for the positive electrode of lithium ion battery and conductive agent, and binding agent furnishing slurry is coated on aluminium foil and made.Positive electrode used comprises the positive electrode that can be used for arbitrarily lithium ion battery, as cobalt-lithium oxide (LiCoO 2), nickel oxide lithium (LiNiO 2), manganese oxide lithium (LiMn 2o 4), LiFePO 4 (LiFePO 4), ternary composite cathode material and transformed lines show etc. thereof.
Described negative plate is by for the negative material of lithium ion battery and conductive agent, and binding agent furnishing slurry is coated on Copper Foil and made.Negative material used comprises the negative material that can be used for arbitrarily lithium ion battery, as graphite, soft carbon, hard carbon etc.
In the present invention, described electrolyte is made up of electrolyte lithium salt and organic solvent.Electrolyte lithium salt can select lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiClO 4), LiBF4 (LiBF 4) etc.Organic solvent can select ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC), vinylene carbonate (VC) etc.Organic solvent can be binary, ternary or even polynary.Electrolyte lithium salt concentration is in organic solvent 0.8-1.5mol/L.
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, be that the PAM of 10000g/mol is dissolved in the water by weight average molecular weight, form the aqueous solution of 0.6wt%, then use NH 3h 2solution is adjusted to pH=8-9 by O, forms dispersant solution.
2, at rotating speed be 800rpm mechanical agitation under by α-Al 2o 3(100wt%, 300nm) slowly joins in the dispersant solution that enough steps 1 obtain, and makes dispersant PAM relative to α-Al 2o 3mass ratio be 1.2wt%.Then, first stir 15min with the rotating speed low-speed machinery of 800rpm, then stir 15min with the rotating speed high speed machine of 4000rpm.Form the dispersion liquid containing inorganic particle.
3, the second polymer emulsion P1040 (T of high glass-transition temperature will be had g=60 DEG C, solid content 50wt%), there is the first polymer emulsion P1005 (T of lower glass transition temperatures g=-18 DEG C, solid content 50wt%), S601 (T g=30 DEG C, solid content 50wt%) mix with the volume ratio of 9:1:10, and be adjusted to pH=8-9, form mixed emulsion.Polymer film after being cast is designated as M1.The calculated value of its glass transition temperature is 40 DEG C, and the second polymer emulsion P1040 is 45% relative to the volume fraction of total emulsion.
4, will relative to α-Al 2o 3mass ratio is that the surfactant SDS of 1wt%, solid content are relative to α-Al 2o 3mass ratio be 9:1 mixed emulsion and relative to α-Al 2o 3mass ratio be the thickener PAM (weight average molecular weight is 500000g/mol) of 0.3wt% join that step 2 obtains successively containing in the dispersion liquid of inorganic particle.Then, first stir 15min with the rotating speed high speed machine of 4000rpm, then stir 15min with the rotating speed low-speed machinery of 800rpm, namely form coating liquid.
5, coating liquid is applied on PE barrier film both sides and PTFE plate, at 25 DEG C after dry 24h, obtains the polymer film Mb1 on polymer film Ma1 and PTFE on PE film respectively.The thickness of Ma1 is (1+1) μm, and the thickness of Mb1 is 10.6 μm.
6, polymer film Ma1 is cut into suitable size according to the requirement that battery is assembled, at 25 DEG C after vacuum bakeout 12h, vacuum buffer memory.By LiCoO 2(100wt%), binding agent PVDF (0.8wt%) and carbon black (0.5wt%) furnishing slurry are coated on aluminium foil and are made positive plate (LiCoO 2).By Graphite (100wt%), binding agent SBR (2wt%) and thickener CMC (1.2wt%) furnishing slurry are coated on Copper Foil and are made negative plate (Graphite), in drying shed, separate LiCoO with polymer film Ma1 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery.
Embodiment 2
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, the concentration of dispersant solution used is 0.8wt%, and all the other are all identical with embodiment 1.Obtain dispersant solution.
2, dispersant PAM is relative to α-Al 2o 3mass ratio be 0.8wt%, all the other are all identical with embodiment 1, obtain the dispersion liquid containing inorganic particle.
3, the volume ratio of the second polymer emulsion P1040, first polymer emulsion P1005, S601 is 65:1:34, and all the other are all identical with embodiment 1, obtain mixed emulsion, and the polymer film after being cast is designated as M2.The calculated value of its glass transition temperature is 48 DEG C, and the second polymer emulsion P1040 is 65% relative to the volume fraction of total emulsion.
4, SDS is relative to α-Al 2o 3mass ratio 0.5wt%, the solid content of mixed emulsion used is relative to α-Al 2o 3mass ratio is 5:5, and the weight average molecular weight of thickener PAM used is 400000g/mol, and thickener PAM used is relative to α-Al 2o 3mass ratio is 0.5wt%.All the other are all identical with embodiment 1, obtain coating liquid.
5, identical with embodiment 1, obtain the polymer film Mb2 on polymer film Ma2 and PTFE on PE film respectively, the thickness of Ma2 is (1+1) μm, and the thickness of Mb2 is 12.0 μm.
