CN114635166A - Flexible lithium extraction device and method - Google Patents
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Abstract
本发明公开了一种柔性提锂装置，所述柔性提锂装置包括由柔性封装膜制成的具有密封腔体的壳体，所述密封腔体中填充有缓冲层；所述壳体上开设有窗口，所述窗口被一固定于壳体上的无机/聚合物复合锂离子筛膜完全覆盖；所述壳体的内表面上固定有一锂沉积电极，所述锂沉积电极上连接一极耳，所述极耳从所述密封腔体中伸出；所述壳体上相对于所述锂沉积电极的另一侧固定有阳极催化层。本发明还提供了所述柔性提锂装置的制备方法以及提锂方法。本发明的柔性提锂装置，解决了现有的利用固态电解质从含锂离子的液体中回收锂的方法中，提锂器件质脆、不可弯折等问题。
The invention discloses a flexible lithium extraction device. The flexible lithium extraction device comprises a casing made of a flexible packaging film and having a sealed cavity, wherein the sealed cavity is filled with a buffer layer; There is a window, the window is completely covered by an inorganic/polymer composite lithium ion sieve film fixed on the shell; a lithium deposition electrode is fixed on the inner surface of the shell, and a pole lug is connected to the lithium deposition electrode , the tabs protrude from the sealed cavity; an anode catalytic layer is fixed on the other side of the casing relative to the lithium deposition electrode. The invention also provides a preparation method of the flexible lithium extraction device and a lithium extraction method. The flexible lithium extraction device of the invention solves the problems of brittleness and inflexibility of the lithium extraction device in the existing method for recovering lithium from a liquid containing lithium ions by using a solid electrolyte.
Description
Technical Field
The invention relates to the technical field of lithium ion recovery, in particular to a flexible lithium extraction device and a lithium extraction method.
Background
The excessive use of fossil fuels causes excessive emission of carbon dioxide, causes environmental problems such as greenhouse effect, and develops and utilizes clean energy to become common knowledge in various countries. However, renewable clean energy sources such as solar energy and wind energy have the problems of discontinuous time distribution, uneven spatial distribution and the like, and a matched energy storage system is required. The lithium battery has the advantages of high discharge voltage, good cyclicity, no memory effect and the like, and becomes an energy storage system with the greatest prospect in the field of energy storage.
If wind power and photoelectric energy are all stored by using lithium iron phosphate batteries, the electricity generated by wind power and solar energy in China every month is expected to be 2.38 multiplied by 10 by 20307t is lithium. It is currently being ascertained that the lithium reserve in global ores is approximately 2.8 x 107t, 5.2X 10 in brine7t, in seawater, reaches 2.3 × 1011t. Obviously, the resource demand of human beings for lithium cannot be met only by mining ores, and if the utilization of lithium resources in seawater (brine) is realized, the human beings can obtain continuous lithium resource supply.
The lithium resource with huge reserve in seawater attracts the attention of governments and scientific researchers of various countries, and people explore a series of methods including a precipitation method, an extraction method, an adsorption method, an electrochemical method and the like, but the effect is very little. Chinese patent CN 109097791B proposes a method and apparatus for extracting lithium from seawater based on lithium ion solid electrolyte, and the patent provides a new idea for directly obtaining metallic lithium. However, the solid electrolyte used in this device has high hardness and is not easily processed into a complicated shape. Meanwhile, the solid electrolyte has high brittleness, so that cracks are easily generated under the impact of external force.
Disclosure of Invention
The invention provides a flexible lithium extraction device and a preparation method thereof, aims to solve the problems that the quality of the lithium extraction device is brittle and cannot be bent in the existing method for recovering lithium from liquid containing lithium ions by using solid electrolyte, and provides a method for recovering lithium resources in liquid by using the flexible lithium extraction device.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a flexible lithium extraction device, which comprises a shell made of a flexible packaging film and provided with a sealed cavity, wherein a buffer layer is filled in the sealed cavity; the shell is provided with a window which is completely covered by an inorganic/polymer composite lithium ion sieve membrane fixed on the shell; a lithium deposition electrode is fixed on the inner surface of the shell, and a tab is connected to the lithium deposition electrode and extends out of the sealed cavity; and an anode catalyst layer is fixed on the other side of the shell body relative to the lithium deposition electrode.
