CN111446490A - Single-layer boron nitride modified PEO polymer electrolyte and preparation method thereof - Google Patents
Single-layer boron nitride modified PEO polymer electrolyte and preparation method thereof Download PDFInfo
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- CN111446490A CN111446490A CN201910282938.XA CN201910282938A CN111446490A CN 111446490 A CN111446490 A CN 111446490A CN 201910282938 A CN201910282938 A CN 201910282938A CN 111446490 A CN111446490 A CN 111446490A
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 78
- 239000002356 single layer Substances 0.000 title claims abstract description 67
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 75
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 (trifluoromethyl) sulfonate imide Chemical class 0.000 claims description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 239000012300 argon atmosphere Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000005303 weighing Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a single-layer boron nitride modified PEO polymer electrolyte, which consists of polyethylene oxide (PEO), lithium salt and inorganic modified filler boron nitride; in the single-layer boron nitride modified PEO polymer electrolyte, polyethylene oxide (PEO) accounts for 80-95 wt% of the total mass of the electrolyte membrane, single-layer boron nitride accounts for 0-15 wt% of the total mass of the electrolyte membrane, lithium salt accounts for 5 wt% of the total mass of the electrolyte membrane, and the molar ratio of lithium elements to ether oxygen groups of EO structural units in the electrolyte membrane is 1: 15. According to the invention, the mechanical property is improved from macroscopic level or microscopic level through the boron nitride with the single-layer structure, the tensile property is improved from macroscopic level, the electrolyte interface is more stable from microscopic level, ions can be transferred more quickly, the ionic conductivity is effectively improved, and the boron nitride has good ionic conductivity, mechanical property, electrochemical stability and thermal stability.
Description
Technical Field
The invention relates to the technical field of electrolytes, in particular to a single-layer boron nitride modified PEO polymer electrolyte and a preparation method thereof.
Background
The urgent need for high safety rechargeable batteries in the field of energy storage has greatly driven the development of solid-state lithium batteries, which replace conventional liquid organic electrolytes with solid electrolytes, and which are more stable when matched with lithium metal and are capable of inhibiting the growth of lithium dendrites in lithium metal batteries, to attract more and more attention.
Inorganic and polymer electrolytes are two mainstream solid electrolytes that are currently being extensively studied. The lithium-conducting ceramic electrolyte has high lithium ion conductivity and lithium ion migration number, good mechanical property and excellent electrochemical and thermodynamic stability. However, ceramic electrolytes are hard and brittle and thus cause a large interfacial resistance between the electrode material and the solid electrolyte. PEO has high lithium ion conductivity at temperatures above its melting point (65 ℃) and low interfacial resistance with the electrode material. PEO can therefore be used as a substrate for a liquid-free solid electrolyte to increase lithium ion conductivity and reduce interfacial resistance. In addition, PEO films also exhibit good mechanical properties, such as good ductility, ease of bending and shaping. The addition of the inorganic filler reduces the crystallinity of the polymer matrix and forms crystal defects at the interface with the polymer, further improving the properties. Meanwhile, the types, the mass fractions and the structures of the inorganic fillers influence the improvement of the performance, the inorganic fillers with rich surface functional groups obviously improve the conductivity and the ion migration number due to the Lewis reaction, and the modification effect of the fillers with large specific surface area is more obvious.
Based on the method, the single-layer boron nitride with rich ether oxygen functional groups on the surface is selected as the inorganic filler to reduce the crystallinity of PEO and achieve the purpose of improving the mechanical property of PEO; and (3) exploring the optimal modification mass fraction of the single-layer boron nitride to prepare the polymer electrolyte membrane. The electrolyte membrane has the advantages of good film forming property, excellent mechanical property, high ionic conductivity and the like.
Disclosure of Invention
The present invention is directed to a single-layer boron nitride-modified PEO polymer electrolyte and a method for preparing the same, which solve the problems of the background art described above.
In order to solve the technical problems, the invention provides the following technical scheme: a single-layer boron nitride modified PEO polymer electrolyte membrane is composed of polyethylene oxide (PEO), lithium salt and inorganic modified filler boron nitride;
in the single-layer boron nitride modified PEO polymer electrolyte, polyethylene oxide (PEO) accounts for 80-95 wt% of the total mass of the electrolyte membrane, single-layer boron nitride accounts for 0-15 wt% of the total mass of the electrolyte membrane, lithium salt accounts for 5 wt% of the total mass of the electrolyte membrane, and the molar ratio of lithium elements to ether oxygen groups of EO structural units in the electrolyte membrane is 1: 15.
Further, the thickness of the boron nitride is 2.0-5.4nm, and the molecular weight of the polyethylene oxide (PEO) is in the range of 60-100W.
Further, the lithium salt is lithium bis (trifluoromethyl) sulfinamide and lithium perchlorate.
Further, the inorganic modified filler boron nitride is of a single-layer structure and is rich in functional groups on the surface, which are favorable for being combined with a polymer substrate, and the inorganic modified filler boron nitride comprises hydroxyl groups, ether oxygen groups and carboxyl functional groups.
The invention also provides a preparation method of the single-layer boron nitride modified PEO polymer electrolyte, which comprises the following steps:
step 1, dispersing block hexagonal phase boron nitride h-BN and methylamine in an aqueous solution according to a stoichiometric ratio of 1:60-1:80, keeping the solid content in the aqueous solution at 10 wt%, carrying out wet ball milling for 10-20 hours by using a planetary ball mill, keeping the ball milling rotation speed at 1000r.p.m under the room temperature of nitrogen protection, and finally obtaining single-layer boron nitride;
step 4, preparing the solution into a film shape, and then heating at 50 ℃ to remove the dispersing solvent to obtain the single-layer boron nitride modified PEO-based polymer electrolyte;
and 5, removing the electrolyte membrane from the polytetrafluoroethylene mold, placing the electrolyte membrane between two polytetrafluoroethylene plates, then placing the electrolyte membrane between two cutting boards of a hot press for pressing, removing the membrane after the temperature is cooled, and placing the membrane in an argon atmosphere glove box for storage.
Further, the dispersion solvent in step 3 is acetonitrile.
Further, in the step 5, the pressing temperature of the hot press is 60 ℃, the pressure is 2Mpa, and the time is 10 minutes.
Compared with the prior art, the invention has the following beneficial effects:
1) the single-layer boron nitride modified PEO polymer electrolyte effectively prevents the recombination of PEO chain segments and inhibits crystallization by adding the single-layer boron nitride, and ion transmission channels can be increased due to the tunnel effect.
2) According to the invention, the mechanical property is improved from macroscopic level or microscopic level through the boron nitride with the single-layer structure, the tensile property is improved from macroscopic level, the electrolyte interface is more stable from microscopic level, ions can be transferred more quickly, the ionic conductivity is effectively improved, and the boron nitride has good ionic conductivity, mechanical property, electrochemical stability and thermal stability.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a characteristic of SEM and TEM morphology of single layer boron nitride in the present invention;
FIG. 2 is a HRTEM feature of single layer boron nitride in the present invention;
fig. 3 is a graph of ionic conductivity as a function of mass fraction of single layer boron nitride for single layer boron nitride modified PEO-based polymer electrolytes prepared in the present invention;
fig. 4 is an SEM image of a single-layer boron nitride-modified PEO-based polymer electrolyte prepared in the present invention;
FIG. 5 is a graph showing tensile property test results of a PEO-based polymer electrolyte modified with a single layer of boron nitride prepared in the present invention having a mass fraction of 8.6 wt%;
FIG. 6 is a schematic diagram of a test procedure for a PEO-based polymer electrolyte modified with a single layer of boron nitride having a mass fraction of 8.6 wt% prepared in the present invention;
fig. 7 is a schematic view of PEO-based polymer electrolyte membranes with mass fractions of 0 wt% and 15 wt% of single-layer boron nitride prepared in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 was carried out:
a method for preparing a single layer boron nitride modified PEO polymer electrolyte, comprising the steps of:
step 1, firstly, dispersing block hexagonal phase boron nitride h-BN and methylamine in an aqueous solution according to a stoichiometric ratio of 1:60-1:80, keeping the solid content in the aqueous solution at 10 wt%, carrying out wet ball milling for 10-20 hours by using a planetary ball mill, keeping the ball milling rotation speed at 800-1000r.p.m under the room temperature of nitrogen protection, and finally obtaining ball-milled single-layer boron nitride, placing L iClO4, PEO and the single-layer boron nitride in a vacuum oven, drying for 12 hours at 70 ℃, and placing in an argon atmosphere glove box for later use;
and 4, removing the electrolyte membrane from the polytetrafluoroethylene mold, placing the electrolyte membrane between two polytetrafluoroethylene plates, placing the polytetrafluoroethylene membrane between two cutting boards of a hot press for pressing, removing the membrane after the temperature is cooled to obtain a polymer electrolyte membrane, and placing the polymer electrolyte membrane in an argon atmosphere glove box for storage.
Example 2 was carried out:
a method for preparing a single layer boron nitride modified PEO polymer electrolyte, comprising the steps of:
step 1, placing L iTFSI, PEO and single-layer boron nitride in a vacuum oven, drying for 12 hours at 70 ℃, and placing in an argon atmosphere glove box for later use;
and 4, removing the electrolyte membrane from the polytetrafluoroethylene mold, placing the electrolyte membrane between two polytetrafluoroethylene plates, placing the polytetrafluoroethylene membrane between two cutting boards of a hot press for pressing, removing the membrane after the temperature is cooled to obtain a polymer electrolyte membrane, and placing the polymer electrolyte membrane in an argon atmosphere glove box for storage.
Example 3 of implementation:
a method for preparing a single layer boron nitride modified PEO polymer electrolyte, comprising the steps of:
step 1, placing L iClO4, PEO and single-layer boron nitride in a vacuum oven, drying for 12 hours at 70 ℃, and placing in an argon atmosphere glove box for later use;
and 4, removing the electrolyte membrane from the polytetrafluoroethylene mold, placing the electrolyte membrane between two polytetrafluoroethylene plates, placing the polytetrafluoroethylene membrane between two cutting boards of a hot press for pressing, removing the membrane after the temperature is cooled to obtain a polymer electrolyte membrane, and placing the polymer electrolyte membrane in an argon atmosphere glove box for storage.
Example 4 of implementation:
a method for preparing a single layer boron nitride modified PEO polymer electrolyte, comprising the steps of:
step 1, placing L iTFSI, PEO and single-layer boron nitride in a vacuum oven, drying for 12 hours at 70 ℃, and placing in an argon atmosphere glove box for later use;
and 4, removing the electrolyte membrane from the polytetrafluoroethylene mold, placing the electrolyte membrane between two polytetrafluoroethylene plates, placing the polytetrafluoroethylene membrane between two cutting boards of a hot press for pressing, removing the membrane after the temperature is cooled to obtain a polymer electrolyte membrane, and placing the polymer electrolyte membrane in an argon atmosphere glove box for storage.
According to the single-layer boron nitride modified PEO polymer electrolyte, recombination of PEO chain segments is effectively hindered and crystallization is inhibited after the single-layer boron nitride is added, a transmission channel of ions can be increased due to a tunnel effect, the mechanical property is improved from a macroscopic level or a microscopic level through the single-layer boron nitride, the tensile property is improved from a macroscopic level, the electrolyte interface is more stable from a microscopic level, ions can be transmitted more quickly, the ionic conductivity is effectively improved, and the single-layer boron nitride modified PEO polymer electrolyte has good ionic conductivity, mechanical property, electrochemical stability and thermal stability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A single layer boron nitride modified PEO polymer electrolyte characterized by: the single-layer boron nitride modified PEO polymer electrolyte membrane consists of polyethylene oxide (PEO), lithium salt and inorganic modified filler boron nitride;
in the single-layer boron nitride modified PEO polymer electrolyte, polyethylene oxide (PEO) accounts for 80-95 wt% of the total mass of the electrolyte membrane, single-layer boron nitride accounts for 0-15 wt% of the total mass of the electrolyte membrane, lithium salt accounts for 5 wt% of the total mass of the electrolyte membrane, and the molar ratio of lithium elements to ether oxygen groups of EO structural units in the electrolyte membrane is 1: 15.
2. The single layer boron nitride modified PEO polymer electrolyte of claim 1 wherein: the thickness of the boron nitride is 2.0-5.4nm, and the molecular weight of the polyethylene oxide (PEO) is 60-100W.
3. The single layer boron nitride modified PEO polymer electrolyte of claim 1 wherein: the lithium salt is lithium bis (trifluoromethyl) sulfonate imide and lithium perchlorate.
4. The single layer boron nitride modified PEO polymer electrolyte of claim 1 wherein: the inorganic modified filler boron nitride is of a single-layer structure, the surface of the inorganic modified filler boron nitride is rich in functional groups beneficial to being combined with a polymer substrate, and the inorganic modified filler boron nitride comprises hydroxyl groups, ether oxygen groups and carboxyl functional groups.
5. A single layer boron nitride modified PEO polymer electrolyte according to any one of claims 1-4 wherein: also provided is a method for preparing a single layer boron nitride modified PEO polymer electrolyte, comprising the steps of:
step 1, dispersing block hexagonal phase boron nitride h-BN and methylamine in an aqueous solution according to a stoichiometric ratio of 1:60-1:80, keeping the solid content in the aqueous solution at 10 wt%, carrying out wet ball milling for 10-20 hours by using a planetary ball mill, keeping the ball milling rotation speed at 1000r.p.m under the room temperature of nitrogen protection, and finally obtaining single-layer boron nitride;
step 2, placing lithium salt, polyethylene oxide (PEO) and single-layer boron nitride in a vacuum oven, drying for 12 hours at 70 ℃, and placing in an argon atmosphere glove box for later use;
step 3, dispersing lithium salt and single-layer boron nitride in a dispersing solvent, heating to 50 ℃, magnetically stirring to obtain a uniform milky white solution, simultaneously adding polyethylene oxide (PEO), and strongly stirring for 10min before casting to remove bubbles;
step 4, preparing the solution into a film shape, and then heating at 50 ℃ to remove the dispersing solvent to obtain the single-layer boron nitride modified PEO-based polymer electrolyte;
and 5, removing the electrolyte membrane from the polytetrafluoroethylene mold, placing the electrolyte membrane between two polytetrafluoroethylene plates, then placing the electrolyte membrane between two cutting boards of a hot press for pressing, removing the membrane after the temperature is cooled, and placing the membrane in an argon atmosphere glove box for storage.
6. The single layer boron nitride modified PEO polymer electrolyte of claim 5 wherein: and 3, the dispersing solvent is acetonitrile.
7. The single layer boron nitride modified PEO polymer electrolyte of claim 5 wherein: in the step 5, the pressing temperature of the hot press is 60 ℃, the pressure is 2Mpa, and the time is 10 minutes.
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| CN112436188A (en) * | 2020-12-26 | 2021-03-02 | 哈尔滨工业大学 | Polymer-based solid electrolyte with high room temperature ionic conductivity and preparation method and application thereof |
| CN114512715A (en) * | 2022-01-20 | 2022-05-17 | 贵阳学院 | Polyoxyethylene-based solid electrolyte, preparation method thereof and lithium ion battery |
| CN115425283A (en) * | 2022-09-20 | 2022-12-02 | 浙江理工大学 | Boron nitride nanofiber composite solid electrolyte, preparation method and application |
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| CN115425283A (en) * | 2022-09-20 | 2022-12-02 | 浙江理工大学 | Boron nitride nanofiber composite solid electrolyte, preparation method and application |
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