6, in drying shed, LiCoO is separated with polymer film Ma2 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer Li-ion battery.All the other steps are all identical with embodiment 1.
Embodiment 3
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, the concentration of dispersant solution used is 1.0wt%, and all the other are all identical with embodiment 1, obtain dispersant solution.
2, dispersant PAM used is relative to α-Al 2o 3mass ratio be 0.5wt%, all the other are all identical with embodiment 1, obtain the dispersion liquid containing inorganic particle.
3, the volume ratio of the second polymer emulsion P1040, first polymer emulsion P1005, S601 is 85:1:14, all the other are all identical with embodiment 1, obtain mixed emulsion, polymer film after being cast is designated as M3, the calculated value of its glass transition temperature is 54 DEG C, and the second polymer emulsion P1040 is 85% relative to the volume fraction of total emulsion.
4, SDS used is relative to α-Al 2o 3mass ratio 0.8wt%, the solid content of mixed emulsion used is relative to α-Al 2o 3mass ratio is 1:9, and the weight average molecular weight of thickener PAM used is 100000g/mol, and thickener PAM used is relative to α-Al 2o 3mass ratio is 1wt%, and all the other are all identical with embodiment 1, obtain coating liquid.
5, identical with embodiment 1, obtain the polymer film Mb3 on polymer film Ma3 and PTFE on PE film respectively, the thickness of Ma3 is (1+1) μm, and the thickness of Mb3 is 13.1 μm.
6, in drying shed, LiCoO is separated with polymer film Ma3 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer Li-ion battery, all the other are all identical with embodiment 1.
Embodiment 4
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, be that the PVA of 80000g/mol is dissolved in the water by weight average molecular weight, form 0.4wt% dispersant solution.
2, at rotating speed be 800rpm mechanical agitation under by SnO 2(100wt%, 200nm) slowly joins in the dispersant solution that enough steps 1 obtain, and makes dispersant PVA relative to SnO 2mass ratio be 0.4wt%.Then, first stir 15min with the rotating speed low-speed machinery of 800rpm, then stir 15min with the rotating speed high speed machine of 4000rpm.Form the dispersion liquid containing inorganic particle.
3, the second polymer emulsion P1040 (T of high glass-transition temperature will be had g=60 DEG C, solid content 50wt%), there is the first polymer emulsion P850 (T of lower glass transition temperatures, low pick up g=-15 DEG C, solid content 50wt%), S601 (T g=30 DEG C, solid content 50wt%) mix with the volume ratio of 9:1:10, form mixed emulsion.Polymer film after being cast is designated as M4, and the calculated value of its glass transition temperature is 40 DEG C, and the second polymer emulsion P1040 is 45% relative to the volume fraction of total emulsion.
4, will relative to SnO 2mass ratio is that the Surfactant OP-10 of 0.3wt%, solid content are relative to SnO 2mass ratio be 1:9 mixed emulsion and relative to SnO 2mass ratio be the thickener CMC (weight average molecular weight is 700000g/mol) of 0.3wt% join that step 2 obtains successively containing in the dispersion liquid of inorganic particle.Then, first stir 15min with the rotating speed high speed machine of 4000rpm, then stir 15min with the rotating speed low-speed machinery of 800rpm, namely form coating liquid.
5, be applied to by coating liquid on PE barrier film both sides and PTFE plate, at 25 DEG C after dry 24h, obtain the polymer film Mb4 on polymer film Ma4 and PTFE on PE film respectively, the thickness of Ma4 is (1+1) μm, and the thickness of Mb4 is 10.1 μm.
6, in drying shed, LiCoO is separated with polymer film Ma4 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, all the other are all identical with embodiment 1.
Embodiment 5
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, the concentration of dispersant solution used is 0.9wt%, and all the other are all identical with embodiment 4, obtain dispersant solution.
2, dispersant PVA used is relative to SnO 2mass ratio be 0.6wt%, all the other are all identical with embodiment 4, obtain the dispersion liquid containing inorganic particle.
3, the volume ratio of the second polymer emulsion P1040 used, first polymer emulsion P850, S601 is 65:1:34, all the other are all identical with embodiment 4, obtain mixed emulsion, polymer film after being cast is designated as M5, the calculated value of its glass transition temperature is 48 DEG C, and the second polymer emulsion P1040 is 65% relative to the volume fraction of total emulsion.
4, OP-10 used is relative to SnO 2mass ratio 0.6wt%, the solid content of mixed emulsion used is relative to SnO 2mass ratio is 5:5, and the weight average molecular weight of thickener CMC used is 250000g/mol, and thickener CMC used is relative to SnO 2mass ratio is 0.6wt%.All the other are all identical with embodiment 4, obtain coating liquid.
5, identical with embodiment 4, obtain the polymer film Mb5 on polymer film Ma5 and PTFE on PE film respectively, the thickness of Ma5 is (1+1) μm, and the thickness of Mb5 is 12.7 μm.
6, in drying shed, LiCoO is separated with polymer film Ma5 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, all the other are all identical with embodiment 4.
Embodiment 6
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, the concentration of dispersant solution used is 0.7wt%, and all the other are all identical with embodiment 4, obtain dispersant solution.
2, dispersant PVA used is relative to SnO 2mass ratio be 1.0wt%, all the other are all identical with embodiment 4, obtain the dispersion liquid containing inorganic particle.
3, the volume ratio of the second polymer emulsion P1040, first polymer emulsion P850, S601 is 85:1:14, all the other are all identical with embodiment 4, obtain mixed emulsion, polymer film after being cast is designated as M6, the calculated value of its glass transition temperature is 55 DEG C, and the second polymer emulsion P1040 is 85% relative to the volume fraction of total emulsion.
4, OP-10 used is relative to SnO 2mass ratio 0.9wt%, the solid content of mixed emulsion used is relative to SnO 2mass ratio is 9:1, and the weight average molecular weight of thickener CMC used is 250000g/mol, and thickener CMC used is relative to SnO 2mass ratio is 0.8wt%.All the other are all identical with embodiment 4, obtain coating liquid.
5, identical with embodiment 4, obtain the polymer film Mb6 on polymer film Ma6 and PTFE on PE film respectively, the thickness of Ma6 is (1+1) μm, and the thickness of Mb6 is 11.8 μm.
6, in drying shed, LiCoO is separated with polymer film Ma6 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, all the other are all identical with embodiment 4.
Embodiment 7
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, be that the PEG of 10000g/mol is dissolved in the water by weight average molecular weight, form the dispersant solution of 0.6wt%.
2, at rotating speed be 800rpm mechanical agitation under by γ-Al 2o 3(100wt%, 400nm) slowly joins in the aqueous dispersant that enough steps 1 obtain, and makes dispersant PEG relative to γ-Al 2o 3mass ratio be 0.3wt%.Then, first stir 15min with the rotating speed low-speed machinery of 800rpm, then stir 15min with the rotating speed high speed machine of 4000rpm, obtain the dispersion liquid containing inorganic particle.
3, the second polymer emulsion P1040 (T of high glass-transition temperature will be had g=60 DEG C, solid content 50wt%), there is lower glass transition temperatures and anticathode has the first polymer emulsion A202 (T of high viscosity g=-20 DEG C, solid content 55wt%), S601 (T g=30 DEG C, solid content 50wt%) mix with the volume ratio of 9:1:10, form mixed emulsion, the polymer film after being cast is designated as M7.The calculated value of its glass transition temperature is 40 DEG C, and the second polymer emulsion P1040 is 45% relative to the volume fraction of total emulsion.
4, will relative to γ-Al 2o 3mass ratio is that the AE09 of 0.5wt%, solid content are relative to γ-Al 2o 3mass ratio be 5:5 mixing latex and relative to γ-Al 2o 3mass ratio be the thickener PEO (weight average molecular weight is 600000g/mol) of 0.5wt% join that step 2 obtains successively containing in the dispersion liquid of inorganic particle.Then, first stir 15min with the rotating speed high speed machine of 4000rpm, then stir 15min with the rotating speed low-speed machinery of 800rpm, namely form coating liquid.
5, be applied to by coating liquid on PE barrier film both sides and PTFE plate, at 25 DEG C after dry 24h, obtain the polymer film Mb7 on polymer film Ma7 and PTFE on PE film respectively, the thickness of Ma7 is (1+1) μm, and the thickness of Mb7 is 10.3 μm.
6, in drying shed, LiCoO is separated with polymer film Ma7 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, all the other are all identical with embodiment 1.
Embodiment 8
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, the concentration of dispersant solution used is 0.9wt%, and all the other are all identical with embodiment 7, obtain dispersant solution.
2, dispersant PEG used is relative to γ-Al 2o 3mass ratio be 0.7wt%, all the other are all identical with embodiment 7, obtain the dispersion liquid containing inorganic particle.
3, the volume ratio of the second polymer emulsion P1040, first polymer emulsion A202, S601 is 65:1:34, and all the other are all identical with embodiment 7, obtain mixed emulsion, and the film after being cast is designated as M8.The calculated value of its glass transition temperature is 48 DEG C, and the second polymer emulsion P1040 is 65% relative to the volume fraction of total emulsion.
4, AE09 used is relative to γ-Al 2o 3mass ratio 0.7wt%, the solid content of mixed emulsion used is relative to γ-Al 2o 3mass ratio is 9:1, and the weight average molecular weight of thickener PEO used is 900000g/mol, and thickener PEO used is relative to γ-Al 2o 3mass ratio is 0.3wt%.All the other are all identical with embodiment 7, obtain coating liquid.
5, identical with embodiment 7, obtain the polymer film Mb8 on polymer film Ma8 and PTFE on PE film respectively, the thickness of Ma8 is (1+1) μm, and the thickness of Mb8 is 12.9 μm.
6, in drying shed, LiCoO is separated with polymer film Ma8 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery, all the other are all identical with embodiment 7.
Embodiment 9
The present embodiment is for illustration of polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, the concentration of dispersant solution used is 0.5wt%, and all the other are all identical with embodiment 7, obtain dispersant solution.
