CN114050261B - Preparation method of zinc-based battery negative electrode material - Google Patents
Preparation method of zinc-based battery negative electrode material Download PDFInfo
- Publication number
- CN114050261B CN114050261B CN202111297849.6A CN202111297849A CN114050261B CN 114050261 B CN114050261 B CN 114050261B CN 202111297849 A CN202111297849 A CN 202111297849A CN 114050261 B CN114050261 B CN 114050261B
- Authority
- CN
- China
- Prior art keywords
- zinc
- electrode material
- negative electrode
- based battery
- zhs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a zinc-based battery negative electrode material, which comprises the following steps: mixing a metal salt solution and an organic ligand solution, immersing a zinc plate in the mixed solution, reacting to obtain a zinc plate with a precursor ZIF-L growing on the surface, assembling the zinc plate into a symmetrical battery, and electrically converting the precursor ZIF-L on the surface of the zinc plate into basic zinc sulfate (ZHS) by electric drive to obtain a zinc-based battery negative electrode material with a basic zinc sulfate protective layer on the surface; the invention solves the problems of over-fast growth of dendrite of the existing zinc cathode, poor cycle stability and easy short circuit, and converts ZIF-L @ Zn into ZHS to be used as a protective layer of the zinc cathode, and the protective layer can effectively inhibit the growth of the dendrite of zinc; the symmetrical battery assembled by the ZHS @ Zn cathode material is 2mA cm ‑2 The cycling stability tested under the current density is over 800h, and the full cell shows excellent discharge capacity and stability under the conditions of different multiplying powers.
Description
Technical Field
The invention relates to the technical field of nano materials and zinc-based batteries, in particular to a preparation method of a metal zinc negative electrode material based on basic zinc sulfate (ZHS) as a protective layer.
Background
With the rapid development of worldwide industrialization, the exploitation and utilization of fossil energy by human beings are increased, and the reserves of fossil energy are decreased, so that the demand of clean energy and renewable energy is increased. In such cases, sustainable energy sources such as wind, solar, tidal energy, etc. play a crucial role. Batteries are widely used for the storage and transportation of energy due to their good energy density and cycle life. The development and application of the lithium ion battery in the 90 s of the 20 th century bring a new breakthrough for energy storage, but because of the high price and shortage of lithium resources and high processing cost, and the safety problem caused by easy combustion of organic electrolyte, a novel green and environment-friendly energy storage system becomes the key of our exploration. Compared with lithium ion batteries using organic electrolytes which are inflammable and harmful to the environment, zinc Ion Batteries (ZIBs) using aqueous electrolytes are a novel, low-cost, safe and environment-friendly energy storage system, and have a great prospect for future portable, wearable and power grid energy storage systems. However, the application of the water system ZIBs still faces huge challenges, and the practical performance of the ZIBs is seriously influenced by the side reactions of structural stability, zinc dendrite, corrosion, hydrogen evolution and the like of the electrode material.
ZHS is a product (main component of zinc dendrite) in the charge and discharge process of the zinc ion battery, and dendrite is easily formed by uneven deposition of ZHS, so that the battery is short-circuited, and the performance of the battery is influenced. The current research on the stability of the zinc cathode mainly aims at inhibiting dendrite dendrites, such as designing different coatings to protect the surface of a zinc plate, developing novel or introducing different electrolyte additives, and modifying a diaphragm to regulate and control the uniform deposition of zinc ions, and the strategies can optimize the side reaction on the surface of the zinc plate to a certain extent. The direct and uniform preparation of the ZHS protective layer can directly regulate and control Zn 2+ The formation of dendritic ZHS is inhibited, thereby improving the stability of the zinc cathode.
The invention content is as follows:
in order to solve the problems of low ZIBs coulombic efficiency, poor cycle stability and the like of the conventional zinc negative electrode due to growth of dendrites, the invention provides a preparation method of a zinc-based battery negative electrode material.
The invention is not only suitable for zinc ion batteries, but also can be applied to other batteries using zinc metal negative electrodes, such as zinc-air batteries and nickel-zinc batteries.
The technical scheme of the invention is as follows:
a preparation method of a zinc-based battery negative electrode material comprises the following steps:
(1) Mixing a metal salt solution and an organic ligand solution, immersing a zinc plate in the mixed solution, reacting at 20-80 ℃ for 0.5-6.0 h, taking out, washing and drying to obtain the zinc plate (marked as ZIF-L @ Zn) with a precursor ZIF-L growing on the surface;
the thickness of the zinc plate is 0.01-0.2 mm, and the zinc plate is pretreated as follows before use: soaking the zinc plate in 0.1mol/L hydrochloric acid solution for 3min, then taking out and placing in ethanol: acetone: water volume ratio 1:1:1, removing surface impurities by ultrasonic treatment for 5min, then washing with deionized water, naturally drying, and polishing with 1000-mesh abrasive paper until the surface is smooth for later use;
the concentration of the metal salt solution is 0.01-10 mol/L, the solvent is deionized water, and the metal salt is zinc nitrate, zinc chloride, zinc acetate or zinc sulfate;
the concentration of the organic ligand solution is 0.01-10 mol/L, the solvent is deionized water, and the organic ligand is methylimidazole or 2-methylimidazole;
the volume ratio of the metal salt solution to the organic ligand solution is 1:1;
(2) Assembling the zinc plate with the precursor ZIF-L grown on the surface obtained in the step (1) into a symmetrical battery, and electrically converting the precursor ZIF-L on the surface of the zinc plate into basic zinc sulfate (ZHS) by electric drive to obtain a zinc-based battery negative electrode material (marked as ZHS @ Zn) with a basic zinc sulfate protective layer on the surface;
the electric drive time is 5min, and the current density is set to 1-5 mAcm -2 。
The invention carries out in-situ growth of flaky ZIF-L on the surface of a zinc plate and utilizes the porous structure and Zn of the flaky ZIF-L 2+ The characteristics of the metal center are taken as a precursor, when the precursor is assembled into a symmetrical battery and electrified, ZIF-L on the surface of a zinc plate is converted into basic zinc sulfate (ZHS @ Zn), the ZHS @ Zn symmetrical battery after electric drive conversion has the current density of 2mA cm -2 Can reach over 800h of ultra-long cycle under the test condition, and simultaneously, the full battery assembled by utilizing the ZHS @ Zn of the invention also has good performance.
The invention has the following beneficial effects:
(1) The preparation conditions are simple and mild, and the morphology of the prepared ZHS @ Zn can be controlled to change along with the experimental conditions;
(2) Can be produced in large scale or in industrialization;
(3) The ZIF-L @ Zn precursor prepared by the method has a uniform morphology structure, and the electrically-driven converted ZHS @ Zn electrode material can effectively improve the cycle performance of a symmetrical battery and is used for the use of a full battery.
Drawings
FIG. 1 is an SEM photograph of ZIF-L @ Zn and ZHS @ Zn samples obtained in example 1 (a-b are ZIF-L @ Zn and c is ZHS @ Zn).
FIG. 2 is an XRD pattern of ZIF-L, ZIF-L @ Zn, bare Zn and ZHS @ Zn obtained in example 1 (a is ZIF-L, ZIF-L @ Zn and Bare Zn, and b is ZHS @ Zn).
FIG. 3 shows symmetric cells at 2mA cm for ZHS @ Zn// ZHS @ Zn and Zn// Zn cells prepared in example 1 -2 Cycling performance plot at current density (a) and XRD plot after 50 cycles of cycling (b).
FIG. 4 shows ZHS @ Zn// MnO obtained in example 1 2 And Zn// MnO 2 Rate performance diagram of full cell.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Unless otherwise specified, the reagents used in the examples are all conventionally commercially available.
Example 1:
a preparation method of a zinc-based battery negative electrode material comprises the following steps:
(1) Surface treatment of pure zinc plates: soaking a 0.05mm thick zinc plate in 0.1mol L -1 In hydrochloric acid solution for 3min, then placed in ethanol: acetone: ultrasonic treatment is carried out in a container with water = 1.
(2) Preparing a ZIF-L @ Zn precursor: respectively adding 5.80g of zinc nitrate hexahydrate and 3.38g of 2-methylimidazole into a 100mL beaker containing 30mL of water at room temperature, mixing the two solutions, stirring to completely dissolve the two solutions, adding the mixture into the zinc plate treated in the step (1), reacting for 6 hours at room temperature, washing the zinc plate clean by using deionized water after the reaction is finished, and naturally airing the zinc plate. SEM of the prepared ZIF-L @ Zn precursor is shown as a-b in FIG. 1, and XRD contrast of ZIF-L, ZIF-L @ Zn and Bare Zn is shown as a in FIG. 2.
Preparing ZIF-L powder: respectively adding 5.80g of zinc nitrate hexahydrate and 3.38g of 2-methylimidazole into a 100mL beaker containing 30mL of water at room temperature, mixing the two solutions, uniformly stirring, reacting for 6h, centrifugally washing the obtained precipitate for 3 times by using deionized water, and performing vacuum drying at 60 ℃ for 12h to obtain ZIF-L powder.
(3) Preparation of ZHS @ Zn electrode: assembling the precursors in the step (2) into a symmetrical battery, taking ZIF-L @ Zn as a positive electrode plate and a negative electrode plate, taking glass fiber as a diaphragm and taking 2m ZnSO 4 As electrolyte, the button cell is assembled by a cell packaging machine at 2mA cm -2 And electrically driving for 5min under the current density, wherein the surface morphology of the driven material is shown as c in figure 1, and XRD is shown as b in figure 2.
(4)MnO 2 Preparation of electrode Material (MnO) 2 Electrode material as positive electrode material of full cell): 0.38g of MnSO 4 ·H 2 O was added to 15mL of deionized water to form solution A. 0.23g of KMnO 4 Dissolve in 15mL of deionized water to form solution B. Adding the solution B into the solution A to form a solution C, uniformly stirring, transferring the stirred solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 12 hours at 160 ℃. After cooling to room temperature, the precipitate was washed several times with deionized water and dried under vacuum. Taking the prepared MnO 2 : conductive carbon black (ECP): polyvinylidene fluoride (PVDF) =7:2:1 to 100mg, adding 100 mu L of N-methyl pyrrolidone to prepare slurry, coating the slurry on the surface of a Ti foil, drying the Ti foil in vacuum at 80 ℃ for 12 hours, and cutting the Ti foil into circular electrode slices, wherein the loading capacity of each slice is 1.4-1.6 mg.
The ZHS @ Zn zinc ion battery cathode material electrically driven and converted by the precursor ZIF-L @ Zn prepared in the embodiment is used as a positive electrode and a negative electrode to assemble a symmetrical battery, ZHS @ Zn is used as a positive electrode plate and a negative electrode plate, glass fiber is used as a diaphragm, and 2m ZnSO is used 4 As electrolyte, the button cell is assembled by a cell packaging machine and has the power of 2mA cm -2 The current density of (2) was measured for cycle performance, and the results of the test (a) in FIG. 3 show that the current density of ZHS @ Zn zinc in example 1The overpotential platform of the negative electrode material of the ion battery is stable after more than 800h of circulation, and b in fig. 3 is surface XRD after 50 cycles of circulation, which shows that the surface appearance of the assembled symmetrical battery is stable in the circulation process.
Meanwhile, the ZHS @ Zn zinc ion battery cathode material prepared in the embodiment is used as a cathode to be assembled into a full battery, ZHS @ Zn is used as a cathode electrode slice, and MnO is prepared 2 A circular electrode plate as a positive electrode plate, glass fiber as a diaphragm, 2m ZnSO 4 And 0.2mM MnSO 4 The mixed aqueous solution is used as electrolyte, and is assembled into a button cell by a cell packaging machine, and the weight of the button cell is 0.1A g -1 、0.2A g -1 、0.5Ag -1 、1.0A g -1 、2.0A g -1 、0.2A g -1 And circulating for 10 circles under the current density to carry out a multiplying power performance test. As shown by the test results of fig. 4, the full cell assembled by the negative electrode in example 1 shows higher discharge capacity and stability under different rate conditions.
Example 2:
(1) Surface treatment of pure zinc plates: a zinc plate with a thickness of 0.1mm was immersed in 0.1mol hydrochloric acid solution for 3min, followed by being placed in ethanol: acetone: ultrasonic treatment is carried out in a container with water =1
(2) Preparing a ZIF-L @ Zn precursor: respectively adding 5.80g of zinc chloride and 3.38g of imidazole into a 100mL beaker containing 30mL of water at room temperature, mixing the two solutions, stirring to completely dissolve the two solutions, adding the zinc plate treated in the step (1), reacting for 6 hours at room temperature, washing the zinc plate with deionized water after the reaction is finished, and naturally airing the zinc plate.
(3) