CN109755630A - A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery - Google Patents
A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery Download PDFInfo
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Abstract
The invention discloses a kind of Recombination gel polymer dielectric preparation method and its lithium ion batteries, the preparation process of the Recombination gel polymer dielectric includes: the dissolution of polymer, the introducing of crosslinking agent, the dispersion of inorganic filler, the dissolution of lithium salts and slurry cast film forming, the Recombination gel polymer electrolytic mass-energy of preparation effectively improves Solvent migration existing for conventional gel electrolyte and volatility is larger, electrochemical stability and thermal stability are poor, ionic conductivity is low, mechanical strength is low, the problems such as electrolyte and electrode interface stability are poor, with conductivity at room temperature height, electrochemical voltage window is wide, mechanical performance is high and electrolyte is to the preferable advantage of the caking property of positive and negative anodes, so that the security performance and chemical property of lithium ion battery are largely increased；Preparation method is simple and quick simultaneously, at low cost, and the lithium ion battery appearance assembled by it is frivolous, electrochemical performance, has very wide market application prospect.
Description
Technical field
The invention belongs to polymer Li-ion battery technical fields, and in particular to a kind of Recombination gel polymer dielectric
Preparation method and its lithium ion battery.
Background technique
Since lithium ion battery has many advantages, such as that energy density is high, output voltage is high, have extended cycle life, environmental pollution is small,
Therefore since lithium ion battery the 1990s realizes industrialization, lithium ion battery just not only in portable electronic product and
Electric vehicle field has all obtained extensive research and application, and holding to Energy restructuring and energy and environment
There is important facilitation in terms of supervention exhibition.Lithium ion battery has become the mobile electrons such as mobile phone, laptop and sets at present
Standby standard configuration power supply, and be widely used in electric car and hybrid-electric car field.
It is passed using carbonic ester as the liquid electrolyte of solvent as ion currently, commercialized lithium ion battery is mainly used
Lead medium.But the electrolyte leakage of liquid lithium ionic cell, organic solvent is volatile, burning leads to the problem of thermal runaway, can produce
Raw serious security risk, so liquid electrolyte can not fully meet requirement of the extensive energy storage to safety.Therefore, simultaneous
The high ionic conductivity for caring for polymer excellent machinability and liquid electrolyte, can be effectively improved the leakage of liquid lithium ionic cell
The problems such as liquid, inflammable and explosion, and the configuration design of battery is flexible, can quantity-produced gel polymer electrolyte (GPE) by
Extensive concern and research are arrived.
Polymer dielectric (PEs) is the important component of polymer Li-ion battery, since scientific research personnel is to polymerization
The more extensive research of application of object lithium ion battery, therefore the requirement to polymer dielectric performance is continuously improved, therefore opens
It issues the verify development in the field of the polymer electrolytic that has excellent performance and plays important impetus.Polymer dielectric is mainly
There are polymer and lithium salts to constitute a kind of novel ion conductor, there are the advantages such as light weight, the good, controlled shape of viscoplasticity.Due to
Solid polymer electrolyte does not contain any organic solvent, because substantially increasing security performance without leaking；And it is poly-
Polymer electrolyte has good flexibility and processability, and the volume that can alleviate active material during the charging process becomes
Change, significantly improves circulation and security performance.Gel polymer electrolyte (GPEs) is exactly that polymer monomer, plasticizer and lithium salts are logical
The polymer dielectric film crossing certain method and preparing.As a kind of special physical form, gel is between solid-state and liquid
Between, this duality, which ensure that gel both, has the caking property of solid, while also having the property of liquid diffusion transport substance,
Therefore gel polymer electrolyte had not only had the excellent machinability of polymer, but also had liquid organic electrolyte ion-conductance
The high performance of conductance, becomes the emphasis studied at present.Currently, mainly there is the material of polymer most study in polymer dielectric
PEO(polyethylene glycol oxide), PMMA(polymethyl methacrylate), PAN(polyacrylonitrile), PVDF(Kynoar) and PVDF-
HFP(Kynoar-hexafluoropropene) copolymer.But the conductivity at room temperature of gel polymer electrolyte it is relatively low, cannot
Meet high-power charge and discharge needs, electrode electrolyte interface contacts machinery caused by bad and higher proportion plasticizer exists
The problems such as low strength, poor heat resistance, limits gel polymer electrolyte in lithium ion battery in certain degree
Application.