2, dispersant PEG used is relative to γ-Al 2o 3mass ratio be 1.1wt%, all the other are all identical with embodiment 7, obtain the dispersion liquid containing inorganic particle.
3, the volume ratio of the second polymer emulsion P1040, first polymer emulsion A202, S601 is 85:1:14, and all the other are all identical with embodiment 7, obtain mixed emulsion, and the film after being cast is designated as M9.The calculated value of its glass transition temperature is 54 DEG C, and the second polymer emulsion P1040 is 85% relative to the volume fraction of total emulsion.
4, AE09 used is relative to γ-Al 2o 3mass ratio 1wt%, the solid content of mixed emulsion used is relative to γ-Al 2o 3mass ratio is 1:9, and the weight average molecular weight of thickener PEO used is 400000g/mol, and thickener PEO used is relative to γ-Al 2o 3mass ratio is 0.9wt%.All the other are all identical with embodiment 7, obtain coating liquid.
5, identical with embodiment 7, obtain the polymer film Mb9 on polymer film Ma9 and PTFE on PE film respectively, the thickness of Ma9 is (1+1) μm, and the thickness of Mb9 is 9.9 μm.
6, in drying shed, LiCoO is separated with polymer film Ma9 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery.All the other are all identical with embodiment 7.
Comparative example 1
This comparative example is used for comparative illustration polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, employing glass transition temperature is the pure-acrylic emulsion P1020 (solid content 50wt%) of 38 DEG C, its cast membrane is designated as R1, be applied on PE barrier film both sides and PTFE plate, 24h is toasted at 50 DEG C, obtain the polymer film Rb1 of the densification on the polymer film Ra1 of the densification on PE barrier film and PTFE plate, the thickness of Ra1 is (1+1) μm, and the thickness of Rb1 is 12.3 μm.
2, the polymer film Ra1 film of densification is cut into suitable size according to the requirement that battery is assembled, at 50 DEG C after vacuum bakeout 12h, vacuum buffer memory.By LiCoO 2(100wt%), binding agent PVDF (0.8wt%) and carbon black (0.5wt%) furnishing slurry are coated on aluminium foil and are made positive plate (LiCoO 2).By Graphite (100wt%), binding agent SBR (2wt%) and thickener CMC (1.2wt%) furnishing slurry are coated on Copper Foil and are made negative plate (Graphite), in drying shed, separate LiCoO with polymer film Ra1 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery.
Comparative example 2
This comparative example is used for comparative illustration polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, identical with embodiment 1, form the aqueous solution of 0.6wt% dispersant PAM.
2, identical with embodiment 1, formed containing inorganic particle α-Al 2o 3dispersion liquid.
3, be that the P1020 (solid content 50wt%) of 38 DEG C is adjusted to pH=8-9 by glass transition temperature.Its cast membrane is designated as R2.
4, identical with embodiment 1, form coating liquid.
5, coating liquid is applied on PE barrier film both sides and PTFE plate, 24h is toasted at 50 DEG C, obtain the polymer film Rb2 of the densification on the polymer film Ra2 of the densification on PE barrier film and PTFE plate, the thickness of Ra2 is (1+1) μm, and the thickness of Rb2 is 10.9 μm.
6, the polymer film Ra2 of densification is cut into suitable size according to the requirement that battery is assembled, at 50 DEG C after vacuum bakeout 12h, vacuum buffer memory.By LiCoO 2(100wt%), binding agent PVDF (0.8wt%) and carbon black (0.5wt%) furnishing slurry are coated on aluminium foil and are made positive plate (LiCoO 2).By Graphite (100wt%), binding agent SBR (2wt%) and thickener CMC (1.2wt%) furnishing slurry are coated on Copper Foil and are made negative plate (Graphite), in drying shed, separate LiCoO with polymer film Ra2 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery.
Comparative example 3
This comparative example is used for comparative illustration polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, identical with embodiment 4, form the aqueous solution of 0.4wt% dispersant PVA.
2, identical with embodiment 4, formed containing inorganic particle SnO 2dispersion liquid.
3, be that the P1005 (solid content 50wt%) of-18 DEG C is adjusted to pH=8-9 by glass transition temperature.Its cast membrane is designated as R3.
4, identical with embodiment 4, form coating liquid.
5, coating liquid is applied on PE barrier film both sides and PTFE plate, 24h is toasted at 50 DEG C, obtain the polymer film Rb3 of the densification on the polymer film Ra3 of the densification on PE barrier film and PTFE plate, the thickness of Ra3 is (1+1) μm, and the thickness of Rb3 is 10.5 μm.
6, in drying shed, LiCoO is separated with polymer film Ra3 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery.All the other are all identical with comparative example 2.
Comparative example 4
This comparative example is used for comparative illustration polymer film disclosed by the invention and preparation method thereof, gel electrolyte and polymer battery.
1, identical with embodiment 7, form the aqueous solution of 0.6wt% dispersant PEG.
2, identical with embodiment 7, formed containing inorganic particle γ-Al 2o 3dispersion liquid.
3, use glass transition temperature is P1005 (solid content 50wt%) emulsion of-18 DEG C.Its cast membrane is designated as R4.All the other are all identical with embodiment 7.
4, identical with embodiment 7, form coating liquid.
5, coating liquid is applied on PE barrier film both sides and PTFE plate, 24h is toasted at 50 DEG C, obtain the polymer film Rb4 of the densification on the polymer film Ra4 of the densification on PE barrier film and PTFE plate, the thickness of Ra4 is (1+1) μm, and the thickness of Rb4 is 10.5 μm.
6, in drying shed, LiCoO is separated with polymer film Ra4 in a winding manner 2positive plate and Graphite negative plate, add enough electrolyte, seals into Soft Roll SL435573 type LiCoO 2/ Graphite polymer battery.All the other are all identical with comparative example 2.
Performance test
1, surface topography:
Scanning electron microscopy (SEM, JEOL, JSM-7600FE) is adopted to observe the microscopic appearance on the polymer film Ma2 surface that embodiment 2 obtains.As shown in Figure 1.As can be known from Fig. 1: between the second polymer beads and inorganic particle, there is more gap.
2, air permeability test:
The air permeability (Gurley index) of barrier film refers to 100mL gas and pass through 961.6mm under about 3170Pa pressure 2the time of diaphragm paper.The dense film Ra1-4 that the polymer film Ma1-9 adopting ion-exchange membrane performance tester to obtain embodiment 1-9 and comparative example 1-4 obtains carries out air permeability test.
Test result lists in table 1.
Table 1
Air permeability (sec/100mL) Pick up (%) Conductivity (mS/cm)
Embodiment 1 314 263 6.41
Embodiment 2 241 301 7.53
Embodiment 3 220 367 8.31
Embodiment 4 216 271 6.85
Embodiment 5 238 309 7.48
Embodiment 6 308 373 8.11
Embodiment 7 253 235 7.16
Embodiment 8 311 296 7.92
Embodiment 9 226 362 7.55
Comparative example 1 >1451 600 5.18
Comparative example 2 >1451 600 5.31
Comparative example 3 >1451 760 5.49
Comparative example 4 615 760 5.83
As seen from the results in Table 1: polymer film provided by the invention has excellent permeability.
3, pick up test:
The cast membrane R1-3 that the cast membrane M1-9 obtained by embodiment 1-9 and comparative example 1-3 obtains is cut into the disk that diameter is 17mm, after room temperature in vacuo drying, 24h in electrolyte is immersed in after weighing up quality, then taking-up filter paper blots the liquid on film surface and the quality weighed now, and operation is all carried out in the glove box being full of argon gas.
According to formulae discovery pick up: pick up %=(W i-W)/W × 100%
W is the quality of dry film;
W ifor dry film has soaked the quality after 24h in the electrolytic solution.
The test result of pick up is in table 1.
From table 1 data: the pick up of polymer film provided by the invention obtains suitable reduction.
4, conductivity test:
The ionic conductivity AC impedence method of gel electrolyte is tested.The polymer film Rb1-4 of the densification that the polymer film Mb1-9 obtained by embodiment 1-9 and comparative example 1-4 obtains is under the stripping of PTFE plate, be cut into the disk that diameter is 17mm, after room temperature in vacuo drying, be placed between two stainless steel (SS) electrodes, absorb the electrolyte of q.s, after being sealed in 2016 type button cells, carry out AC impedance experiment, intersection point that is linear and real axis is the bulk resistance of gel electrolyte, the ionic conductivity of gel electrolyte can be obtained thus: (wherein L represents the thickness of gel electrolyte to σ=L/AR, A is the contact area of corrosion resistant plate and film, R is the bulk resistance of gel electrolyte).
The conductivity calculating gel electrolyte lists in table 1.
As shown in Table 1: the conductivity of gel electrolyte prepared by polymer film provided by the invention is very high.
5, viscosity test:
The resultant battery (through room temperature seamless) that embodiment 2 obtains is dissected, and obtained positive/negative plate and barrier film are taken pictures.
Result is as Fig. 2.
As shown in Figure 2: the polymer film that the present invention obtains all has high viscosity to lithium ion battery plus-negative plate after Electolyte-absorptive, thus improve the hardness of soft-package battery.
6, electrochemical stability window test:
The test of electrochemical stability window adopts electrochemical workstation (Shanghai occasion China, CHI660C) to carry out.The polymer film Ma2 obtained with embodiment 2 separates metal lithium sheet and platinized platinum, after injecting enough electrolyte, seals into 2016 type Li/Pt polymer batteries.Pt is work electrode, and Li is to electrode and reference electrode.
Wherein, namely polymer film Ma2 becomes gel electrolyte after absorbing enough electrolyte, and adopt linear sweep voltammetry to test the electrochemical window of gel electrolyte, sweep speed is 0.0005V/s, and sweep limits is: 3V-7V.
Test result as shown in Figure 3.
Test result shows: the decomposition voltage of the gel electrolyte that polymer film provided by the invention prepares, up to 6.5V, can be used for high voltage withstanding polymer battery.
7, battery high rate performance test
Adopt (Guangzhou is blue strange, BK6016) performance of lithium ion battery test cabinet, the polymer battery after the partial volume obtain embodiment 1-9 and comparative example 1-4 carries out multiplying power discharging property test.
Multiplying power discharging method of testing is: by battery 0.5C (1C=2520mA) constant-current constant-voltage charging to 4.35V, cut-off current is 0.02C, shelves 5min, is discharged to 3.0V with 0.2C/0.5C/1C/2C/3C/4C, record discharge capacity.
Rate discharge test results lists in table 2.
Table 2
Test result in table 2 shows: the polymer battery that polymer film provided by the invention prepares has excellent high-rate discharge ability.
8, cycle performance test
Adopt (Guangzhou is blue strange, BK6016) performance of lithium ion battery test cabinet, the polymer battery after the partial volume obtain embodiment 2 and comparative example 3, carries out the test of cycle performance.
Method of testing is: battery is charged to 4.35V with 1C, and 0.1C ends; Shelve 10min, put to 3.0V with 1C, so circulate.
Cycle performance test result is shown in Fig. 4.
Test result shows: the polymer battery adopting polymer film provided by the invention to prepare has excellent cycle performance.
9, high-temperature storage performance test
60 DEG C of 7 days storge qualities tests are carried out to the polymer battery that embodiment 2 and comparative example 3 obtain.
Method of testing is as follows: 1, adopt (Guangzhou is blue strange, BK6016) performance of lithium ion battery test cabinet that battery is charged to 4.35V with 0.5C, 0.02C ends; Shelve 5min, be discharged to 3.0V with 0.2C, discharge capacity before record; 2, battery is charged to 4.35V with 0.5C, 0.02C ends; Voltage, internal resistance, thickness before testing after shelving 1h; 3, battery is put into 60 DEG C of baking boxs and store 7 days; 4, test thickness immediately after storing, after normal temperature places 2h, test cools thickness, rear voltage, rear internal resistance; 5, battery is discharged to 3.0V with 0.2C, record residual capacity, and calculated capacity surplus ratio (residual capacity is except former discharge capacity); 6, be full of electricity with 0.5C, shelve 5min, be discharged to 3.0V with 0.2C, record recovery capacity, and calculated capacity recovery rate (recovering capacity except former capacity).
Test result is in table 3.
Table 3
Embodiment 2 Comparative example 3
Front voltage (V) 4.344 4.343
Front internal resistance (m Ω) 25.7 27.7
Front thickness (mm) 4.45 4.87
Front capacity (mAh) 2581 2507
Rear voltage (V) 4.271 3.981
Rear internal resistance (m Ω) 29.5 35.0
Thickness (mm) immediately 4.54 5.12
Cooling thickness (mm) 4.53 5.06
Residual capacity (mAh) 2372 1398
Recovery capacity (mAh) 2503 2180
Thickness change immediately 2％ 5％
Cooling thickness change 2％ 4％
Capacity surplus ratio 92％ 56％
Capacity restoration rate 97％ 87％
Voltage change ratio 2％ 8％
Test result from table 3: the polymer battery adopting polymer film provided by the invention to prepare has higher capability retention and capacity restoration rate, and voltage change ratio and thickness change little.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (25)

1. a polymer film, is characterized in that, comprises the first polymeric matrix and the second polymer beads of being distributed in described first polymeric matrix and inorganic particle; The glass transition temperature of described first polymeric matrix is less than 40 DEG C, and the glass transition temperature of described second polymer beads is more than 40 DEG C;
The glass transition temperature of described polymer film is 30-60 DEG C, and air permeability is 150-600sec/100mL.
2. polymer film according to claim 1, is characterized in that, the glass transition temperature of described first polymeric matrix is more than-70 DEG C and is less than 40 DEG C, and the glass transition temperature of described second polymer beads is 40-70 DEG C.
3. polymer film according to claim 1, is characterized in that, the average grain diameter of described second polymer beads is 0.1-1.0 μm; The average grain diameter of described inorganic particle is 0.01-10 μm.
4. according to the polymer film in claim 1-3 described in any one, it is characterized in that, described first polymeric matrix be selected from the copolymer of acrylate copolymer, copolymer in cinnamic acrylic ester, vinyl chloride-acrylate copolymer, AN-AE, polyurethane, vinylacetate-ethylene one or more;
Described second polymer beads is selected from acrylate copolymer particle.
5. according to the polymer film in claim 1-3 described in any one, it is characterized in that, described inorganic particle is selected from Al 2o 3, SiO 2, SnO 2, ZrO 2, TiO 2, SiC, Si 3n 4, CaO, MgO, ZnO, BaTiO 3, LiAlO 2, BaSO 4in one or more.
6. polymer film according to claim 4, it is characterized in that, also containing auxiliary polyalcohol in described polymer film, described auxiliary polyalcohol choosing is containing one or more in the acrylate of polystyrene copolymerization unit, the acrylate containing polybutadiene copolymer unit, the acrylate containing polyacrylonitrile copolymerization units.
7. according to the polymer film in claim 1-3,6 described in any one, it is characterized in that, in described polymer film, the first polymeric matrix, the second polymer beads, containing or containing the gross mass of auxiliary polyalcohol and the mass ratio of inorganic particle be not: 1:10-10:1.
