CN104022306A - Solid porous polymer electrolyte, and preparation method and application thereof - Google Patents
Solid porous polymer electrolyte, and preparation method and application thereof Download PDFInfo
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- CN104022306A CN104022306A CN201410208140.8A CN201410208140A CN104022306A CN 104022306 A CN104022306 A CN 104022306A CN 201410208140 A CN201410208140 A CN 201410208140A CN 104022306 A CN104022306 A CN 104022306A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007787 solid Substances 0.000 title claims description 12
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 8
- 238000005187 foaming Methods 0.000 claims abstract description 6
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 238000013012 foaming technology Methods 0.000 claims description 5
- 239000011218 binary composite Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 abstract description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 13
- 229920000728 polyester Polymers 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 229940021013 electrolyte solution Drugs 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 6
- -1 carbonic acid lipid Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation method for a polyvinylidene fluoride/polyester porous polymer electrolyte. For example, by taking polyvinylidene fluoride and polycaprolactone as raw materials, the preparation process comprises: performing compounding on polyvinylidene fluoride and polycaprolactone according to different ratios, performing blending in a mixer or a double-screw extruder to obtain a polyvinylidene fluoride/polycaprolactone composite material; employing a supercritical CO2 foaming method to process the composite material, so as to obtain a porous material; and performing electrolytic-solution activation on the porous material to obtain the porous polymer electrolyte which is finally assembled into an electrochemical device. The prepared polyvinylidene fluoride/polyester porous polymer electrolyte has relatively high ionic conductivity, the assembled electrochemical device has relatively high specific capacitance and energy density, the production process of the polymer electrolyte is simple and environment-friendly, and the porous material as an electrolyte has the characteristics of being safe, free of leakage accidents and the like and is capable of replacing liquid electrolyte solutions.
Description
Technical field
The present invention relates to electrolyte field, more specifically, relate to a kind of solid porous polymer dielectric and its preparation method and application.
Background technology
Porous polymer electrolyte is a special case of gel polymer electrolyte, and it is kept in structure plasticizer and salt etc. with the loose structure of polymer, reaches the effect of ion transfer.Compare its gel polymer electrolyte, it has solved the shortcoming of bad mechanical property, also have good ionic conductivity, so it is to have as the most promising base polymer electrolyte of lithium ion battery electrolyte simultaneously.Generally in porous polymer electrolyte structure, comprise three-phase, the one, be kept at the electrolyte in loose structure, the 2nd, polymeric matrix, the 3rd, the gel being formed by the polymer after electrolyte swelling.Therefore it has at room temperature ionic conductivity and approaches the ability of liquid electrolyte conductivity, and aspect fail safe, is far superior to liquid electrolyte, and in addition, due to the existence of polymeric matrix, its good processability, can meet difform device.In the middle of the relevant matrix investigation of materials of porous polymer electrolyte, Kynoar is because it has the focus that strong electron withdraw group and high-k become the extensive concern of researcher.
Kynoar is a kind of excellent machinability that has, outstanding mechanical plastics, contain strong electron-withdrawing group group (C-F), and it has dielectric constant higher in polymer (being about 10), it has the dissociation that special chemical constitution contributes to lithium salts, the concentration of the electric charge carrier in electrolyte is improved, in addition, PVDF has good chemical stability, acid-fast alkali-proof, it is not dissolved in carbonic acid lipid organic solvent, the skeleton that can keep polymer porous material, the poromeric network stabilization forming, therefore the polymer dielectric that the PVDF of take is matrix has more wide application prospect.But due to the hemicrystalline of PVDF, its degree of crystallinity is higher, can affect the migration of ion, therefore to consider to utilize the ability of its skeleton, add another one matrix, form porous polymer electrolyte.In the polymer of polyesters and supercritical carbon dioxide, there is good intermiscibility, can in supercritical carbon dioxide fluid, foam and form porous material, and many polyester polymers and Kynoar also have certain compatibility, the polymer that therefore selected the second matrix is polyesters.
Summary of the invention
One of object of the present invention is to obtain the good solid electrolyte of a kind of performance.
First a kind of solid porous polymer dielectric is provided, by Kynoar and polycaprolactone, mixes, then adopt supercritical carbon dioxide foaming technology preparation and obtain.
The cell density of described solid porous polymer dielectric is 5.65 * 10
10~ 1.62 * 10
11/ cm
3, the aperture in described hole is 500nm ~ 10 μ m.
A kind of solid porous method for preparing polymer electrolytes is further provided, comprises the following steps,
S1. melt blending 10 ~ 15min at 200 ℃ ~ 220 ℃ temperature by Kynoar and polycaprolactone, obtain this binary composite material that Kynoar is main matrix of take, Kynoar in material is 1:1～9:1 with the quality of polycaprolactone than scope, the binary material obtaining is prepared certain thickness film with 200 ℃ ~ 220 ℃ temperature in mould, film thickness scope is 0.05mm～0.5mm
S2. by the preheating temperature to 90 ℃ in the container of sealing, and film is placed in container and injects supercritical carbon dioxide fluid, more than swelling 3h, in container, pressure controls as 18MPa～25MPa.The speed of the about 10MPa/s of container is unloaded and is depressed into normal pressure, in 5min, container is opened and film is taken out, can obtain binary foaming porous material,
S3. utilize electrolyte to porous material soak activation 12h ~ 36h, after just can obtain porous polymer electrolyte.
Electrolyte described in S3 is that the organic solution of the dimethylacetylamide of lithium perchlorate, trifluoromethyl sulfonic acid lithium, lithium salts is, the organic solution of the organic solution of the dimethyl formamide of lithium salts or the dimethyl sulfoxide (DMSO) of lithium salts.
The application of a kind of above-mentioned solid porous polymer dielectric in substituting traditional neat liquid electrolyte system is provided in addition.
The invention has the advantages that:
1. to utilize Kynoar be main matrix in the present invention, and polyester, as the second matrix, utilizes supercritical carbon dioxide foaming method to prepare a kind of porous polymer material, obtains a kind of polymer dielectric of porous after electrolyte soaks activation.
2. one aspect of the present invention has been utilized the special construction of Kynoar and the high-k of itself, brought into play its dissociating power to lithium salts, add on the other hand second matrix, greatly reduce the degree of crystallinity of Kynoar, reduce because the impact that its degree of crystallinity is moved for ion, finally utilize the second matrix in supercritical carbon dioxide, to foam and formed the characteristic of loose structure, prepared loose structure Electolyte-absorptive, increased the passage of lithium ion transmission.
3. Kynoar/polyesters porous polymer electrolyte that prepared by the present invention has high ionic conductivity, good mechanical property, and it is higher to be assembled into ratio electric capacity and energy density that electrochemical device records, the simple environmental protection of production process, material has safety as electrolyte, can not produce the characteristics such as leakage accident, can be used for substituting traditional neat liquid electrolyte system.
Accompanying drawing explanation
Fig. 1 is system composite material (PVDF/PCL=83:17) shape appearance figure under SEM after foaming for this reason.
Fig. 2 is the AC impedance curve of the ultracapacitor of PVDF/PCL porous polymer electrolyte for this reason.
Fig. 3 is the charging and discharging curve of the ultracapacitor of PVDF/PCL porous polymer electrolyte for this reason.
Embodiment
Below in conjunction with the drawings and specific embodiments, further describe the present invention.Unless stated otherwise, reagent, equipment and the method that the present invention adopts is the conventional commercial reagent of the art, equipment and the conventional method of using.
Embodiment is investigated is that the ternary porous material that Kynoar is main matrix of take prepared by supercritical carbon dioxide foaming is assembled into the chemical property of ultracapacitor device after electrolyte activation.
Embodiment 1
Fusion method prepares PVDF/PCL binary composite material, wherein the PVDF of composite material and the mass ratio of PCL are 83/17, prepare the composite material film of thickness between 100 μ m ~ 300 μ m, utilize supercritical carbon dioxide foaming technology to foam to composite material, pressure is 25 MPa, swelling time is 3 h, temperature 90 in container
oc, the porous material of gained is at the shape appearance figure of SEM as Fig. 1, and its hot strength is 33.1 MPa, and the porous material finally obtaining is the N of the lithium perchlorate of 1 mol/L in concentration, in N-dimethylacetylamide electrolyte, soak activation 24 h, electrode adopts active carbon (specific area approximately 1800 cm
2/ g), stock quality proportioning is according to active carbon: the mixed slurry of acetylene black: polytetrafluoroethylene=82:10:8, on workbench, suppress film forming, by the film of compacting in vacuum drying chamber in 80
omore than C freeze-day with constant temperature 24h.Collector adopts stainless steel briquetting, and order is dressed up button cell by collector/carbon electrode/porous polymer electrolyte/carbon electrode/collector/spring plate group, the ac impedance spectroscopy of test capacitors, gained as Fig. 2, ionic conductivity is 9.34E-04 S/cm.The charging and discharging curve that test capacitors is different, as Fig. 3, the ratio electric capacity that calculates gained by discharge curve is 125.48 F/g, energy density is 156.85 Wh/Kg.
Embodiment 2
Fusion method prepares PVDF/PCL/CNT binary composite material, wherein the PVDF of composite material and the mass ratio of PCL are 83/17, prepare the composite material film of thickness between 100 μ m ~ 300 μ m, utilize supercritical carbon dioxide foaming technology to foam to composite material, pressure is 25MPa, swelling time is 3h, temperature 90 in container
oc, the porous material finally obtaining is at electrolyte 1-ethyl-3-methylimidazole tetrafluoroborate (EMIMBF
4) soaking activation 24 h in ionic liquid, electrode adopts active carbon (specific area approximately 1800 cm
2/ g), stock quality proportioning is according to active carbon: the mixed slurry of acetylene black: polytetrafluoroethylene=82:10:8, on workbench, suppress film forming, by the film of compacting in vacuum drying chamber in 80
omore than C freeze-day with constant temperature 24 h.Collector adopts stainless steel briquetting, and order is dressed up button cell by collector/carbon electrode/porous polymer electrolyte/carbon electrode/collector/spring plate group, the ac impedance spectroscopy of test capacitors, gained as Fig. 1, ionic conductivity is 2.99E-03S/cm.The charging and discharging curve that test capacitors is different, as Fig. 3, the ratio electric capacity that calculates gained by discharge curve is 157.83 F/g, energy density is 197.29 Wh/Kg.
Embodiment 3
Two step fusion methods prepare PVDF/PCL/CNT composite material, wherein the PVDF of composite material and the mass ratio of PCL are 62/38, prepare the composite material film of thickness between 100 μ m ~ 300 μ m, utilize supercritical carbon dioxide foaming technology to foam to composite material, pressure is 25MPa, swelling time is 3h, temperature 90oC in container, the porous material finally obtaining soaks activation 24h in electrolyte 1-ethyl-3-methylimidazole tetrafluoroborate (EMIMBF4) ionic liquid, electrode adopts active carbon (specific area is 1800 cm2/g approximately), stock quality proportioning is according to active carbon: the mixed slurry of acetylene black: polytetrafluoroethylene=82:10:8, on workbench, suppress film forming, by compacting film in vacuum drying chamber more than 80oC freeze-day with constant temperature 24h.Collector adopts stainless steel briquetting, and order is dressed up button cell by collector/carbon electrode/porous polymer electrolyte/carbon electrode/collector/spring plate group, the ac impedance spectroscopy of test capacitors, gained as Fig. 1, ionic conductivity is 2.24E-03 S/cm.The charging and discharging curve that test capacitors is different, as Fig. 3, the ratio electric capacity that calculates gained by discharge curve is 112.91F/g, energy density is 141.13Wh/Kg.
Claims (5)
1. a solid porous polymer dielectric, is characterized in that, mixes, then adopt supercritical carbon dioxide foaming technology preparation and obtain by Kynoar and polycaprolactone.
2. solid porous polymer dielectric according to claim 1, is characterized in that, the cell density of described solid porous polymer dielectric is 5.65 * 10
10~ 1.62 * 10
11/ cm
3, the aperture in described hole is 500nm ~ 10 μ m.
3. a solid porous method for preparing polymer electrolytes, is characterized in that, comprise the following steps,
S1. melt blending 10 ~ 15min at 200 ℃ ~ 220 ℃ temperature by Kynoar and polycaprolactone, obtain this binary composite material that Kynoar is main matrix of take, Kynoar in material is 1:1～9:1 with the quality of polycaprolactone than scope, the binary material obtaining is prepared certain thickness film with 200 ℃ ~ 220 ℃ temperature in mould, film thickness scope is 0.05mm～0.5mm
S2. by the preheating temperature to 90 ℃ in the container of sealing, and film is placed in container and injects supercritical carbon dioxide fluid, more than swelling 3h, in container, pressure controls as 18MPa～25MPa, the speed of the about 10MPa/s of container is unloaded and is depressed into normal pressure, in 5min, container opened and film is taken out, can obtain binary foaming porous material
S3. utilize electrolyte to porous material soak activation 12h ~ 36h, after just can obtain porous polymer electrolyte.
4. preparation method according to claim 3, it is characterized in that, the electrolyte described in S3 is that the organic solution of the dimethylacetylamide of lithium perchlorate, trifluoromethyl sulfonic acid lithium, lithium salts is, the organic solution of the organic solution of the dimethyl formamide of lithium salts or the dimethyl sulfoxide (DMSO) of lithium salts.
5. a solid porous polymer dielectric according to claim 1 application in substituting traditional neat liquid electrolyte system.
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| CN104022306B CN104022306B (en) | 2016-06-08 |
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Cited By (7)
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| CN109473716A (en) * | 2018-11-01 | 2019-03-15 | 深圳清华大学研究院 | Lithium ion battery polymer electrolyte film and preparation method thereof |
| CN109616697A (en) * | 2018-11-01 | 2019-04-12 | 深圳清华大学研究院 | Magnesium ion battery polymer dielectric film and preparation method thereof |
| CN110571480A (en) * | 2019-09-20 | 2019-12-13 | 河南理工大学 | Preparation method of high-strength high-tensile alkaline solid polymer electrolyte |
| CN113054248A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN114432732A (en) * | 2020-11-04 | 2022-05-06 | 上海科技大学 | Supercritical extraction device and method for porous material |
| CN116387612A (en) * | 2023-02-13 | 2023-07-04 | 北京纯锂新能源科技有限公司 | Polymer electrolyte membrane, preparation method and metal lithium battery |
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