Polymeric substrates are modified using inorganic nano-filler, and prepare Recombination gel electrolyte, are existing ranks
One of the active path of Duan Gaishan gel polymer electrolyte film performance.Its SiO2、Al2O3, zeolite, γ-AlLiO2、TiO2With
ZnO etc. is most common inorganic filler.Inorganic nano-filler, which is added, can significantly improve mechanical strength and ionic conductivity, and
Increase in a certain range with the increase of filer content, more than certain value since stereo-electronic effect then will lead to conductivity
Decline.In addition to this, inorganic oxide nanoparticles can also adsorb micro-moisture and electrolyte lithium in colloidal electrolyte
Salt decomposes the acidic materials generated, the interfacial property being effectively improved between polymer dielectric and electrode.
Currently, repeatedly reporting Recombination gel method for preparing polymer electrolytes and in lithium ion battery both at home and abroad
In application.As CN201610929634.4 discloses a kind of in-situ polymerization SiO2Bead/LiPF6/ PVDF-HFP gel electrolyte
And preparation method thereof.Its preparation process mainly comprises the steps that (1) in atmosphere of inert gases by PVDF-HFP and NPGDA
It is scattered in LiPF6/ EC+DEC is stirred evenly and is obtained mixed system；(2) by monodisperse SiO2Bead is added to above-mentioned mixture
In system, AIBN is initiator, and in-situ polymerization forms gel electrolyte.But the preparation method is complex, wants to environmental condition
It asks more stringent, is difficult to control and required time is longer.
CN201610261909.1 discloses a kind of preparation method of composite gel polymer electrolyte, by epoxy resin-matrix
Electrolyte and mesoporous TiO2It carries out compound and is prepared.Specifically includes the following steps: dissolving electrolyte salt is being plasticized by (1)
In agent, it is uniformly mixed and obtains electrolyte salt solution；(2) mesoporous TiO2It is dissolved in mixed solution, ultrasound, stirring are placed 1 ~ 3 day；
(3) polymer substrate, curing agent are added in above-mentioned mixed solution, heating polymerization；(4) casting film, 80oC solidifies to obtain compound
Gel electrolyte membrane.Although higher (5.0 V or more) by the gel electrolyte membrane voltage window that this method is prepared, its
Conductivity at room temperature is relatively low, and mechanical performance is poor so that gel polymer electrolyte in lithium ion battery application by
Considerable restraint.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of Recombination gel polymer dielectric preparation methods
And its lithium ion battery.
The technical solution of the present invention is as follows: a kind of Recombination gel polymer dielectric is prepared using solution-cast technology,
Preparation method the following steps are included:
(1) polymer substrate is pre-processed, and is dissolved completely in organic solvent；
(2) crosslinking agent is added into step (1) resulting solution and carries out dissolution dispersion；
(3) inorganic filler is added into step (2) acquired solution and is dispersed；
(4) lithium salts is added into step (3) acquired solution to be dissolved, obtains mixed glue solution；
(5) organic solvent in mixed glue solution obtained in step (4) is subjected in substrate volatilization and drying and forming-film, prepared
Recombination gel polymer dielectric.
In the step (1), polymer substrate is Kynoar-hexafluoro-propylene (PVDF-HFP), polyacrylonitrile
(PAN), in polymethyl methacrylate (PMMA), polyethylene glycol oxide (PEO), polypropylene oxide and polyvinyl pyridine at least
It is a kind of.
In the step (1), molecular weight ranges Mw=2.0 × 10 of the polymer substrate5~7.0×105.If
Molecular weight is too small, is unfavorable for forming gel and mechanical strength is not high；If molecular weight is larger, it is unfavorable for the molten of polymer substrate
Solution.
In the step (1), the pretreatment condition of the polymer substrate are as follows: in 80 DEG C ~ 100 DEG C temperature and
Under 0.01MPa air pressure, 3h is toasted, makes its water content lower than 0.1%.
In the step (1), organic solvent is N-Methyl pyrrolidone (NMP), N, dinethylformamide, hexamethylene
One kind of the mixed solution of ketone, tetrahydrofuran, acetonitrile, acetone or acetone and alcohol.
In the step (1), the mass ratio of polymer substrate and organic solvent is between 1:1 ~ 1:9.
In the step (2), crosslinking agent is dimethoxymethane, ethylene glycol diethyl ether, branched polyethylene imine
(PEI), at least one of polyethyleneglycol diglycidylether.
In the step (2), the mass ratio of crosslinking agent and polymer substrate is 0.01 ~ 1.0.
In the step (3), inorganic filler is silica (SiO2), aluminum oxide (Al2O3), titanium dioxide
(TiO2), zinc oxide (ZnO) zeolite, one or more of montmorillonite and molecular sieve ZMS-5.
In the step (3), the mass fraction of inorganic filler is 0.1% ~ 20.0%.
In the step (3), the partial size of inorganic filler is between 50 ~ 500 nm.
In the step (4), lithium salts electrolyte is lithium perchlorate (LiClO4), LiBF4 (LiBF4), hexafluoro
Lithium phosphate (LiPF6), hexafluoroarsenate lithium (LiAsF6), double trifluoromethanesulfonimide lithiums (LiTFSI), trifluoromethanesulfonimide
At least one of lithium (LiFSI) or dioxalic acid lithium borate (LiBOB).
In the step (4), the mass fraction of lithium salts electrolyte is 5.0% ~ 30.0%.
In above-mentioned step (2) (3) (4), dissolution or dispersion are carried out under high speed machine stirring.
In the step (5), the volatilization of organic solvent and drying and forming-film be by way of casting or scratching
Progress is sprawled in substrate.
In the step (5), the substrate is glass plate or polytetrafluoroethylene (PTFE) plate.
In the step (5), the drying is to be dried in vacuo 6 ~ 8 h at a temperature of 40 ~ 55 DEG C for the first time, second
Secondary is to continue dry 10 ~ 14h at a temperature of being increased to 60 ~ 80 DEG C.
The thickness of Recombination gel polymer dielectric film prepared by the above method between 20 ~ 100 μm, divide by aperture
Cloth is between 0.2 ~ 2 μm.
A kind of polymer Li-ion battery, wherein the lithium ion battery uses Recombination gel polymer as described above
Electrolyte is fixed between a positive electrode and a negative electrode, functions simultaneously as the diaphragm and electrolyte of battery.
Preferably, the just extremely cobalt acid lithium (LiCoO of the lithium ion battery2), LiMn2O4 (LiMn2O4), nickel ion doped
(LiNixMn2-xO4), LiFePO4 (or ferric phosphate) (LiFePO4/ FePO4) and ternary material nickle cobalt lithium manganate (NCM), five
V 2 O (V2O5), molybdenum trioxide (MoO3One or more of).
Preferably, the lithium ion battery cathode selection graphite, hard carbon, silicon, Si oxide, tin alloy, lithium metal and
One or more of lithium alloy.
The beneficial effects of the present invention are: the Recombination gel polymer dielectric prepared has conductivity at room temperature
Height, electrochemical voltage window is wide, and mechanical performance is high and electrolyte is to the preferable advantage of the caking property of positive and negative anodes, so that polymer lithium
The security performance and chemical property of ion battery are greatly improved；Meanwhile the preparation method have it is simple and quick, at
This low advantage.
Detailed description of the invention
Fig. 1 is SiO used in the embodiment of the present invention2Scanning electron microscope (SEM) figure of nanometer bead.
Fig. 2 is scanning electron microscope (SEM) figure of the Recombination gel polymer dielectric of preparation of the embodiment of the present invention.
Fig. 3 is the Recombination gel polymer dielectric of preparation of the embodiment of the present invention in LiFePO4 half-cell system
Cycle performance test curve.
Specific embodiment
Particular content of the invention is made below in conjunction with the drawings and specific embodiments further elucidated above.
A kind of Recombination gel polymer dielectric, preparation method includes the following steps:
(1) polymer substrate is pre-processed, and is dissolved completely in organic solvent；
(2) crosslinking agent is added into step (1) resulting solution and carries out dissolution dispersion；
(3) inorganic filler is added into step (2) acquired solution and is dispersed；
(4) lithium salts is added into step (3) acquired solution to be dissolved, obtains mixed glue solution；
(5) organic solvent in mixed glue solution obtained in step (4) is subjected in substrate volatilization and drying and forming-film, prepared
Recombination gel polymer dielectric.
In the step (1), polymer substrate is Kynoar-hexafluoro-propylene (PVDF-HFP), polyacrylonitrile
(PAN), in polymethyl methacrylate (PMMA), polyethylene glycol oxide (PEO), polypropylene oxide and polyvinyl pyridine at least
It is a kind of.Preferably, Kynoar-hexafluoropropene (PVDF-HFP) is used as polymer substrate, crosslinking agent, inorganic filler and lithium salts
It is dispersed in Kynoar-hexafluoropropene (PVDF-HFP).
In the step (1), molecular weight ranges Mw=2.0 × 10 of the polymer substrate5~7.0×105.It is preferred that
, molecular weight ranges Mw=4.0 × 10 of PVDF-HFP5~6.0×105.If molecular weight is too small, it is unfavorable for forming gel and machine
Tool intensity is not high；If molecular weight is larger, it is unfavorable for the dissolution of polymer substrate.
In the step (1), the pretreatment condition of the polymer substrate are as follows: in 80 DEG C ~ 100 DEG C temperature and
Under 0.01MPa air pressure, 3h is toasted, makes its water content lower than 0.1%.
In the step (1), organic solvent is N-Methyl pyrrolidone (NMP), N, dinethylformamide, hexamethylene
One kind of the mixed solution of ketone, tetrahydrofuran, acetonitrile, acetone or acetone and alcohol.Preferably, organic solvent is N- methylpyrrole
The mass ratio of alkanone (NMP), PVDF-HFP and NMP are preferably 1:4 ~ 1:6.
In the step (1), the mass ratio of polymer substrate and organic solvent is between 1:1 ~ 1:9.
In the step (2), crosslinking agent is dimethoxymethane, ethylene glycol diethyl ether, branched polyethylene imine
(PEI), at least one of polyethyleneglycol diglycidylether.Preferably, used crosslinking agent be ethylene glycol diethyl ether or
The mass ratio of person's branched polyethylene imine, crosslinking agent and PVDF-HFP are preferably 0.4 ~ 0.6.
In the step (2), the mass ratio of crosslinking agent and polymer substrate is 0.01 ~ 1.0.
In the step (3), inorganic filler is silica (SiO2), aluminum oxide (Al2O3), titanium dioxide
(TiO2), zinc oxide (ZnO) zeolite, one or more of montmorillonite and molecular sieve ZMS-5.Preferably, SiO is selected2As
Inorganic nano packing material, SiO2Partial size be 100 ~ 400 nm, SiO2It is preferably 0.05 ~ 0.1 with PVDF-HPF mass ratio.
In the step (3), the mass fraction of inorganic filler is 0.1% ~ 20.0%.
In the step (3), the partial size of inorganic filler is between 50 ~ 500 nm.
In the step (4), lithium salts electrolyte is lithium perchlorate (LiClO4), LiBF4 (LiBF4), hexafluoro
Lithium phosphate (LiPF6), hexafluoroarsenate lithium (LiAsF6), double trifluoromethanesulfonimide lithiums (LiTFSI), trifluoromethanesulfonimide
At least one of lithium (LiFSI) or dioxalic acid lithium borate (LiBOB).Preferably, use LiFSI and LiTFSI for lithium salts,
Lithium salts mass ratio is preferably 10% ~ 25%.
In the step (4), the mass fraction of lithium salts electrolyte is 5.0% ~ 30.0%.
In above-mentioned step (2) (3) (4), dissolution or dispersion are carried out under high speed machine stirring.
In the step (5), the volatilization of organic solvent and drying and forming-film be by way of casting or scratching
Progress is sprawled in substrate.
In the step (5), the substrate is glass plate or polytetrafluoroethylene (PTFE) plate.
In the step (5), the drying is to be dried in vacuo 6 ~ 8 h at a temperature of 40 ~ 55 DEG C for the first time, second
Secondary is to continue dry 10 ~ 14h at a temperature of being increased to 60 ~ 80 DEG C.
The thickness of Recombination gel polymer dielectric film prepared by the above method between 20 ~ 100 μm, divide by aperture
Cloth is between 0.2 ~ 2 μm.
A kind of polymer Li-ion battery, wherein the lithium ion battery uses Recombination gel polymer as described above
Electrolyte is fixed between a positive electrode and a negative electrode, functions simultaneously as the diaphragm and electrolyte of battery.
Preferably, the just extremely cobalt acid lithium (LiCoO of the lithium ion battery2), LiMn2O4 (LiMn2O4), nickel ion doped
(LiNixMn2-xO4), LiFePO4 (or ferric phosphate) (LiFePO4/ FePO4) and ternary material nickle cobalt lithium manganate (NCM), five
V 2 O (V2O5), molybdenum trioxide (MoO3One or more of).
Preferably, the lithium ion battery cathode selection graphite, hard carbon, silicon, Si oxide, tin alloy, lithium metal and
One or more of lithium alloy.
The following are specific implementation steps:
Implementation steps 1
The following are the specific preparation steps of Recombination gel polymer dielectric:
In mechanical stirring, by 3.0 g Kynoar-hexafluoropropene, (PVDF-HFP, molecular weight are 5.3 × 105) molten
In the NMP of 15.0 g, makes it completely dissolved and obtain clear glue.Then 1.5 g or so ethylene glycol diethyl ether is added
Or branched polyethylene imine, it makes it completely dissolved, continues thereafter with and 0.5g SiO is added2Nano particle (Fig. 1 SiO2Nanometer is small
The SEM of ball schemes), it is lasting to stir, it is fully dispersed in it in mixed glue solution, 0.6 g LiTFSI is eventually adding, after being completely dissolved
It obtains containing SiO2With the uniform sizing material of lithium salts, obtained slurry is uniformly cast or is scratched in clean glass plate or
It is to be increased to 60 ~ 80 for the second time then for the first time in 40 ~ 55 DEG C of at a temperature of 6 ~ 8 h of vacuum drying on polyfluortetraethylene plate
Continue dry 10 ~ 14 h at a temperature of DEG C；Finally, being stripped out from glass plate or PTFE plate by it and obtaining thickness and be about
35 ~ 80 μm, aperture is about 0.5 ~ 1.5 μm of gel polymer electrolyte.Attached drawing 2 is poly- for plural gel manufactured in the present embodiment
The SEM of polymer electrolyte schemes.
Implementation steps 2
Conductivity test is carried out to the Recombination gel polymer dielectric of preparation:
The test method of composite gel polymer electrolyte conductivity are as follows: addition prepares solidifying between two stainless steel gaskets
Xanthan polymer electrolyte constructs polymer electrolyte battery system, then uses CH660D pairs of Shanghai Chen Hua electrochemical workstation
Battery system carries out ac impedance measurement, and test frequency range is 10Hz ~ 100kHz, finally obtains plural gel polymer electrolytic
The AC impedance spectroscopy of matter, therefore the conductivityσ of sample can be by formula (1) calculates.
σ=d/Rb* (1) S
D is the thickness of polymer dielectric film, and S is the contact area of polymer dielectric film and electrode, RbFor polymer electrolytic
The intersection value of the intrinsic impedance of electrolyte cell system, i.e. curve in high frequency region and horizontal axis.
By measuring and calculation, the conductivity of composite gel polymer electrolyte prepared by the present embodiment is 8.3 × 10-3
S/cm。
Implementation steps 3
The composite gel polymer electrolyte prepared is assembled into lithium ion battery, the LiFePO4 prepared is used as anode,
Lithium metal is placed between positive and negative anodes as cathode, composite gel polymer electrolyte film as diaphragm and electrolyte, sealing preparation
At button cell, cycle performance test finally is carried out using blue electricity button electric tester LAND CT2001A, test voltage range is
It is recycled under 3.0 ~ 4.95 V, 0.1C charge-discharge magnification, test results are shown in figure 3.After test result shows circulation 30 times,
Specific discharge capacity still possesses 153 mAh/g, coulombic efficiency 96.7%.
Claims (21)
1. a kind of Recombination gel polymer dielectric preparation method, which is characterized in that method includes the following steps:
(1) polymer substrate is pre-processed, and is dissolved completely in organic solvent；
(2) crosslinking agent is added into step (1) resulting solution and carries out dissolution dispersion；
(3) inorganic filler is added into step (2) acquired solution and is dispersed；
(4) lithium salts is added into step (3) acquired solution to be dissolved, obtains mixed glue solution；
(5) organic solvent in mixed glue solution obtained in step (4) is subjected in substrate volatilization and drying and forming-film, prepared
Recombination gel polymer dielectric.
2. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (1) in, polymer substrate be Kynoar-hexafluoro-propylene (PVDF-HFP), polyacrylonitrile (PAN), poly- methyl-prop
At least one of olefin(e) acid formicester (PMMA), polyethylene glycol oxide (PEO), polypropylene oxide and polyvinyl pyridine.
3. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (1) in, molecular weight ranges Mw=2.0 × 10 of the polymer substrate5~7.0×105。
4. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (1) in, the pretreatment condition of the polymer substrate are as follows: at 80 DEG C ~ 100 DEG C temperature and 0.01MPa air pressure, baking
3h makes its water content lower than 0.1%.
5. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (1) in, organic solvent be N-Methyl pyrrolidone (NMP), N, dinethylformamide, cyclohexanone, tetrahydrofuran, second
One kind of the mixed solution of nitrile, acetone or acetone and alcohol.
6. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (1) in, the mass ratio of polymer substrate and organic solvent is between 1:1 ~ 1:9.
7. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (2) in, crosslinking agent be dimethoxymethane, ethylene glycol diethyl ether, branched polyethylene imine (PEI), polyethylene glycol two
At least one of glycidol ether.
8. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (2) in, the mass ratio of crosslinking agent and polymer substrate is 0.01 ~ 1.0.
9. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that described
The step of (3) in, inorganic filler be silica (SiO2), aluminum oxide (Al2O3), titanium dioxide (TiO2), zinc oxide
(ZnO) one or more of zeolite, montmorillonite and molecular sieve ZMS-5.
10. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (3), the mass fraction of inorganic filler is 0.1% ~ 20.0%.
11. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (3), the partial size of inorganic filler is between 50 ~ 500 nm.
12. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (4), lithium salts electrolyte is lithium perchlorate (LiClO4), LiBF4 (LiBF4), lithium hexafluoro phosphate
(LiPF6), hexafluoroarsenate lithium (LiAsF6), double trifluoromethanesulfonimide lithiums (LiTFSI), trifluoromethanesulfonimide lithium
(LiFSI) or at least one of dioxalic acid lithium borate (LiBOB).
13. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (4), the mass fraction of lithium salts electrolyte is 5.0% ~ 30.0%.
14. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that upper
In the step of stating (2) (3) (4), dissolution or dispersion are carried out under high speed machine stirring.
15. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (5), the volatilization of organic solvent and drying and forming-film be sprawled in substrate by way of casting or scratching into
Row.
16. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (5), the substrate is glass plate or polytetrafluoroethylene (PTFE) plate.
17. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that in institute
In the step of stating (5), it is to be increased to for the second time that the drying, which is to be dried in vacuo 6 ~ 8 h at a temperature of 40 ~ 55 DEG C for the first time,
Continue dry 10 ~ 14h at a temperature of 60 ~ 80 DEG C.
18. a kind of Recombination gel polymer dielectric preparation method according to claim 1, which is characterized in that made
The thickness of standby Recombination gel polymer dielectric film out is between 20 ~ 100 μm, and pore-size distribution is between 0.2 ~ 2 μm.
19. a kind of polymer Li-ion battery, which is characterized in that the lithium ion battery uses Recombination gel as described above
Polymer dielectric is fixed between a positive electrode and a negative electrode, functions simultaneously as the diaphragm and electrolyte of battery.
20. a kind of polymer Li-ion battery according to claim 19, which is characterized in that the just extremely cobalt acid lithium
(LiCoO2), LiMn2O4 (LiMn2O4), nickel ion doped (LiNixMn2-xO4), LiFePO4 (or ferric phosphate) (LiFePO4/
FePO4) and ternary material nickle cobalt lithium manganate (NCM), vanadic anhydride (V2O5), molybdenum trioxide (MoO3) one of or it is more
Kind.
21. a kind of polymer Li-ion battery according to claim 19, which is characterized in that the cathode selection graphite,
One or more of hard carbon, silicon, Si oxide, tin alloy, lithium metal and lithium alloy.
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| CN113889663A (en) * | 2021-10-09 | 2022-01-04 | 北京化工大学 | Composite structure gel polymer electrolyte for lithium battery and preparation method and application thereof |
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| CN114142099A (en) * | 2021-11-24 | 2022-03-04 | 蜂巢能源科技有限公司 | Preparation method of composite solid electrolyte membrane and electrochemical energy storage device |
| CN116169352A (en) * | 2023-02-13 | 2023-05-26 | 北京纯锂新能源科技有限公司 | Fluorinated cross-linked polymer film, preparation method and all-solid-state battery |
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| CN116960575A (en) * | 2023-08-08 | 2023-10-27 | 沧州中孚新能源材料有限公司 | High-strength gel electrolyte diaphragm and preparation method and application thereof |
| CN117736388A (en) * | 2024-02-21 | 2024-03-22 | 瑞浦兰钧能源股份有限公司 | Porous buffer material, secondary battery and preparation method of secondary battery |
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