8. polymer film according to claim 7, is characterized in that, in described polymer film, the volume fraction of described second polymer beads is 40-90vol%.
9. polymer film according to claim 8, is characterized in that, the pick up of described polymer film is 40-380wt%.
10. according to the polymer film in claim 1-3,6,8,9 described in any one, it is characterized in that, also containing one or more in dispersant, surfactant and thickener in described polymer film;
With the content of described inorganic particle for benchmark, the content of described dispersant is 0.05-10wt%, and the content of described surfactant is 0.05-10wt%, and the content of described thickener is 0.05-10wt%.
11. polymer films according to claim 10, it is characterized in that, described dispersant is selected from the one in polyacrylic acid, polymine, softex kw, polyamide, polyacrylamide, acrylic acid and acrylic ester copolymers, acrylic acid-acrylamide copolymer, ammonium acrylate-acrylate copolymer, styrene-maleic anhydride copolymer, Styrene-acrylic copolymer, acrylic acid-maleic anhydride copolymer, maleic anhydride-acrylamide copolymer, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, AEO; The weight average molecular weight of described dispersant is 100-500000g/mol;
Described surfactant be selected from lauryl sodium sulfate, neopelex, dioctyl succinate disulfonate acid, sodium glycocholate, sodium sulfate of polyethenoxy ether of fatty alcohol, aliphatic alcohol polyethenoxy ammonium sulfate, AEO, APES, NPE, alkyl, polyether one or more;
Described thickener be selected from polyacrylate, polyethylene glycol oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, acrylic acid and acrylic ester copolymers, polyurethane, methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose one or more; The weight average molecular weight of described thickener is 1000-2000000g/mol.
The preparation method of 12. polymer films as claimed in claim 1, is characterized in that, comprise the steps:
S1, by the first polymer emulsion and the second polymer emulsion mixing, obtain mixed emulsion; The glass transition temperature of described mixed emulsion is 30-60 DEG C; The glass transition temperature of described first polymer emulsion is less than 40 DEG C, and the glass transition temperature of described second polymer emulsion is more than 40 DEG C;
S2, described mixed emulsion to be mixed with the dispersion liquid containing inorganic particle, obtain coating liquid; In described coating liquid, the total solid content of mixed emulsion and the mass ratio of inorganic particle are: 1:10-10:1.
S3, apply described coating liquid, form liquid film, after solidification, obtain described polymer film; The temperature of described solidification is greater than the glass transition temperature of described first polymer emulsion, is less than the glass transition temperature of described second polymer emulsion.
13. preparation methods according to claim 12, is characterized in that, in described step S1, the glass transition temperature of the first polymer emulsion is more than-70 DEG C and is less than 40 DEG C, and the glass transition temperature of described second polymer emulsion is 40-70 DEG C.
14. preparation methods according to claim 12 or 13, it is characterized in that, described first polymer emulsion be selected from self-crosslinking pure-acrylic emulsion, self-crosslinking styrene-acrylic copolymer emulsion, self-crosslinking chlorine acrylic emulsion, self-crosslinking acrylonitrile compolymer emulsion, self-crosslinkable polyurethane emulsion, EVA emulsion one or more;
Described second polymer emulsion is selected from self-crosslinking pure-acrylic emulsion; In described second polymer emulsion, latex particle average grain diameter is 0.1-1.0 μm.
15. preparation methods according to claim 12, is characterized in that, in described step S1, comprise and auxiliary polyalcohol emulsion jointly being mixed with the first polymer emulsion, the second polymer emulsion, obtain described mixed emulsion;
Described auxiliary polyalcohol emulsion be selected from the acrylic acid ester emulsion containing polystyrene copolymerization unit, the acrylic acid ester emulsion containing polybutadiene copolymer unit, containing one or more in the acrylic acid ester emulsion of polyacrylonitrile copolymerization units.
16., according to the preparation method in claim 12,13,15 described in any one, is characterized in that, the addition of described second polymer emulsion is as the criterion for 40-90vol% to make the volume fraction of the second polymer beads in the polymer film for preparing.
17. preparation methods according to claim 16, is characterized in that, the addition of described auxiliary polyalcohol emulsion is as the criterion for 40-380wt% to make the pick up of the polymer film prepared.
18. according to the preparation method in claim 12,13,15,17 described in any one; it is characterized in that; also comprise before described step S2 and first dispersant solution being mixed with inorganic particle; then stirring at low speed 1-30min under 50-1000rpm rotating speed; high-speed stirred 1-30min under 1100-8000rpm rotating speed, obtains the dispersion liquid containing inorganic particle again.
19. preparation methods according to claim 18, is characterized in that, the anionic dispersing agent solution of described dispersant solution to be pH value be 8-9, also comprises in described step S1 and the pH value of described mixed emulsion is adjusted to 8-9.
20. preparation methods according to claim 18, is characterized in that, the cationic dispersing agent solution of described dispersant solution to be pH value be 4-5, also comprises in described step S1 and the pH value of described mixed emulsion is adjusted to 4-5.
21. preparation methods according to claim 18, it is characterized in that, described dispersant is selected from the one in polyacrylic acid, polymine, softex kw, polyamide, polyacrylamide, acrylic acid and acrylic ester copolymers, acrylic acid-acrylamide copolymer, ammonium acrylate-acrylate copolymer, styrene-maleic anhydride copolymer, Styrene-acrylic copolymer, acrylic acid-maleic anhydride copolymer, maleic anhydride-acrylamide copolymer, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, AEO; The weight average molecular weight of described dispersant is 100-500000g/mol;
The concentration of described dispersant solution is 0.01-10wt%; In described dispersion liquid, the content of dispersant is the 0.05-10wt% of filer content used.
22. according to claim 12,13,15,17, preparation method in 19-21 described in any one, it is characterized in that, described inorganic particle is selected from Al 2o 3, SiO 2, SnO 2, ZrO 2, TiO 2, SiC, Si 3n 4, CaO, MgO, ZnO, BaTiO 3, LiAlO 2, BaSO 4in one or more; The average grain diameter of described inorganic particle is 0.01-10 μm.
23. preparation methods according to claim 12, it is characterized in that, in described step S2, comprise and surfactant and/or thickener and mixed emulsion, dispersion liquid containing inorganic particle are mixed, then high-speed stirred 1-30min under 1100-8000rpm rotating speed, stirring at low speed 1-30min under 50-1000rpm rotating speed, obtains coating liquid again;
Described surfactant be selected from lauryl sodium sulfate, neopelex, dioctyl succinate disulfonate acid, sodium glycocholate, sodium sulfate of polyethenoxy ether of fatty alcohol, aliphatic alcohol polyethenoxy ammonium sulfate, AEO, APES, NPE, alkyl, polyether one or more; The addition of described surfactant is the 0.05-10wt% of described inorganic particle addition;
Described thickener be selected from polyacrylate, polyethylene glycol oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, acrylic acid and acrylic ester copolymers, polyurethane, methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose one or more; The weight average molecular weight of described thickener is 1000-2000000g/mol; The addition of described thickener is the 0.05-10wt% of described inorganic particle addition.
24. 1 kinds of gel electrolytes, is characterized in that, comprise as the electrolyte in the polymer film in claim 1-11 as described in any one and polymer film as described in being adsorbed in.
25. 1 kinds of polymer batteries, is characterized in that, comprise positive pole, negative pole, barrier film and gel electrolyte as claimed in claim 24, described gel electrolyte is between described positive pole and negative pole.
CN201410709371.7A 2014-11-28 2014-11-28 Polymer film and preparation method thereof, gel electrolyte and polymer battery Pending CN105529495A (en)

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CN110416604A (en) * 2019-08-09 2019-11-05 哈尔滨理工大学 A kind of preparation method of the solid electrolyte membrane of high-lithium ion transport number
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CN112510251A (en) * 2020-12-15 2021-03-16 电子科技大学 SiC-based all-solid-state lithium ion battery polymer electrolyte and preparation method thereof
CN113300004A (en) * 2020-02-21 2021-08-24 香港中文大学 Molecular-crowding electrolyte, battery comprising same, and method for manufacturing same
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CN103633367A (en) * 2012-08-28 2014-03-12 比亚迪股份有限公司 Gel polymer electrolyte, polymer lithium ion battery and making method of polymer lithium ion battery

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CN109755630A (en) * 2017-11-03 2019-05-14 深圳格林德能源集团有限公司 A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery
CN110117417A (en) * 2018-02-07 2019-08-13 比亚迪股份有限公司 Polymer dielectric film and preparation method thereof and lithium ion battery
CN110117417B (en) * 2018-02-07 2021-03-26 比亚迪股份有限公司 Polymer electrolyte membrane, preparation method thereof and lithium ion battery
CN109301319A (en) * 2018-09-17 2019-02-01 惠州市典名新能源科技有限公司 A kind of gel polymer electrolyte and the lithium secondary battery including it
CN112117487A (en) * 2019-06-20 2020-12-22 新奥科技发展有限公司 Electrolyte material, preparation method thereof, solid electrolyte and battery
CN112117487B (en) * 2019-06-20 2022-01-18 新奥科技发展有限公司 Electrolyte material, preparation method thereof, solid electrolyte and battery
CN110416604A (en) * 2019-08-09 2019-11-05 哈尔滨理工大学 A kind of preparation method of the solid electrolyte membrane of high-lithium ion transport number
CN110416604B (en) * 2019-08-09 2022-07-12 哈尔滨理工大学 Preparation method of solid electrolyte membrane with high lithium ion transference number
CN113300004A (en) * 2020-02-21 2021-08-24 香港中文大学 Molecular-crowding electrolyte, battery comprising same, and method for manufacturing same
CN112510251A (en) * 2020-12-15 2021-03-16 电子科技大学 SiC-based all-solid-state lithium ion battery polymer electrolyte and preparation method thereof
CN113328203A (en) * 2021-04-21 2021-08-31 惠州锂威新能源科技有限公司 Gel electrolyte diaphragm, preparation method thereof and lithium ion battery

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