CN110459823A - A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode - Google Patents
A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode Download PDFInfo
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- CN110459823A CN110459823A CN201910758015.7A CN201910758015A CN110459823A CN 110459823 A CN110459823 A CN 110459823A CN 201910758015 A CN201910758015 A CN 201910758015A CN 110459823 A CN110459823 A CN 110459823A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode.Method includes the following steps: (1) oxetane monomers prepare polymer under atmosphere of inert gases, ice-water bath, with boron trifluoride ether solution initiation in a manner of cation ring-opening polymerization；(2) polymer obtained and electrolytic salt are dissolved in nonaqueous solvents or after polymer mix with inorganic particle, electrolytic salt are added, each component dissolves uniformly mixed at room temperature；(3) above-mentioned mixed liquor is coated on diaphragm by modes such as blade coating, spin coating, sprayings with certain thickness, makes membrane surface uniform fold one layer of polymeric；(4) it is applied to metal battery cathode after the diaphragm drying after modifying cement-based powder material to protect, enhances metal negative electrode surface stability, reduce battery polarization voltage, realization battery recycles steadily in the long term.
Description
Technical field
This patent disclosure relates generally to field of batteries, and in particular to a kind of polymer-modified diaphragm is protected for metal battery cathode
Method
Background technique
For new-energy automobile field, the development trend of power battery is just towards the higher direction of safer, energy density
Development.The theoretical specific capacity for the graphite cathode material being commonly used is only 372mAhg-1, much it is unable to satisfy high specific energy
The design requirement of battery, and lithium an- ode has height ratio capacity (3860mAhg-1) and low redox potential (- 3.04V
Vs. standard hydrogen electrode), itself has splendid electric conductivity again, therefore is a kind of ideal lithium ion battery negative material, simultaneously
Sodium metal has advantage similar with lithium, theoretical specific capacity 1165mAhg-1, electrochemical potentials are -2.714V and price is low
It is honest and clean.However lithium metal, metallic sodium etc. in use lithium metal due to its extremely strong reproducibility, can and electrolyte in it is organic
Solvent reacts, in one layer of fragile solid electrolyte film (SEI) of its Surface Creation, SEI membrane mass transfer inhomogeneities and electric current
The influence of density, cause lithium can not uniform deposition, generate dendrite, the fracture of dendrite and fall off and will cause " dead lithium ", " dead sodium "
The problems such as, the dendrite for causing the capacitance loss of battery and cycle life to shorten, while constantly growing can pierce through diaphragm and cause seriously
Security risk.
In order to solve these problems existing for metal negative electrode, scientific research personnel mainly in terms of following four dendrite inhibition life
At: first is that directly improving the stability of solid electrolyte SEI film by adjusting electrolysis additive；Second is that Multifunctional protective sheath
Building, the especially application of the solid electrolyte with high mechanical modulus；Third is that 3D collector guides metal ion uniform deposition；
Fourth is that construction clad metal electrode.Although the above method inhibits the generation of metallic dendrite to a certain extent, applying
It is restricted in journey, such as the techniques such as 3D collector and composite metal negative pole are more complex；Multifunctional protective sheath, patent
In 105789695A, Guo etc. in a kind of composite polymer electrolyte of lithium piece surface structure for battery cathode by protecting.This hair
The bright a kind of method being intended to through polymer-modified diaphragm promotes the uniformity of lithium metal deposition, polarizing voltage is effectively reduced, and presses down
The growth of dendrite processed promotes the cycle life and security performance of lithium metal battery.
Summary of the invention
The first purpose of the invention is to provide it is a kind of with protection metal battery cathode function polymer dielectric,
The polymer is prepared by cation ring-opening polymerization mode, and polymer obtained is miscible with inorganic particle and electrolytic salt respectively
Afterwards, for modifying diaphragm.
A second object of the present invention is to provide a kind of methods for protecting metal negative electrode by modification diaphragm, by that will gather
It closes object decorating liquid and membrane surface, assembled battery is coated on controllable thickness with the modes such as blade coating, spin coating, spraying.This method
Easy to operate, at low cost, the diaphragm after cement-based powder material modification assembles metal Symmetrical cells, and battery polarization voltage is small and stable circulation
Property is good.
The method that a kind of polymer-modified diaphragm of the invention is used for the protection of metal battery cathode, this method includes following step
It is rapid:
(1) oxetane monomer is dissolved in organic solvent, under atmosphere of inert gases, ice-water bath, use is borontrifluoride
Borate ether solution causes, and polymer is prepared in a manner of cation ring-opening polymerization；Organic solvent can for methylene chloride, ethyl alcohol,
Toluene, tetrahydrofuran etc..
(2) by the electrolytic salt of polymer obtained and different quality containing be added in nonaqueous solvents or polymer with
It is mixed again with electrolytic salt after the mixing of different quality containing inorganic particle, each component dissolution at room temperature is uniformly mixed.
(3) by above-mentioned mixed liquor by the modes such as blade coating, spin coating, spraying with controllable thickness be coated on diaphragm on, make every
Film surface uniform fold one layer of polymeric.
(4) after the diaphragm drying after modifying cement-based powder material, it is symmetrical that metal is assembled in esters or ethers electrolyte respectively
Battery.
For described in step (1), oxetane monomer is 3- substituent methyl oxetanes (HMO), 3- (2- itrile group second
Oxygroup) methyl -3 '-methy oxetane (CMMO), 3- (methoxyl group triethoxy) methyl -3 '-methy oxetane
(MEMO) or 3- (2- acryloyloxymethyl) -3 '-methy oxetanes (AMO) etc., such monomer are poly- through cationic open loop
Polyether-based polymers can be obtained after conjunction.Preferably 3- substituent methyl oxetanes (HMO).
For described in step (1), initiator boron trifluoride in the solubility range in ether between 0.02~0.4g/ml,
The molar ratio of initiator boron trifluoride and oxetane monomer is between 1:2000~1:100.
For described in step (1), inert gas is nitrogen or argon gas, inert gas flow 0.1-40L/h
(101325Pa, 20 DEG C), ice water bath temperature are 0~10 DEG C, and when reaction adds magnetic agitation, and magneton mixing speed is 100rpm-
1000rpm.It is highly preferred that inert gas is nitrogen；Inert gas flow is 1-10L/h (101325Pa, 20 DEG C), magneton stirring
Speed is 400rpm-800rpm.
For described in step (2), electrolytic salt can refer to metal ion or ammonium ion (NH4+) with acid ion or nonmetallic
Ions binding, the conductive compound of energy under solution or molten condition.Further, electrolytic salt is lithium salts, sodium salt, magnesium
At least one of salt, aluminium salt and sylvite etc..Under concrete condition, the lithium salts is double difluoro sulfimide lithium (LiFSI), double three
Methyl fluoride sulfimide lithium (LiTFSI), lithium perchlorate (LiClO4), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6)
And lithium hexafluoro phosphate (LiPF6At least one of)；The sodium salt is sodium perchlorate (NaClO4), double difluoro sulfimide sodium
(NaFSI), bis trifluoromethyl sulfimide sodium (NaTFSI), sodium tetrafluoroborate (NaBF4), hexafluoroarsenate lithium (NaAsF6) and six
Lithium fluophosphate (NaPF6At least one of)；The aluminium salt is aluminium chloride (AlCl3), 1- ethyl-3-methylimidazole aluminium salt
(EMIm) and 1- butyl -3- methylimidazole aluminium salt (BMIm)；The sylvite is Potassium Hexafluorophosphate (KPF6), bis- (fluorosulfonyls) it is sub-
Amine potassium (KFSI) and potassium carbonate (K2CO3).It is highly preferred that lithium salts is bis trifluoromethyl sulfimide lithium (LiTFSI), sodium salt is double
Trifluoromethanesulp-onyl -onyl imide sodium (NaTFSI), aluminium salt are 1- butyl -3- methylimidazole aluminium salt (BMIm), and sylvite is Potassium Hexafluorophosphate
(KPF6)。
For described in step (2), inorganic particle is that LiSICON type, NaSICON type, carbuncle type, Ca-Ti ore type etc. are inorganic
The inorganic particulates such as solid electrolyte or silica, titanium dioxide and aluminum oxide, but it is not limited only to this.Preferably, inorganic
Particle is LISICON type solid electrolyte Li1+xAlxGe2-x(PO4)3(LAGP)。
For described in step (2), electrolytic salt described in step (2) and polymer (polymer and inorganic particle mixture)
Mass ratio between 0.1~2, the ratio between inorganic particle and polymer quality are between 0.01~0.1.Under preferable case, institute
The mass ratio of the electrolytic salt and polymer (polymer and inorganic particle mixture) stated is 1, inorganic particle and polymeric material
The ratio between amount is 0.05.
For described in step (2), nonaqueous solvents be methanol, ethyl alcohol, propyl alcohol, ethylene glycol, acetone, butyl ester, glycerol, pyridine,
At least one of propane, acetic acid, tetrahydrofuran, n,N-dimethylacetamide, preferably dehydrated alcohol.
It is controllable with a thickness of 25 μm -300 μm for described in step (3), more preferably 25 μm -75 μm.
For described in step (4), diaphragm include PP film, PE film, PP/PE film, PP/PE/PP film, glass fibre element diaphragm and
Nonwoven cloth diaphragm etc..Preferably, diaphragm is PP film.
For described in step (4), drying process process can be vacuum, it is also possible to antivacuum, temperature may be provided at 20
DEG C -200 DEG C, drying time 0.5h~48h；Under preferable case, drying temperature is 60 DEG C -120 DEG C, drying time 8h-24h.
For described in step (4), esters electrolyte can be ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid two
One of methyl esters (DMC), propene carbonate (PC) or several combinations and the mixed solution of corresponding electrolyte, preferably
LiPF6+ ethylene carbonate (EC)+diethyl carbonate (DEC), wherein for EC and DEC as solvent, the volume ratio of EC:DEC is 1:
0.9-1.1, LiPF6Concentration in a solvent is 0.8-1.1M；Ethers electrolyte can be glycol dimethyl ether (DME), 1,3-
The combination of one or more of dioxolanes (DOL), diphenyl ether (DPE) and the mixed solution of corresponding electrolyte, preferably
LiTFSI+ glycol dimethyl ether (DME)+1,3- dioxolanes (DOL)+lithium nitrate (LiNO3), the wherein volume ratio of DME:DOL
For 1:0.9-1.1, the concentration of LiTFSI in a solvent is 0.8-1.1M, LiNO3As additive, the concentration in system is 3-
5wt%.
For described in step (4), metal is the alkali or alkaline earth metals classes such as lithium, sodium, aluminium, magnesium, potassium, calcium in metal battery
Element, more preferably lithium.
The invention has the following beneficial technical effects:
First, oxetane monomer at inert atmosphere, 0~10 DEG C of ice-water bath, is dissolved in organic solvent by the present invention
In, cation ring-opening polymerization is carried out with boron trifluoride ether solution initiation, polymerizate passes through multiple dissolution-precipitating-dissolution
Homopolymer is made in process.There is the polymer ether-oxygen bond functional group can provide higher power supply subnumber, can match with metal ion
It can be uniformly distributed and deposit with polymer segment displacement after position, metal ion and polymer complex, it is poly- to improve metal ion
Collect phenomenon, inhibits the generation of metallic dendrite.
Second, in the present invention polymer-modified layer by the modes such as blade coating, spin coating, spraying with controllable thickness (25 μm-
300 μm) it is evenly applied to membrane surface, after solvent vaporization at high temperature, a thin layer of polymer-modified of membrane surface uniform fold
Layer, the polymer-modified thickness degree after drying is only 5-7 μm.The controllable decorative layer thickness of controllable polymer-coated thickness, just
In determining optimal value.
Third, the diaphragm in the present invention after the modification of very thin polymeric layer assemble metal battery, it is negative not to increase battery component
It carries on a shoulder pole and preparation method is simple, it is at low cost.
4th, method of the polymer-modified diaphragm provided by the invention for the protection of metal battery cathode can reduce metal
Symmetrical cells polarizing voltage enhances circulating battery stability.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the 3 75 polymer-modified diaphragm of μ m thick PHMO of embodiment and comparative example 1 without modification diaphragm assembling
CR2025 tests polarizing voltage figure of the button cell in ethers electrolyte.
Fig. 2 is that embodiment 7PHMO-5wt%LAGP mixture modifies diaphragm and comparative example 2 without modification diaphragm assembling
CR2025 tests polarizing voltage figure of the button cell in esters electrolyte.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In following embodiment and comparative example, glove box is German Braun LABSTAR (1950/780) model, purchased from Germany
Braun inert gas system Co., Ltd；LAND CT2001A tester is purchased from Wuhan Land Electronic Co., Ltd..
Embodiment 1
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
(1) under ice-water bath, 2ml dichloromethane solvent is injected into 25ml with syringe, in the round-bottomed flask full of argon gas；
Initiator boron trifluoride ether solution is injected into reaction flask with microsyringe, wherein initiator boron trifluoride and list
Body molar ratio is 1:1000, and initiator solution injection rate is 0.1ml, and magneton injects 2.5g 3- substituent methyl oxygen after stirring 5min
Azetidine (HMO).
(2) 12h is reacted into above-mentioned reaction under nitrogen protection, obtained polymer using dehydrated alcohol as solvent, with just oneself
Alkane is precipitating reagent, and three times, product is placed in 80 DEG C of dryings of vacuum for 24 hours to repeated precipitation-dissolution-precipitating, after polymer P HMO solid
With spare.
(3) 0.25g LiTFSI salt is weighed in glove box, and 200ul dehydrated alcohol is added sufficiently to dissolve.
(4) 0.25g PHMO polymer is weighed, is added in step (3) mixed solution, adds 800ul dehydrated alcohol,
Polymer is set sufficiently to be dissolved to solution under magneton stirring slightly sticky.
(5) viscous solution will be omited obtained by step (4) to be evenly applied on PP diaphragm with scraper, coating thickness is 25 μm.
(6) by the diaphragm for being coated with polymer-modified layer be placed in 80 DEG C of vacuum ovens it is dry for 24 hours, after drying will be every
Film is cut into 19mm diameter, battery to be assembled.
(7) with lithium piece be respectively anode and cathode, it is polymer-modified after PP film make diaphragm, electrolyte is electrolysed with ethers
Liquid: 1M LiTFSI+ glycol dimethyl ether (DME)+1,3- dioxolanes (DOL)+5wt% lithium nitrate (LiNO3), wherein DME:
The volume ratio of DOL is 1:1, and model CR2025 experiment button cell is assembled into the glove box full of argon atmosphere, is stood
It is tested on LAND CT2001A tester after 12h.
Embodiment 2
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
According to method described in embodiment 1, the difference is that, coating thickness is changed to 50 μm in step (5).
Embodiment 3
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
According to method described in embodiment 1, the difference is that, coating thickness is changed to 75 μm in step (5).
Embodiment 4
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
According to method described in embodiment 1, the difference is that electrolyte esters electrolyte in step (7): 1M LiPF6+ ethylene carbonate
(EC)+diethyl carbonate (DEC), wherein the volume ratio of EC:DEC is 1:1.
Embodiment 5
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
According to method as described in example 4, the difference is that, inorganic solid electrolyte is not added in step (4) is changed to addition
Mass fraction is changed to the LiSICON type inorganic solid electrolyte LAGP of 1% (mass ratio with PHMO polymer is 0.01).
Embodiment 6
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
According to method described in embodiment 5, the difference is that, LiSICON type inorganic solid electrolyte LAGP matter in step (4)
Amount score is changed to 3%.
Embodiment 7
The present embodiment is used to illustrate a kind of method of polymer-modified diaphragm of the invention for the protection of metal battery cathode.
According to method described in embodiment 5, the difference is that, LiSICON type inorganic solid electrolyte LAGP matter in step (4)
Amount score is changed to 5%.
Comparative example 1
This comparative example acts on metal battery cathode unprotect without polymer-modified diaphragm for illustrating.
(1) PP diaphragm is placed in drying in 80 DEG C of vacuum ovens and for 24 hours, it is big that diaphragm is cut into 19mm diameter after drying
It is small, battery to be assembled.
It (2) is respectively that anode and cathode, PP film do diaphragm, electrolyte ethers electrolyte: 1MLiTFSI+ second two with lithium piece
Diethylene glycol dimethyl ether (DME)+1,3- dioxolanes (DOL)+5wt% lithium nitrate (LiNO3), wherein the volume ratio of DME:DOL is 1:1,
Full of argon atmosphere glove box in be assembled into model CR2025 experiment button cell, stand 12h after in LAND
It is tested on CT2001A tester.
Comparative example 2
This comparative example acts on metal battery cathode unprotect without polymer-modified diaphragm for illustrating.
(1) PP diaphragm is placed in drying in 80 DEG C of vacuum ovens and for 24 hours, it is big that diaphragm is cut into 19mm diameter after drying
It is small, battery to be assembled.
It (2) is respectively that anode and cathode, PP film do diaphragm, electrolyte esters electrolyte: 1MLiPF with lithium piece6+ carbonic acid
Vinyl acetate (EC)+diethyl carbonate (DEC), wherein the volume ratio of EC:DEC is 1:1, the group in the glove box full of argon atmosphere
Model CR2025 experiment button cell is dressed up, is tested on LAND CT2001A tester after standing 12h.
Table 1: metal Symmetrical cells stablize after-polarization voltage and circulation duration table in embodiment and comparative example
By the result of embodiment 1-3 and comparative example 1 can be seen that the embodiment of the present invention 1-3 it is polymer-modified after
Polarizing voltage of the lithium metal Symmetrical cells of diaphragm assembling in ethers electrolyte is stablized in 15mV-20mV, hence it is evident that is less than comparison
Metal battery of the example 1 without modification diaphragm；Lithium metal Symmetrical cells after modifying diaphragm simultaneously can stablize circulation 1000h or more, surely
Surely circulation duration is unmodified metal battery more than twice.
By the result of embodiment 4-7 and comparative example 2 can be seen that the embodiment of the present invention 4-7 it is polymer-modified after
Polarizing voltage of the lithium metal Symmetrical cells of diaphragm assembling in esters electrolyte is stablized in 50mV or so, hence it is evident that is less than comparative example
The 2 metal Symmetrical cells without modification diaphragm；Lithium metal Symmetrical cells cyclical stability after modifying diaphragm simultaneously is better than unmodified
Battery.Above embodiments explanation, by the method for polymer-modified diaphragm, can improve lithium metal surface nonuniform deposition, hence it is evident that
Reduce polarizing voltage, enhances metal Symmetrical cells cyclical stability.
By embodiment 1-7 result can be seen that 1-3 of the embodiment of the present invention it is polymer-modified after diaphragm assembling lithium gold
Belong to Symmetrical cells and is less than polarizing voltage of the embodiment 4-7 in esters electrolyte, and its in the polarizing voltage in ethers electrolyte
Cyclical stability is better than in esters electrolyte.This is the result is that due to compared to esters electrolyte, ethers electrolyte itself is right
Lithium metal is more stable.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode, which is characterized in that this method includes following
Step:
(1) oxetane monomer is dissolved in organic solvent, under atmosphere of inert gases, ice-water bath, with boron trifluoride second
Ethereal solution causes, and polymer is prepared in a manner of cation ring-opening polymerization；
(2) it by polymer obtained or polymer and inorganic particle mixture, is dissolved in nonaqueous solvents with electrolytic salt, at room temperature
Dissolution is uniformly mixed；
(3) above-mentioned mixed liquor is coated on diaphragm by blade coating, spin coating or spraying method with controllable thickness, makes membrane surface
Uniform fold one layer of polymeric；
(4) after the diaphragm drying after modifying cement-based powder material, metal Symmetrical cells are assembled in esters or ethers electrolyte respectively.
2. according to the method described in claim 1, oxetane monomer described in step (1) is 3- substituent methyl oxa- ring
Butane (HMO), 3- (2- itrile group ethyoxyl) methyl -3 '-methy oxetane (CMMO), 3- (methoxyl group triethoxy) first
Base -3 '-methy oxetane (MEMO) or 3- (2- acryloyloxymethyl) -3 '-methy oxetanes (AMO).
3. according to the method described in claim 1, electrolytic salt described in step (2) be selected from lithium salts, sodium salt, magnesium salts, aluminium salt and
At least one of sylvite.
4. according to the method described in claim 1, electrolytic salt described in step (2) and polymer or polymer and inorganic particle
The mass ratio of mixture is between 0.1~2, and the ratio between inorganic particle and polymer quality are between 0.01~0.1.
5. according to the method described in claim 1, nonaqueous solvents described in step (2) be methanol, ethyl alcohol, propyl alcohol, ethylene glycol,
At least one of acetone, butyl ester, glycerol, pyridine, propane, acetic acid, tetrahydrofuran, DMAC N,N' dimethyl acetamide.
6. according to the method described in claim 1, controllable with a thickness of 25 μm -300 μm described in step (3).
7. according to the method described in claim 1, diaphragm described in step (3) includes polypropylene (PP) film, polyethylene (PE)
Film, bilayer PP/PE composite membrane, three layers of PP/PE/PP composite membrane, glass fibre element diaphragm and nonwoven cloth diaphragm.
8. according to the method described in claim 1, esters electrolyte includes ethylene carbonate (EC), carbonic acid diethyl in step (4)
One of ester (DEC), dimethyl carbonate (DMC), propene carbonate (PC) or several combinations.
9. according to the method described in claim 1, ethers electrolyte includes glycol dimethyl ether (DME), 1,3- in step (4)
One of dioxolanes (DOL), diphenyl ether (DPE) or several combinations.
10. according to the method described in claim 1, in metal Symmetrical cells described in step (4) metal be lithium, sodium, aluminium, magnesium,
Potassium or calcium.
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| CN110429333B (en) * | 2019-07-29 | 2021-02-02 | 北京理工大学 | All-solid-state sodium ion battery and composite polymer electrolyte thereof |
| CN112133867A (en) * | 2020-08-17 | 2020-12-25 | 浙江工业大学 | Self-assembled monolayer modified alumina diaphragm and preparation and application thereof |
| CN112133867B (en) * | 2020-08-17 | 2023-04-07 | 浙江工业大学 | Self-assembled monolayer modified alumina diaphragm and preparation and application thereof |
| CN112226064A (en) * | 2020-10-12 | 2021-01-15 | 东北师范大学 | Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery |
| CN112226064B (en) * | 2020-10-12 | 2023-02-10 | 吉林省东驰新能源科技有限公司 | Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery |
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