CN110459823B - Method for applying polymer modified diaphragm to metal battery negative electrode protection - Google Patents

Method for applying polymer modified diaphragm to metal battery negative electrode protection Download PDF

Info

Publication number
CN110459823B
CN110459823B CN201910758015.7A CN201910758015A CN110459823B CN 110459823 B CN110459823 B CN 110459823B CN 201910758015 A CN201910758015 A CN 201910758015A CN 110459823 B CN110459823 B CN 110459823B
Authority
CN
China
Prior art keywords
polymer
diaphragm
metal
battery
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910758015.7A
Other languages
Chinese (zh)
Other versions
CN110459823A (en
Inventor
白莹
吴锋
张锟
吴川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN201910758015.7A priority Critical patent/CN110459823B/en
Publication of CN110459823A publication Critical patent/CN110459823A/en
Application granted granted Critical
Publication of CN110459823B publication Critical patent/CN110459823B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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

A method for using a polymer modified diaphragm for metal battery negative electrode protection. The method comprises the following steps: (1) under the inert gas atmosphere and ice water bath, initiating an oxetane monomer by using boron trifluoride-diethyl ether solution to prepare a polymer in a cation ring-opening polymerization mode; (2) dissolving the prepared polymer and electrolyte salt in a non-aqueous solvent, or mixing the polymer and inorganic particles, adding the electrolyte salt, and dissolving and uniformly mixing the components at room temperature; (3) coating the mixed solution on a diaphragm in a certain thickness by blade coating, spin coating, spray coating and other modes to uniformly cover a layer of polymer on the surface of the diaphragm; (4) the diaphragm modified by the polymer is dried and then applied to the protection of the metal battery cathode, so that the surface stability of the metal cathode is enhanced, the polarization voltage of the battery is reduced, and the long-term stable circulation of the battery is realized.

Description

Method for applying polymer modified diaphragm to metal battery negative electrode protection
Technical Field
The invention relates to the field of batteries in general, and in particular relates to a method for protecting a metal battery cathode by using a polymer modified diaphragm
Background
For the field of new energy automobiles, the development trend of power batteries is developing towards safer and higher energy density. The theoretical specific capacity of the graphite negative electrode material commonly used at present is only 372mAh g-1Far from meeting the design requirement of high specific energy battery, while the lithium metal cathode has high specific capacity (3860mAh g)-1) And a low oxidation-reduction potential (-3.04V vs. standard hydrogen electrode), and has excellent conductivity, so that the material is an ideal lithium ion battery cathode material, and simultaneously, sodium metal has the advantages similar to lithium, and the theoretical specific capacity is 1165mAh g-1The electrochemical potential is-2.714V and the price is low. However, in the using process of lithium metal, sodium metal and the like, lithium metal reacts with an organic solvent in an electrolyte due to extremely strong reducibility of the lithium metal and the sodium metal, a layer of fragile Solid Electrolyte Interface (SEI) is generated on the surface of the lithium metal, the SEI is affected by mass transfer nonuniformity and current density, lithium cannot be uniformly deposited, dendrite is generated, the problems of 'dead lithium' and 'dead sodium' are caused by fracture and shedding of the dendrite, and the capacity of the battery is causedLosses and cycle life are shortened while growing dendrites can pierce the membrane causing serious safety concerns.
In order to solve these problems of the metal negative electrode, researchers mainly suppress the generation of dendrites from four aspects: firstly, the stability of the solid electrolyte SEI film is directly improved by adjusting the electrolyte additive; the construction of a multifunctional protective layer, in particular to the application of a solid electrolyte with high mechanical modulus; thirdly, the 3D current collector guides metal ions to be uniformly deposited; fourthly, constructing the composite metal electrode. Although the method inhibits the generation of metal dendrites to a certain extent, the method is limited in the application process, and processes such as a 3D current collector and a composite metal negative electrode are complex; multifunctional protective layers, Guo et al in patent 105789695a, are used for battery negative electrode protection by structuring a composite polymer electrolyte on the surface of a lithium sheet. The invention aims to improve the uniformity of lithium metal deposition, effectively reduce polarization voltage, inhibit the growth of dendritic crystals and improve the cycle life and safety performance of a lithium metal battery by a method for modifying a diaphragm by a polymer.
Disclosure of Invention
The first purpose of the invention is to provide a polymer electrolyte with the function of protecting the negative electrode of a metal battery, wherein the polymer is prepared in a cation ring-opening polymerization mode, and the prepared polymer is respectively mixed with inorganic particles and electrolyte salt for modifying a diaphragm.
The second purpose of the invention is to provide a method for protecting a metal cathode by modifying a diaphragm, wherein a polymer modification liquid is coated on the surface of the diaphragm in a controllable thickness by blade coating, spin coating, spray coating and the like, so as to assemble a battery. The method is simple to operate and low in cost, and the metal symmetrical battery is assembled by the diaphragm modified by the polymer, so that the battery has small polarization voltage and good cycling stability.
The invention discloses a method for protecting a metal battery cathode by a polymer modified diaphragm, which comprises the following steps:
(1) dissolving an oxetane monomer in an organic solvent, initiating by using boron trifluoride-diethyl ether solution in an inert gas atmosphere and an ice water bath, and preparing a polymer in a cationic ring-opening polymerization mode; the organic solvent may be dichloromethane, ethanol, toluene, tetrahydrofuran, etc.
(2) Adding the prepared polymer and electrolyte salt with different mass fractions into a non-aqueous solvent, or mixing the polymer and inorganic particles with different mass fractions and then mixing the mixture with the electrolyte salt, and dissolving and uniformly mixing the components at room temperature.
(3) The mixed solution is coated on the diaphragm in a controllable thickness by blade coating, spin coating, spray coating and other modes, so that the surface of the diaphragm is uniformly covered with a layer of polymer.
(4) And drying the diaphragm modified by the polymer, and respectively assembling the metal symmetrical battery in ester or ether electrolyte.
