CN112467083A - Method for 3D printing of three-dimensional cathode - Google Patents
Method for 3D printing of three-dimensional cathode Download PDFInfo
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- CN112467083A CN112467083A CN202011310242.2A CN202011310242A CN112467083A CN 112467083 A CN112467083 A CN 112467083A CN 202011310242 A CN202011310242 A CN 202011310242A CN 112467083 A CN112467083 A CN 112467083A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of secondary batteries, and discloses a method for 3D printing of a three-dimensional cathode, which comprises the steps of preparing printing ink by taking a cathode material as a raw material, preparing a three-dimensional porous network structure by using a micro injection printing head by using a 3D printing technology, drying after phase inversion to obtain a prefabricated cathode, and finally performing 3D printing end capping on the top end of the prefabricated cathode by using an insulating polymer. The 3D printing method is adopted, the process is simple, accurate and controllable, the prepared electrode material has good conductivity and large specific surface area, meanwhile, the three-dimensional porous end-capped negative electrode prepared by the method can effectively change the dendritic growth direction of the secondary battery so as to improve the safety performance of the battery, in addition, the porous structure of the 3D printing negative electrode improves the diffusion speed of ions, and meanwhile, the battery has higher ionic and electronic conductivity.
Description
Technical Field
The invention relates to a method for 3D printing of a three-dimensional cathode, and belongs to the technical field of preparation of new energy nano-materials by using a 3D technology.
Background
As researchers seek the next generation of rechargeable batteries, sodium, magnesium, aluminum, zinc metal batteries are in the row. Metal batteries are considered to be the most ideal negative electrode material for batteries due to their high theoretical specific capacity and low potential. However, the application of the metal battery still cannot be popularized because of the volume expansion problem of the negative electrode in the cyclic charge-discharge process and the short circuit and even explosion problem of the battery caused by the penetration of the dendritic crystal formed in the cyclic process on the diaphragm.
Therefore, how to restrain the problem of dendrite formation during the cyclic charge and discharge of the battery under the condition of ensuring that the metal battery has high coulombic efficiency becomes a main research hotspot.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a secondary battery negative electrode that changes the growth direction of dendrites.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of 3D printing a three-dimensional negative electrode, comprising:
(1) adding 11-13 parts by weight of thickening agent to every 100 parts by weight of negative electrode slurry to prepare 3D printing negative electrode slurry (printing ink);
(2) modeling by utilizing three-dimensional software according to the three-dimensional negative electrode as a three-dimensional mesh structure;
(3) 3D printing is carried out, and a 3D printing prefabricated negative electrode is prepared;
(4) carrying out phase inversion on the prefabricated negative electrode in the step (3), removing the solvent in the prefabricated negative electrode, and carrying out vacuum drying;
(5) and (5) continuously printing an insulating polymer on the three-dimensional mesh structure of the prefabricated negative electrode in the step (4) in a 3D mode to obtain the three-dimensional negative electrode.
Preferably, the negative electrode slurry comprises 50-85 wt% of negative electrode material powder, 5-50 wt% of solvent and 5-15 wt% of conductive agent.
Specifically, the negative electrode material powder comprises one or more of natural graphite, artificial graphite, mesocarbon microbeads, soft carbon, hard carbon, carbon nanotubes, graphene, carbon fibers, silicon-based and other non-metallic materials, and further comprises one or more of zinc-based materials, copper-based materials, titanium-based materials and other metallic materials.
Specifically, the solvent is 1,1 dioxane or N-methyl pyrrolidone.
Specifically, the conductive agent is carbon black.
Preferably, the thickener is any one of polyvinyl alcohol PVA, sodium carboxymethyl cellulose CMC or polyvinylidene fluoride PVDF.
Preferably, the mesh shape in the three-dimensional network structure may be any geometric shape, such as circular, square, polygonal, preferably with a mesh area of 0.0025-0.25mm2The diameter of the printed line is controlled to be 5-200 mu m according to different cathode materials; the number of printing layers is 2-50.
Preferably, the vacuum drying temperature is 40-90 ℃ and the time is 10-30 hours.
Preferably, the insulating polymer is any one of polyethylene, polystyrene, polytetrafluoroethylene and the like, and the printing thickness is 20% -50% of the thickness of the single-layer three-dimensional cathode.
The invention has the advantages that: the three-dimensional cathode is prepared by 3D printing, is formed in one step, is high in speed and accurate and controllable in structure, and the prepared porous structure has a large specific surface area, so that the diffusion speed of ions is improved, and meanwhile, the battery has high ionic and electronic conductivity. More importantly, the three-dimensional porous end-capped negative electrode prepared by the method can effectively change the dendritic growth direction of the secondary battery so as to improve the safety performance of the battery.
Drawings
Fig. 1 is a schematic diagram of 3D printing of a three-dimensional negative electrode according to the present invention.
Fig. 2 is an SEM image of a negative electrode copper mesh of a lithium metal battery printed in 3D, in which (a-c) and (D-f) phases are reversed before and after the three-dimensional copper mesh morphology, and (g-i) three-dimensional Cu mesh internal microstructure.
FIG. 3 shows a copper mesh electrode of a lithium metal battery using 3D printing and lithium metal on a common copper foilElectrochemical performance test curve of anode, wherein (a) deposition stripping capacity is 1mah cm−2Constant current circulation (1 mA cm) of three-dimensional Cu and planar Cu foil electrodes−2) (ii) a (b) At a capacity of 50 mAh cm −25 mA cm−2Cycling 3D Cu and planar Cu foil electrodes under conditions.
Detailed Description
The invention aims to provide a method for 3D printing of a three-dimensional cathode, which is described with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic diagram of 3D printing of a three-dimensional negative electrode according to the present invention, in which 1 represents an insulating polymer layer, 2 represents a printing substrate (glass sheet), 3 represents a three-dimensional negative electrode, 4 represents printing lines, and 5 represents meshes, and in combination with fig. 1, the negative electrode having a three-dimensional porous network structure is prepared by a 3D printing technique according to the present invention, and dendrites originally growing perpendicular to a separator are changed to grow parallel to the separator, which can effectively avoid short circuits due to dendrites and a secondary battery exothermic combustion phenomenon caused by short circuits, and is helpful to increase the diffusion rate of ions, and simultaneously, the battery has higher ionic and electronic conductivities, and is a safer and superior secondary battery negative electrode.
Example 1
Taking a zinc metal battery as an example, the three-dimensional cathode printing process is as follows:
(1) taking 8g of zinc powder (the diameter of the powder is 10-100 mu m), 1g of conductive carbon black and 1g of polyvinylidene fluoride PVDF, and uniformly mixing in a planetary ball mill (the rotating speed is 250rpm, and the time is 30 min); and adding 3ml of N-methyl pyrrolidone into the uniformly mixed powder and uniformly stirring to obtain the cathode slurry.
(2) Under room temperature environment, adopt negative pole thick liquids to carry out 3D and print to glass is the printing basement, adopts the atmospheric pressure drive cylinder (to print the shower nozzle) directly to write the preparation negative pole: when the three-dimensional negative electrode single-layer structure of the three-dimensional network structure is printed, the periphery of the three-dimensional negative electrode single-layer structure is provided with a closed printing line, the interior of the three-dimensional negative electrode single-layer structure is provided with a grid structure, and the grid and the closed printing line are connected and fused into a whole. Wherein the mesh area is 0.01mm2The diameter of the printed line is controlled to be 100 mu m according to different cathode materials(ii) a The three-dimensional cathode three-dimensional structure is a single-layer structure and is superposed, and the number of layers is 3.
(3) And (3) immediately putting the printed and molded three-dimensional negative electrode structure into water, soaking for 5min, reversing the organic phase and the water phase in the electrode by utilizing a phase inversion principle, and removing the organic solvent from the electrode to leave the prefabricated electrode containing the organic binder, the thickening agent and the electrode active material group.
(4) And then, putting the prefabricated negative electrode after phase inversion into a vacuum oven for drying, wherein the temperature is set to be 80 ℃, and the time duration is 20 hours.
(5) And 3D printing the top end of the three-dimensional network structure of the printed three-dimensional cathode by adopting a polyethylene polymer, wherein the thickness is 30 mu m, covering the top end of the three-dimensional network structure and reserving the grid holes to obtain the three-dimensional cathode of the zinc metal battery.
Example 2
The three-dimensional cathode printing process of the lithium metal battery is as follows:
(1) taking 7g of zinc powder (the diameter of the powder is 10-100 mu m), 1.5g of conductive carbon black and 1.5g of polyvinylidene fluoride PVDF, and uniformly mixing in a planetary ball mill (the rotating speed is 250rpm, and the time is 30 min); and adding 5ml of 1, 1-dioxane into the uniformly mixed powder, and uniformly stirring to obtain the cathode slurry.
(2) Under room temperature environment, adopt negative pole thick liquids to print the shower nozzle and carry out 3D and print the step to glass adopts the air pressure drive cylinder to directly write the preparation negative pole for printing the basement: the three-dimensional negative electrode single-layer structure is printed as a peripheral closed printing line, the inside is a grid structure, and the grid is connected with the ring and is integrated. Wherein the gaps of the meshes are 250 μm square, and the mesh area is 0.0625mm2The diameter of a printed line is controlled to be 200 mu m; the three-dimensional cathode three-dimensional structure is a single-layer structure and is superposed, and the number of layers is 3.
(3) And (3) immediately putting the printed and molded three-dimensional negative electrode structure into water, soaking for 10min, reversing the organic phase and the water phase in the electrode by utilizing a phase inversion principle, and removing the organic solvent from the electrode to leave the prefabricated electrode containing the organic binder, the thickening agent and the electrode active material group.
(4) And then, putting the prefabricated negative electrode after phase inversion into a vacuum oven for drying, wherein the temperature is set to be 90 ℃, and the time duration is 24 hours.
(5) And 3D printing is carried out on the top end of the printed three-dimensional negative electrode by adopting a polyethylene polymer, the thickness is 25 mu m, the first layer of the three-dimensional negative electrode is covered, and the grid holes are reserved.
Fig. 2 is an SEM image of a negative electrode copper mesh of a lithium metal battery using 3D printing, in which (a-c) and (D-f) are three-dimensional copper mesh morphologies before and after phase inversion. (g-i) three-dimensional Cu mesh internal microstructure.
To further evaluate the cycling stability of lithium metal anodes deposited on 3D printed copper mesh electrodes and plain copper foil for lithium metal batteries, we performed cycling experiments on half-cells of lithium metal batteries at different current densities. The galvanostatic deposition lift-off voltage curves at different cycle numbers are shown in fig. 3. Copper mesh electrode of lithium metal battery with 3D printing at 1mA cm per cycle-2Shows a stable voltage plateau with a circulating capacity of 1mAh cm-2(gray curve in fig. 3 a). The overpotential can be maintained for 500 cycles at 20 mV, while the overpotential of a conventional copper foil electrode gradually increases after 150 cycles, exceeding 40 mV after 200 cycles (black voltage curve in FIG. 3 a). This represents a continuously increasing polarization of the plating and stripping processes. When the current density increased to 5 mA cm-2And the capacity is increased to 50 mAh cm-2In time, the copper mesh electrode of the 3D printed lithium metal battery was still able to run stably for 50 cycles (fig. 3 b). When the copper foil electrode is 50 mAh cm-2In the first (discharge) cycle, the cell has been short circuited. This is because of the rapid growth of lithium dendrites, resulting in membrane puncture. In addition, at ultra high current densities (10 mA cm)-2And 50 mA cm-2) The copper mesh electrode of the lithium metal battery using 3D printing also showed excellent cycling stability during the following charge and discharge tests. At 10 mA cm-2After 1000 cycles, the coulomb efficiency of the copper mesh electrode of the 3D printed lithium metal battery can reach 99.4%, and is maintained above 98%. This reflects that the three-dimensional structure of the 3D Cu grid favors passage of sufficient electrolysisMass storage forms a stable SEl film on metallic Li. The low value of coulombic efficiency in the initial cycle is related to the SEI film forming process. In contrast, after 82 th cycle, the coulombic efficiency of the copper foil electrode rapidly decreased. It can be at 50 mA cm thanks to the large number of active sites and spaces for dendrite growth inside the copper mesh electrode of the 3D printed lithium metal battery-2Is stably cycled for 500 times at the ultrahigh current density, which has never been reported before. After the 63 rd cycle, the coulombic efficiency of the plain copper foil dropped rapidly, probably due to short circuit by dendrite penetration through the separator. Thus, the layered porous structure of the copper mesh electrode of the 3D printed lithium metal battery can achieve a long lithium anode cycle life even at ultra-high current densities.
Example 3
For sodium-carbon dioxide battery
(1) Putting 7.8g of graphene, 1.3g of conductive carbon black and 1.2g of sodium carboxymethylcellulose (CMC) into a planetary ball mill, and uniformly mixing (the rotating speed is 250rpm, and the time is 30 min); 6.3ml of 1,1 dioxane is added into the uniformly mixed powder and is uniformly stirred, and then the cathode slurry is obtained.
(2) Under room temperature environment, adopt negative pole thick liquids to print the shower nozzle and carry out 3D and print the step to glass adopts the air pressure drive cylinder to directly write the preparation negative pole for printing the basement: the three-dimensional negative electrode single-layer structure is printed as a peripheral closed printing line, the inside is a grid structure, and the grid is connected with the ring and is integrated. Wherein the mesh gap is 150 μm, and the mesh area is 0.0225mm2The diameter of the printing filament is controlled to be 160 mu m according to different cathode materials; the three-dimensional cathode three-dimensional structure is a single-layer structure and is superposed, and the number of layers is 4.
(3) And (3) immediately putting the printed and molded three-dimensional negative electrode structure into water, soaking for 8min, reversing the organic phase and the water phase in the electrode by utilizing a phase inversion principle, and removing the organic solvent from the electrode to leave the prefabricated electrode containing the organic binder, the thickening agent and the electrode active material group.
(4) And then putting the prefabricated negative electrode after phase inversion into a vacuum oven for drying, wherein the temperature is set to be 85 ℃, and the time duration is 30 hours.
(5) And 3D printing is carried out on the top end of the printed three-dimensional negative electrode by adopting polyethylene polymer, the thickness is 45 mu m, the first layer of the three-dimensional negative electrode is covered, and grid holes are reserved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A method of 3D printing a three-dimensional anode, comprising:
(1) adding 11-13 parts by weight of thickening agent to every 100 parts by weight of negative electrode slurry to prepare 3D printing negative electrode slurry;
(2) modeling by utilizing three-dimensional software according to the three-dimensional negative electrode as a three-dimensional mesh structure;
(3) 3D printing is carried out, and a 3D printing prefabricated negative electrode is prepared;
(4) carrying out phase inversion on the prefabricated negative electrode in the step (3), removing the solvent in the prefabricated negative electrode, and carrying out vacuum drying;
(5) and (5) continuously printing an insulating polymer on the three-dimensional mesh structure of the prefabricated negative electrode in the step (4) in a 3D mode to obtain the three-dimensional negative electrode.
2. The method of claim 1, wherein the negative electrode slurry comprises 50-85 wt% of negative electrode material powder, 5-50 wt% of solvent, and 5-15 wt% of conductive agent.
3. The method of claim 2, wherein the negative electrode material powder comprises one or more of natural graphite, artificial graphite, mesocarbon microbeads, soft carbon, hard carbon, carbon nanotubes, graphene, carbon fibers and silicon-based non-metallic materials, and further comprises one or more of zinc-based materials, copper-based materials and titanium-based metal materials.
4. The method of claim 2, wherein the solvent is 1,1 dioxane or N-methylpyrrolidinone.
5. The method of claim 2, wherein the conductive agent is carbon black.
6. The method of claim 1, wherein the thickener is any one of polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), or polyvinylidene fluoride (PVDF).
7. The method of claim 1, wherein the three-dimensional network has a mesh area of 0.0025 mm to 0.25mm2The diameter of the printed line is 5-200 μm; the number of printing layers is 2-50.
8. The method of claim 1, wherein the vacuum drying temperature is 40 to 90 ℃ and the duration is 10 to 30 hours.
9. The method of claim 1, wherein the insulating polymer is any one of polyethylene, polystyrene and polytetrafluoroethylene, and the printing thickness is 20% to 50% of the thickness of the single-layer three-dimensional negative electrode.
10. A three-dimensional negative electrode prepared by the 3D printing method of any one of claims 1 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113497220A (en) * | 2021-07-13 | 2021-10-12 | 长春交大高能科技有限公司 | Preparation method of lithium ion battery cathode and related equipment |
| CN115513406A (en) * | 2022-09-30 | 2022-12-23 | 华中科技大学 | Zinc ion battery cathode, preparation method thereof and zinc ion battery |
| US20230238541A1 (en) * | 2022-01-27 | 2023-07-27 | GM Global Technology Operations LLC | Electrode structure for a battery and method of manufacturing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409727A (en) * | 2014-05-31 | 2015-03-11 | 福州大学 | Method for preparing lithium ion battery porous electrode based on 3D printing technology |
| CN104409774A (en) * | 2014-05-31 | 2015-03-11 | 福州大学 | 3D printing method of lithium battery |
| CN106099128A (en) * | 2016-07-05 | 2016-11-09 | 深圳大学 | A kind of three-dimensional lithium battery manufacture method |
| CN107696471A (en) * | 2017-10-10 | 2018-02-16 | 东莞华南设计创新院 | A kind of 3D printing method of flexible battery |
-
2020
- 2020-11-20 CN CN202011310242.2A patent/CN112467083A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409727A (en) * | 2014-05-31 | 2015-03-11 | 福州大学 | Method for preparing lithium ion battery porous electrode based on 3D printing technology |
| CN104409774A (en) * | 2014-05-31 | 2015-03-11 | 福州大学 | 3D printing method of lithium battery |
| CN106099128A (en) * | 2016-07-05 | 2016-11-09 | 深圳大学 | A kind of three-dimensional lithium battery manufacture method |
| CN107696471A (en) * | 2017-10-10 | 2018-02-16 | 东莞华南设计创新院 | A kind of 3D printing method of flexible battery |
Non-Patent Citations (1)
| Title |
|---|
| CHENGLONG CHEN等: "3D Printed High-Loading lithium-Sulfur Battery Toward Wearable Energy storage", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113497220A (en) * | 2021-07-13 | 2021-10-12 | 长春交大高能科技有限公司 | Preparation method of lithium ion battery cathode and related equipment |
| US20230238541A1 (en) * | 2022-01-27 | 2023-07-27 | GM Global Technology Operations LLC | Electrode structure for a battery and method of manufacturing the same |
| US11769884B2 (en) * | 2022-01-27 | 2023-09-26 | GM Global Technology Operations LLC | Electrode structure for a battery and method of manufacturing the same |
| CN115513406A (en) * | 2022-09-30 | 2022-12-23 | 华中科技大学 | Zinc ion battery cathode, preparation method thereof and zinc ion battery |
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