Further, the inorganic/polymer composite lithium ion sieve membrane includes a polymer membrane and inorganic electrolyte particles embedded in the polymer membrane, and at least a portion of the inorganic electrolyte particles penetrate the polymer membrane.
In the inorganic/polymer composite lithium ion sieve membrane prepared by the invention, at least part of inorganic electrolyte particles penetrate through the polymer membrane, and lithium ions are not conducted by the polymer, so that the lithium ions can pass through the composite membrane through the inorganic electrolyte particles, and other ions cannot pass through the composite membrane, therefore, the sieve membrane has high selectivity on the lithium ions, and meanwhile, the sieve membrane also has good flexibility and can be bent.
In the invention, the inorganic/polymer composite lithium ion sieve membrane is prepared by the following method:
s1, placing thermoplastic polymer particles between two high-temperature-resistant films, heating to soften the thermoplastic polymer particles, and rolling the thermoplastic polymer particles into a polymer film;
s2, removing the high-temperature-resistant film on one side of the polymer film, heating to soften the polymer film, and uniformly paving inorganic electrolyte particles on the surface of the polymer film;
s3, applying pressure to enable the inorganic electrolyte particles to be adhered to the polymer film, and then removing the inorganic electrolyte particles which are not adhered;
s4, placing the polymer membrane adhered with the inorganic electrolyte particles between two high-temperature-resistant membranes, and embedding the inorganic electrolyte particles into the polymer membrane through hot pressing to obtain the inorganic/polymer composite lithium ion sieve membrane.
Further, in step S1, the thermoplastic polymer is a polymer that does not conduct lithium ions, including but not limited to one or more of Polyethylene (PE), polypropylene (PP), Thermoplastic Polyurethane (TPU), and Polyoxymethylene (POM). Preferably, the thermoplastic polymer is PE.
Further, in step S1, the thickness of the polymer film is 1 to 1000 μm, preferably 20 to 100 μm.
According to the invention, when the polymer film is prepared, the roller is not directly contacted with the thermoplastic polymer particles, but the thermoplastic polymer particles are placed between two high-temperature resistant films and then are subjected to hot pressing, so that the polymer film is prevented from being polluted, meanwhile, the high-temperature resistant films are used as flexible buffer layers, after the inorganic electrolyte particles are laid on the surface of the polymer film, the particles can directly penetrate through the polymer film and are exposed through hot pressing, subsequent etching and other processes are not needed, the preparation process is simplified, and meanwhile, no polymer residue exists on the surface of the particles, so that the conductivity of the composite film is not influenced.
Further, in step S1, the high temperature resistant film is preferably a perfluoroethylene propylene (FEP) film with a thickness of 10 to 1000 μm, preferably 100 to 500 μm.
Further, in step S2, the particle size of the inorganic electrolyte particles is 5 to 1000 μm, and the particle size of the inorganic electrolyte particles is not less than the thickness of the polymer film, so that it is ensured that both ends of the inorganic electrolyte particles in the composite lithium ion sieve film penetrate through the surface of the polymer film.
The inorganic electrolyte particles selected in the present invention are LAGPs, which themselves sinter more densely and harder than LATPs, and thus are less likely to break under pressure, thereby ensuring that at least some of the LAGP particles penetrate the polymer film under pressure. Further, the inorganic electrolyte is an NASICON-structured oxide, a perovskite-structured oxide, or a garnet-structured oxide; the NASICON structure oxide is Li1+xAlxGe2-x(PO4)3Or Li1+xAlxTi2-x(PO4)3X is more than or equal to 0.2 and less than or equal to 0.8; the garnet-structure oxide is Li7-yLa3Zr2-yTayO12Y is more than or equal to 0 and less than or equal to 1; the perovskite structure oxide is Li3zLa2/3-zTiO3，0＜z≤2/3。
Further, the flexible packaging film is a polymer film material which is waterproof and resistant to electrolyte corrosion, and can be an adhesive tape, for example.
Further, the lithium deposition electrode is composed of a metal foil and a metal tab attached to the metal foil. Preferably, the metal foil of the lithium deposition electrode is a copper foil, and the metal tab is a nickel tab.
Further, the anode catalyst layer comprises a current collector, and an anode catalyst and a binder coated on the current collector. Preferably, the current collector used in the anode catalyst layer is carbon cloth, and the anode catalyst is Fe, Co, Ni-based composite OER catalyst or Pt-based catalyst. The binder is preferably an aqueous binder such as Polytetrafluoroethylene (PTFE) or the like.
Further, the buffer layer is a liquid organic electrolyte containing a lithium salt, a polymer gel electrolyte, or a solid electrolyte. Preferably, the buffer layer is an organic electrolyte containing lithium ions, wherein the lithium salt is LiClO4The solvent is organic solvent Propylene Carbonate (PC), and the concentration of lithium salt is at least 0.1 mol/L.
The invention also provides a preparation method of the flexible lithium extraction device, which comprises the following steps:
a. taking a flexible packaging film, cutting the surface of the flexible packaging film to form a window, and attaching an inorganic/polymer composite lithium ion sieve film on the flexible packaging film to completely cover the window;
connecting a metal tab to the metal foil to obtain a lithium deposition electrode; taking another flexible packaging film, attaching the lithium deposition electrode to the side surface of the other flexible packaging film, and enabling the metal tab to partially extend out of the flexible packaging film;
b. packaging the buffer layer and the two flexible packaging films together to form a sealed cavity, so that the buffer layer is packaged in the sealed cavity; the lithium deposition electrode is positioned in the sealed cavity, and the metal tab extends out of the sealed cavity;
c. and attaching an anode catalyst layer to the other side of the flexible packaging film attached to the lithium deposition electrode to obtain the flexible lithium extraction device.
The invention also provides a lithium extraction method based on the flexible lithium extraction device, which comprises the following steps:
i. placing the flexible lithium extraction device in liquid containing free lithium ions, so that an inorganic/polymer composite lithium ion sieve membrane in the device is immersed below the liquid level, and a metal tab of a lithium deposition electrode is not contacted with the liquid;
ii, connecting a metal tab of the lithium deposition electrode with the anode catalyst layer by using a wiring, and then connecting an external power supply to form a loop;
and iii, applying a certain current to the loop through the external power supply, wherein under the action of bias voltage, lithium ions in the liquid selectively enter the buffer layer through the inorganic/polymer composite lithium ion sieve membrane and are deposited on the lithium deposition electrode in the form of elemental lithium.
In the present invention, the liquid containing free lithium ions includes, but is not limited to, seawater, brine, lithium-containing wastewater, lithium-containing organic solution.
Compared with the prior art, the invention has the beneficial effects that:
1. in the flexible lithium extraction device, the adopted sieve membrane is the inorganic/polymer composite lithium ion sieve membrane, and lithium ions can only pass through the inorganic/polymer composite lithium ion sieve membrane through inorganic electrolyte particles, so the composite lithium ion sieve membrane has high selectivity on the lithium ions, has higher ionic conductivity at room temperature, can meet the requirement of lithium resource recovery, and has better flexibility and mechanical strength.
2. The flexible lithium extraction device adopts flexible packaging materials, and can ensure that the whole device has good mechanical properties.
3. Compared with the existing method, the flexible lithium extraction device can recover the metal lithium from the liquid containing the free lithium ions more quickly, and has the characteristics of simple preparation, convenient operation during lithium extraction and the like.
Drawings
FIG. 1(a) is a schematic front view of a flexible lithium extraction device;
FIG. 1(b) is a schematic rear view of a flexible lithium extraction device;
FIG. 1(c) is a schematic view showing the arrangement sequence of the components of the flexible lithium extracting apparatus;
FIG. 2 is an XRD signal of a grey deposit on copper foil after a lithium extraction operation based on the apparatus;
the reference numbers in the figures illustrate: 1, 5, a flexible packaging film; 2. inorganic/polymer composite lithium ion sieve membrane; 3. a buffer layer; 4. a lithium deposition electrode; 6. and an anode catalysis layer.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1: preparation of inorganic/polymer composite lithium ion sieve membrane
1. Weighing Li according to the mass ratio of 0.74g to 0.305g to 1.878g to 4.128g2CO3，Al2O3，GeO2And NH4H2PO4Ball-milling and mixing the precursor, wherein the ball-material ratio is 4:1, the rotating speed is 400rpm, standing is carried out for 5min every 20min of ball milling, and the circulation is carried out for 20 times; then the precursor is thermally treated, and the precursor is heated,heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 1h and then naturally cooling; and then, ball-milling the precursor after heat treatment again, wherein the ball-material ratio is 4:1, the rotating speed is 400rpm, standing for 5min every 20min of ball milling, and circulating for 20 times.
2. Heating the ball-milled precursor powder to 900 ℃ at the heating rate of 2 ℃/min for sintering, preserving the heat for 6 hours, and naturally cooling to obtain Li1.5Al0.5Ge1.5(PO4)3. Li obtained by sintering1.5Al0.5Ge1.5(PO4)3Placing in a mortar, and grinding into LAGP particles; and screening by using an ultrasonic screening system to obtain LAGP particles with the particle size of 49.4-59.3 mu m.
3. PE melt particles (flow rate standard substance: 3.94mg/min) are placed between two FEP release films with the thickness of 1mm, and the softened PE particles are rolled into a PE film at the temperature of 150 ℃; removing the FEP release film on one side of the PE film, spreading LAGP electrolyte particles on the softened PE film at 160 ℃, applying slight pressure to enable a single layer of LAGP particles to be adhered on the softened PE film, and removing the non-adhered LAGP particles. And (3) placing the PE film adhered with the single-layer LAGP particles between two FEP release films, applying a pressure of 1.5MPa by using a tablet press, naturally cooling and separating the FEP release films to obtain the LAGP-PE composite lithium ion sieve film.
Example 2: device for preparing flexible lithium
1. The inorganic/polymer composite lithium ion sieve membrane prepared in example 1 was cut into a square of 50mm × 30mm at room temperature. The packaging material is Australian Brand butyl waterproof adhesive tape, a piece of 100mm × 60mm adhesive tape is cut by scissors, and a window of 40mm × 20mm is arranged in the middle of the adhesive tape. The window is sealed by attaching an inorganic/polymer composite lithium ion sieve membrane.
2. Shearing a 65 mm-45 mm square copper foil by using scissors to serve as a lithium deposition electrode, and welding a metal nickel tab and the copper foil by using an electric welding machine to form the lithium deposition electrode; a100 mm x 60mm piece of Australian brand butyl waterproof adhesive tape is cut by scissors, the lithium deposition electrode is adhered to the middle position of the adhesive tape, and a part of the metal tab extends out of the adhesive tape. And bonding the part adhered with the inorganic/polymer composite lithium ion sieve membrane and the part adhered with the lithium deposition electrode into a whole.
3. The adhesive tape adhered with the inorganic/polymer composite lithium ion sieve membrane and the adhesive tape adhered with the lithium deposition electrode are packaged with the buffer layer to form a sealed whole, and the placing sequence refers to the schematic diagram 1. The buffer layer is made of 0.5mol/L LiClO4A PC solution.
4. Cutting a piece of carbon cloth by using scissors, wherein the shape of the carbon cloth is as shown in a schematic diagram 1, uniformly mixing PTFE and OER catalyst FeNi double hydroxide according to the proportion of 1:9, coating the mixture on the carbon cloth to form an anode catalyst layer, and fixing the anode catalyst layer on the other side of a packaging adhesive tape with a lithium deposition electrode adhered on one side to obtain the flexible lithium extraction device.
Lithium extraction test
1000mL of deionized water was accurately weighed with a measuring cylinder and poured into a glass basin. 27.23g of NaCl and 1.038mg of LiCl were weighed on a balance, placed in the above glass pot, and stirred with a glass rod to dissolve NaCl and LiCl. The prepared flexible lithium extraction device is immersed below the water level in a glass basin, so that the inorganic/polymer composite lithium ion sieve membrane is completely immersed, and the tab of the lithium deposition electrode is not immersed in the water level.
By using an electrochemical workstation, a working electrode binding clip is connected with a tab of a lithium deposition electrode, a counter electrode and a reference electrode binding clip are connected with an anode catalyst layer to form a closed loop, and the constant current is set to be 200 muA. After a period of time, a grey deposit was observed on the surface of the copper foil. And after a period of time, stopping the current of the electrochemical workstation, and disconnecting the electrochemical workstation from the lithium extraction device. The lithium extraction device was removed from the water, wiped dry of surface moisture and carefully transferred to an argon glovebox.
And taking the lithium deposition electrode out of the lithium extraction device, placing the lithium deposition electrode in a sealed XRD mold, removing the mold from a glove box, and carrying out XRD test on the gray deposit on the surface of the copper foil. The XRD set angle ranges from 30 to 60 °, and the test results are shown in fig. 2.
The results of fig. 2 demonstrate that the metal deposit on the copper foil is metallic lithium.
In conclusion, the flexible lithium extraction device can be used for recovering lithium resources in liquid containing lithium ions, such as seawater, brine and the like. When an external power supply forms a closed loop, lithium ions selectively pass through the inorganic/polymer composite lithium ion sieve membrane from the liquid to enter the organic electrolyte chamber, and are finally deposited on the lithium deposition electrode in the form of elemental lithium, so that the lithium extraction is realized. Compared with the existing method, the flexible lithium extraction device can recover the metallic lithium more quickly, and has the characteristics of simple preparation, convenient operation during lithium extraction and the like.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A flexible lithium extraction device is characterized by comprising a shell which is made of a flexible packaging film and is provided with a sealed cavity, wherein a buffer layer is filled in the sealed cavity; the shell is provided with a window, and the window is completely covered by an inorganic/polymer composite lithium ion sieve membrane fixed on the shell; a lithium deposition electrode is fixed on the inner surface of the shell, and a tab is connected to the lithium deposition electrode and extends out of the sealed cavity; and an anode catalyst layer is fixed on the other side of the shell body relative to the lithium deposition electrode.
2. The flexible lithium extraction device according to claim 1, wherein the inorganic/polymer composite lithium ion sieve membrane comprises a polymer membrane and inorganic electrolyte particles embedded in the polymer membrane, and at least part of the inorganic electrolyte particles penetrate through the polymer membrane;
the inorganic/polymer composite lithium ion sieve membrane is prepared by the following method:
s1, placing thermoplastic polymer particles between two high-temperature-resistant films, heating to soften the thermoplastic polymer particles, and rolling the thermoplastic polymer particles into a polymer film;
s2, removing the high-temperature-resistant film on one side of the polymer film, heating to soften the polymer film, and uniformly paving inorganic electrolyte particles on the surface of the polymer film;
s3, applying pressure to enable the inorganic electrolyte particles to be adhered to the polymer film, and then removing the inorganic electrolyte particles which are not adhered;
s4, placing the polymer membrane adhered with the inorganic electrolyte particles between two high-temperature-resistant membranes, and embedding the inorganic electrolyte particles into the polymer membrane through hot pressing to obtain the inorganic/polymer composite lithium ion sieve membrane.
3. The flexible lithium extraction device according to claim 2, wherein in step S1, the thermoplastic polymer comprises one or more of polyethylene, polypropylene, thermoplastic polyurethane, and polyoxymethylene; the high-temperature resistant film is a perfluoroethylene propylene film, and the thickness of the high-temperature resistant film is 10-1000 mu m; the thickness of the polymer film is 1-1000 μm.
4. The flexible lithium extraction device according to claim 2, wherein in step S2, the particle size of the inorganic electrolyte particles is 5-1000 μm, and the particle size of the inorganic electrolyte particles is not less than the thickness of the polymer film.
5. The flexible lithium extraction device according to claim 2, wherein the inorganic electrolyte is a NASICON-structured oxide, a perovskite-structured oxide, or a garnet-structured oxide; the NASICON structure oxide is Li1+ xAlxGe2-x(PO4)3Or Li1+xAlxTi2-x(PO4)3X is more than or equal to 0.2 and less than or equal to 0.8; the garnet-structure oxide is Li7-yLa3Zr2- yTayO12Y is more than or equal to 0 and less than or equal to 1; the perovskite structure oxide is Li3zLa2/3-zTiO3，0＜z≤2/3。
6. The flexible lithium extraction device as claimed in claim 1, wherein the flexible packaging film is a polymer film material which is waterproof and electrolyte-resistant.
7. The flexible lithium extraction device of claim 1, wherein the lithium deposition electrode is composed of a metal foil and a metal tab attached to the metal foil; the anode catalyst layer comprises a current collector, and an anode catalyst and a binder coated on the current collector.
8. The flexible lithium extraction device of claim 1, wherein the buffer layer is a liquid organic electrolyte containing lithium salt, a polymer gel electrolyte or a solid electrolyte.
9. The method for preparing a flexible lithium extraction device according to any one of claims 1 to 8, comprising the steps of:
a. taking a flexible packaging film, cutting the surface of the flexible packaging film to form a window, and attaching an inorganic/polymer composite lithium ion sieve film on the flexible packaging film to completely cover the window;
connecting a metal tab to the metal foil to obtain a lithium deposition electrode; taking another flexible packaging film, attaching the lithium deposition electrode to the side surface of the other flexible packaging film, and enabling the metal tab to partially extend out of the flexible packaging film;
b. packaging the buffer layer and the two flexible packaging films together to form a sealed cavity, so that the buffer layer is packaged in the sealed cavity; the lithium deposition electrode is positioned in the sealed cavity, and the metal tab extends out of the sealed cavity;
c. and attaching an anode catalyst layer to the other side of the flexible packaging film attached to the lithium deposition electrode to obtain the flexible lithium extraction device.
10. The lithium extraction method based on the flexible lithium extraction device of any one of claims 1 to 8, characterized by comprising the following steps:
i. placing the flexible lithium extraction device in liquid containing free lithium ions, so that an inorganic/polymer composite lithium ion sieve membrane in the device is immersed below the liquid level, and a metal tab of a lithium deposition electrode is not contacted with the liquid;
ii, connecting a metal tab of the lithium deposition electrode with the anode catalyst layer by using a wiring, and then connecting an external power supply to form a loop;
and iii, applying a certain current to the loop through the external power supply, wherein under the action of bias voltage, lithium ions in the liquid selectively enter the buffer layer through the inorganic/polymer composite lithium ion sieve membrane and are deposited on the lithium deposition electrode in the form of elemental lithium.
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| CN104194020A (en) * | 2014-08-03 | 2014-12-10 | 北京化工大学 | Method for preparing flexible inorganic/polymer composite film with high dielectric property |
| CN105990591A (en) * | 2015-02-06 | 2016-10-05 | 上海交通大学 | Flexible composite electrolyte membrane and preparation method thereof |
| DE102015202972A1 (en) * | 2015-02-19 | 2016-08-25 | Robert Bosch Gmbh | Flexible inorganic-polymer composite separator for a lithium-oxygen cell |
| CN105619991A (en) * | 2016-03-16 | 2016-06-01 | 东华大学 | Composite lithium-ion battery separator material and preparation method thereof |
| CN106784993A (en) * | 2016-12-29 | 2017-05-31 | 中国电子科技集团公司第十八研究所 | Flexible polymer thin lithium ion battery and preparation method thereof |
| CN109097791A (en) * | 2018-07-23 | 2018-12-28 | 南京大学 | Extracting Lithium from Seawater method and apparatus based on lithium ion solid electrolyte |
| CN109781698A (en) * | 2018-12-28 | 2019-05-21 | 厦门大学 | A kind of in-situ Raman spectral cell and electrochemical in-situ spectral testing method |
| CN111384316A (en) * | 2019-12-31 | 2020-07-07 | 武汉瑞科美新能源有限责任公司 | Flexible lithium ion battery packaging film, lithium ion battery packaging method and battery |
| CN112054244A (en) * | 2020-08-21 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Composite solid electrolyte and preparation method and application thereof |
| CN112838266A (en) * | 2021-03-23 | 2021-05-25 | 上海电气集团股份有限公司 | Composite electrolyte membrane, preparation method and application thereof, and solid-state lithium battery |
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