In the step (1), the oxetane monomer is 3-substituted methyloxetane (HMO), 3- (2-cyanoethoxy) methyl-3 ' -methyloxetane (CMMO), 3- (methoxytriethoxy) methyl-3 ' -methyloxetane (MEMO), 3- (2-acryloyloxymethyl) -3 ' -methyloxetane (AMO), or the like, and the polyether polymer can be obtained by cationic ring-opening polymerization of such monomer. 3-substituted methyloxetanes (HMOs) are preferred.
For the step (1), the solubility range of the initiator boron trifluoride in diethyl ether is 0.02-0.4 g/ml, and the molar ratio of the initiator boron trifluoride to the oxetane monomer is 1: 2000-1: 100.
And (2) as for the step (1), the inert gas is nitrogen or argon, the flow rate of the inert gas is 0.1-40L/h (101325Pa, 20 ℃), the temperature of the ice water bath is 0-10 ℃, magnetic stirring is carried out during reaction, and the stirring speed of magnetons is 100-1000 rpm. More preferably, the inert gas is nitrogen; the flow rate of the inert gas is 1-10L/h (101325Pa, 20 ℃), and the stirring speed of the magnetons is 400-800 rpm.
As for step (2), the electrolyte salt may refer to a metal ion or an ammonium ion (NH)4+) A compound capable of conducting electricity in a solution or molten state in combination with an acid ion or a non-metal ion. Further, the electrolyte salt is at least one of a lithium salt, a sodium salt, a magnesium salt, an aluminum salt, a potassium salt, and the like. In a specific case, the lithium salt is difluoroLithium sulfonimide (LiFSI), lithium bistrifluoromethylsulfonimide (LiTFSI), lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) And lithium hexafluorophosphate (LiPF)6) At least one of; the sodium salt is sodium perchlorate (NaClO)4) Sodium bis (difluorosulfonimide) (NaFSI), sodium bis (trifluoromethylsulfonimide) (NaTFSI), and sodium tetrafluoroborate (NaBF)4) Lithium hexafluoroarsenate (NaAsF)6) And lithium hexafluorophosphate (NaPF)6) At least one of; the aluminum salt is aluminum chloride (AlCl)3) 1-ethyl-3-methylimidazolium salt (EMIm) and 1-butyl-3-methylimidazolium salt (BMIm); the potassium salt is potassium hexafluorophosphate (KPF)6) Potassium bis (fluorosulfonyl) imide (KFSI) and potassium carbonate (K)2CO3). More preferably, the lithium salt is lithium bistrifluoromethylsulfonyl imide (LiTFSI), the sodium salt is sodium bistrifluoromethylsulfonyl imide (NaTFSI), the aluminum salt is 1-butyl-3-methylimidazolium salt (BMIm), and the potassium salt is potassium hexafluorophosphate (KPF)6)。
In the step (2), the inorganic particles are inorganic solid electrolytes such as LiSICON type, NaSICON type, garnet type and perovskite type, or inorganic particles such as silica, titania and alumina, but not limited thereto. Preferably, the inorganic particles are LISICON-type solid electrolytes Li1+xAlxGe2-x(PO4)3(LAGP)。
In the step (2), the mass ratio of the electrolyte salt to the polymer (mixture of the polymer and the inorganic particles) in the step (2) is 0.1 to 2, and the mass ratio of the inorganic particles to the polymer is 0.01 to 0.1. Preferably, the mass ratio of the electrolyte salt to the polymer (mixture of the polymer and the inorganic particles) is 1, and the mass ratio of the inorganic particles to the polymer is 0.05.
The non-aqueous solvent used in step (2) is at least one selected from methanol, ethanol, propanol, ethylene glycol, acetone, butyl ester, glycerol, pyridine, propane, acetic acid, tetrahydrofuran and N, N-dimethylacetamide, and preferably is absolute ethanol.
For step (3), the thickness is controlled to be 25 μm to 300. mu.m, more preferably 25 μm to 75 μm.
The diaphragm in the step (4) includes a PP film, a PE film, a PP/PE/PP film, a glass cellulose diaphragm, a non-woven fabric diaphragm and the like. Preferably, the separator is a PP film.
As for the step (4), the drying process can be vacuum or non-vacuum, the temperature can be set to be 20-200 ℃, and the drying time is 0.5-48 h; preferably, the drying temperature is 60-120 ℃, and the drying time is 8-24 h.
For the step (4), the ester electrolyte may be a mixed solution of one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and Propylene Carbonate (PC) with a corresponding electrolyte, preferably LiPF6+ Ethylene Carbonate (EC) + diethyl carbonate (DEC), with EC and DEC as solvents, with a volume ratio of EC to DEC of 1:0.9-1.1, LiPF6The concentration in the solvent is 0.8-1.1M; the ether electrolyte can be a mixed solution of one or more of ethylene glycol dimethyl ether (DME), 1, 3-Dioxolane (DOL) and diphenyl ether (DPE) and corresponding electrolyte, and preferably LiTFSI + ethylene glycol dimethyl ether (DME) +1, 3-Dioxolane (DOL) + lithium nitrate (LiNO)3) Wherein the volume ratio of DME to DOL is 1:0.9-1.1, the concentration of LiTFSI in the solvent is 0.8-1.1M, and LiNO3As an additive, the concentration in the system is 3 to 5 wt%.
In the step (4), the metal in the metal battery is an alkali metal or alkaline earth metal element such as lithium, sodium, aluminum, magnesium, potassium, calcium, and more preferably lithium.
The invention has the following beneficial technical effects:
firstly, dissolving an oxetane monomer in an organic solvent under an inert atmosphere and at a temperature of 0-10 ℃ in an ice water bath, initiating by using boron trifluoride-diethyl ether solution to carry out cationic ring-opening polymerization, and carrying out multiple dissolving-precipitating-dissolving processes on a polymerization product to obtain a homopolymer. The polymer has an ether oxygen bond functional group, can provide a higher electron supply number, can coordinate with metal ions, can directionally move along with a polymer chain segment after the metal ions are coordinated with the polymer, is uniformly distributed and deposited, improves the aggregation phenomenon of the metal ions, and inhibits the generation of metal dendritic crystals.
Secondly, the polymer modification layer is uniformly coated on the surface of the diaphragm in a controllable thickness (25-300 microns) by blade coating, spin coating, spray coating and the like, after the solvent is volatilized at high temperature, the thin polymer modification layer is uniformly coated on the surface of the diaphragm, and the thickness of the dried polymer modification layer is only 5-7 microns. The controllable polymer coating thickness can regulate the thickness of the modified layer, so that an optimal value can be determined conveniently.
Thirdly, the metal battery is assembled by the diaphragm modified by the extremely thin polymer layer, the burden of a battery component is not increased, the preparation method is simple, and the cost is low.
Fourthly, the method for protecting the metal battery cathode by using the polymer modified diaphragm provided by the invention can reduce the polarization voltage of the metal symmetrical battery and enhance the cycling stability of the battery.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is a polarization voltage diagram of a CR2025 experimental coin cell assembled by a PHMO polymer modified separator with a thickness of 375 μm according to example and an unmodified separator according to comparative example 1 in an ether electrolyte.
FIG. 2 is a graph of the polarization voltage of the CR2025 experimental coin cell assembled with the PHMO-5 wt% LAGP mixture modified diaphragm of example 7 and the unmodified diaphragm of comparative example 2 in an ester electrolyte.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the following examples and comparative examples, the glove box was a Braun LABSTAR model (1950/780) from Braun inert gas systems, Inc., Germany; the LAND CT2001A tester was purchased from blue electronics, Inc., Wuhan, Inc.
Example 1
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection.
(1) In an ice-water bath, 2ml of dichloromethane solvent was injected into a 25ml round-bottom flask filled with argon gas by a syringe; a boron trifluoride-diethyl ether solution as an initiator was poured into a reaction flask by a microsyringe in a molar ratio of 1:1000 between the boron trifluoride and the monomer as an initiator and in an amount of 0.1ml, and 2.5g of 3-substituted methyloxetane (HMO) was poured after stirring with magnetons for 5 min.
(2) And (3) reacting the reaction for 12h under the protection of nitrogen, repeatedly precipitating, dissolving and precipitating the obtained polymer for three times by using absolute ethyl alcohol as a solvent and n-hexane as a precipitator, and drying the product at the vacuum temperature of 80 ℃ for 24h to obtain a polymer PHMO solid for later use.
(3) 0.25g of LiTFSI salt was weighed out in a glove box and dissolved thoroughly in 200ul of absolute ethanol.
(4) 0.25g of PHMO polymer is weighed and added into the mixed solution in the step (3), then 800ul of absolute ethyl alcohol is added, and the polymer is fully dissolved under the stirring of magnetons until the solution is slightly viscous.
(5) And (5) uniformly coating the slightly viscous solution obtained in the step (4) on a PP diaphragm by using a scraper, wherein the coating thickness is 25 mu m.
(6) And (3) drying the diaphragm coated with the polymer modification layer in a vacuum drying oven at 80 ℃ for 24h, cutting the diaphragm into the size of 19mm in diameter after drying is finished, and assembling the battery.
(7) The lithium sheet is respectively used as a positive electrode and a negative electrode, the PP film modified by the polymer is used as a diaphragm, and the electrolyte is ether electrolyte: 1M LiTFSI + ethylene glycol dimethyl ether (DME) +1, 3-Dioxolane (DOL) +5 wt% lithium nitrate (LiNO)3) And assembling a model CR2025 experimental button cell in a glove box filled with argon atmosphere, standing for 12h, and testing on a LAND CT2001A tester, wherein the volume ratio of DME to DOL is 1: 1.
Example 2
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection.
According to the method described in example 1, except that the coating thickness in step (5) was changed to 50 μm.
Example 3
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection.
According to the method described in example 1, except that the coating thickness in step (5) was changed to 75 μm.
Example 4
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection. The process of example 1, except that in step (7) the electrolyte is an ester electrolyte: 1M LiPF6+ Ethylene Carbonate (EC) + diethyl carbonate (DEC), with the volume ratio of EC to DEC being 1: 1.
Example 5
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection.
According to the method described in example 4, except that no inorganic solid electrolyte was added in step (4) instead of adding 1% by mass of the LiSICON-type inorganic solid electrolyte lag (mass ratio to the PHMO polymer is 0.01).
Example 6
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection.
The method according to example 5, except that the LiSICON-type inorganic solid-state electrolyte lag mass fraction in step (4) was 3%.
Example 7
This example illustrates a method of using a polymer modified separator of the present invention for metal battery negative electrode protection.
The method according to example 5, except that the LiSICON-type inorganic solid-state electrolyte lag mass fraction in step (4) was 5%.
Comparative example 1
This comparative example is used to illustrate that the separator, which was not modified with a polymer, did not protect the negative electrode of a metal battery.
(1) And (3) placing the PP diaphragm in a vacuum drying oven at 80 ℃ for drying for 24h, cutting the diaphragm into the diameter of 19mm after drying is finished, and waiting for assembling the battery.
(2) The lithium sheet is respectively used as a positive electrode and a negative electrode, the PP film is used as a diaphragm, and the electrolyte is ether electrolyte: 1MLiTFSI + ethylene glycol dimethyl ether (DME) +1, 3-Dioxolane (DOL) +5 wt% lithium nitrate (LiNO)3) And assembling a model CR2025 experimental button cell in a glove box filled with argon atmosphere, standing for 12h, and testing on a LAND CT2001A tester, wherein the volume ratio of DME to DOL is 1: 1.
Comparative example 2
This comparative example is used to illustrate that the separator, which was not modified with a polymer, did not protect the negative electrode of a metal battery.
(1) And (3) placing the PP diaphragm in a vacuum drying oven at 80 ℃ for drying for 24h, cutting the diaphragm into the diameter of 19mm after drying is finished, and waiting for assembling the battery.
(2) The lithium sheet is respectively used as a positive electrode and a negative electrode, the PP film is used as a diaphragm, and the electrolyte is ester electrolyte: 1MLiPF6The Ethylene Carbonate (EC) and diethyl carbonate (DEC) are assembled into a model CR2025 experimental button cell in a glove box filled with argon gas at a volume ratio of 1:1, and the cell is placed still for 12h and then tested on a LAND CT2001A tester.
Table 1: polarization voltage and cycle length table after metal symmetrical battery stabilization in examples and comparative examples
Figure BDA0002169365830000071
Figure BDA0002169365830000081
As can be seen from the results of examples 1-3 and comparative example 1, the polarization voltage of the lithium metal symmetrical battery assembled by the polymer-modified diaphragm of examples 1-3 of the invention in the ether electrolyte is stabilized at 15mV-20mV, which is obviously smaller than that of the metal battery without the modified diaphragm of comparative example 1; meanwhile, the lithium metal symmetrical battery after the diaphragm is modified can stably circulate for more than 1000 hours, and the stable circulation time is more than twice of that of an unmodified metal battery.
As can be seen from the results of examples 4-7 and comparative example 2, the polarization voltage of the lithium metal symmetrical battery assembled by the polymer-modified diaphragm of examples 4-7 of the invention in the ester electrolyte is stabilized at about 50mV, which is obviously smaller than that of the metal symmetrical battery without the modified diaphragm of comparative example 2; meanwhile, the cycling stability of the lithium metal symmetrical battery after the diaphragm is modified is superior to that of an unmodified battery. The above examples illustrate that the method of modifying the separator with the polymer can improve the uneven deposition on the surface of the lithium metal, significantly reduce the polarization voltage, and enhance the cycling stability of the metal symmetric battery.
It can be seen from the results of examples 1 to 7 that the polarization voltage of the lithium metal symmetric battery assembled by the separator modified by the polymers in examples 1 to 3 of the invention in the ether electrolyte is lower than that of examples 4 to 7 in the ester electrolyte, and the cycling stability of the lithium metal symmetric battery is better than that in the ester electrolyte. This is because the ether electrolyte itself is more stable to lithium metal than the ester electrolyte.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (9)

1. A method for using a polymer modified diaphragm for metal battery negative electrode protection is characterized by comprising the following steps:
(1) dissolving an oxetane monomer in an organic solvent, initiating by using boron trifluoride-diethyl ether solution in an inert gas atmosphere and an ice water bath, and preparing a polymer in a cationic ring-opening polymerization mode;
(2) dissolving the prepared polymer or the mixture of the polymer and the inorganic particles and electrolyte salt in a non-aqueous solvent, and dissolving and mixing uniformly at room temperature;
(3) coating the mixed solution obtained in the step (2) on a diaphragm in a controllable thickness in a blade coating, spin coating or spraying mode, so that the surface of the diaphragm is uniformly covered with a layer of polymer;
(4) drying the diaphragm modified by the polymer, and respectively assembling the metal symmetrical batteries in ester or ether electrolyte;
the oxetane monomer in the step (1) is 3-substituted methyloxetane, 3- (2-cyanoethoxy) methyl-3 ' -methyloxetane, 3- (methoxytriethoxy) methyl-3 ' -methyloxetane or 3- (2-acryloyloxymethyl) -3 ' -methyloxetane;
in the step (1), the solubility range of initiator boron trifluoride in diethyl ether is 0.02-0.4 g/ml, and the molar ratio of initiator boron trifluoride to oxetane monomer is 1: 2000-1: 100; the inert gas is nitrogen or argon, the flow rate of the inert gas is 0.1-40L/h, the temperature of the ice water bath is 0-10 ℃, magnetic stirring is carried out during reaction, and the stirring speed of magnetons is 100-1000 rpm.
2. The method according to claim 1, wherein the electrolyte salt in step (2) is at least one selected from the group consisting of lithium salts, sodium salts, magnesium salts, aluminum salts, and potassium salts.
3. The method according to claim 1, wherein the mass ratio of the electrolyte salt to the polymer or the mixture of the polymer and the inorganic particles in the step (2) is 0.1 to 2, and the mass ratio of the inorganic particles to the polymer is 0.01 to 0.1.
4. The method according to claim 1, wherein the non-aqueous solvent in step (2) is at least one selected from methanol, ethanol, propanol, ethylene glycol, acetone, butyl ester, glycerol, pyridine, propane, acetic acid, tetrahydrofuran, and N, N-dimethylacetamide.
5. The method of claim 1, wherein the controlled thickness in step (3) is 25 μm to 300 μm.
6. The method according to claim 1, wherein the separator in step (3) comprises a polypropylene film, a polyethylene film, a double-layer PP/PE composite film, a triple-layer PP/PE/PP composite film, a glass cellulose separator or a non-woven fabric separator.
7. The method of claim 1, wherein in step (4), the ester electrolyte comprises one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, and propylene carbonate.
8. The method according to claim 1, wherein in the step (4), the ether electrolyte comprises one or more of ethylene glycol dimethyl ether, 1, 3-dioxolane, and diphenyl ether.
9. The method of claim 1, wherein the metal in the metal symmetrical battery in the step (4) is lithium, sodium, aluminum, magnesium, potassium or calcium.
CN201910758015.7A 2019-08-16 2019-08-16 Method for applying polymer modified diaphragm to metal battery negative electrode protection Active CN110459823B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910758015.7A CN110459823B (en) 2019-08-16 2019-08-16 Method for applying polymer modified diaphragm to metal battery negative electrode protection

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910758015.7A CN110459823B (en) 2019-08-16 2019-08-16 Method for applying polymer modified diaphragm to metal battery negative electrode protection

Publications (2)

Publication Number Publication Date
CN110459823A CN110459823A (en) 2019-11-15
CN110459823B true CN110459823B (en) 2020-11-10

Family

ID=68487125

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910758015.7A Active CN110459823B (en) 2019-08-16 2019-08-16 Method for applying polymer modified diaphragm to metal battery negative electrode protection

Country Status (1)

Country Link
CN (1) CN110459823B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407625B (en) * 2008-12-05 2011-04-27 北京理工大学 Hyperbranched polyether type solid polymer elecrolytes and preparation thereof
CN105140449A (en) * 2015-08-14 2015-12-09 中国人民解放军63971部队 Method for protecting anode of lithium sulfur battery
CN109103517B (en) * 2017-06-20 2020-04-24 中国科学院化学研究所 Method for protecting metal secondary battery cathode by using polymer and application thereof
CN109103488B (en) * 2017-06-20 2020-05-26 中国科学院化学研究所 Polymer sodium battery and preparation method and application thereof

Also Published As

Publication number Publication date
CN110459823A (en) 2019-11-15

Similar Documents

Publication Publication Date Title
Zhao et al. Liquid phase therapy to solid electrolyte–electrode interface in solid-state Li metal batteries: a review
Chen et al. Progress and future prospects of high-voltage and high-safety electrolytes in advanced lithium batteries: from liquid to solid electrolytes
Zhang et al. Recent developments of the lithium metal anode for rechargeable non‐aqueous batteries
CN109103517B (en) Method for protecting metal secondary battery cathode by using polymer and application thereof
KR101057523B1 (en) How to Form Electrolyte, Cell, and Passivation Layers
CN111326799A (en) Flame-retardant high-voltage electrolyte for lithium ion battery and preparation method thereof
CN112242561B (en) Eutectic solvent electrolyte, preparation method thereof and lithium metal battery
CN111653822B (en) Gel type ionic liquid electrolyte for lithium ion battery and preparation method and application thereof
CN110459823B (en) Method for applying polymer modified diaphragm to metal battery negative electrode protection
CN111342138B (en) Application method of lithium ion battery electrolyte for improving film forming property
US6558850B2 (en) Method of fabricating an electrolytic cell employing a solid polymer electrolyte
CN104798244B (en) Lithium secondary battery
CN108615941B (en) Additive for preventing thermal runaway and application thereof in secondary lithium metal battery
CN107017432A (en) Nonaqueous electrolytic solution and lithium ion battery
CN110249469A (en) Lithium secondary battery
KR20170103700A (en) A method for manufacturing a secondary battery
KR20220150370A (en) Gel electrolyte precursors and their applications
CN101783422A (en) Additive and electrolyte containing the same and lithium-ion battery
EP3972029A1 (en) Lithium secondary battery electrolyte, preparation method therefor and lithium secondary battery
CN109565038A (en) The preprocess method and lithium metal battery of lithium electrode
CN111864260B (en) Ether gel electrolyte and preparation method and application thereof
CN105762328A (en) Passivation lithium powder and preparing method thereof, positive electrode material with addition of passivation lithium powder and battery
CN113644312A (en) Surface modification method and application of garnet type solid electrolyte
CN114024036A (en) Low-concentration lithium ion battery electrolyte and lithium ion battery prepared from same
CN116154275A (en) Preparation method of in-situ gel

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant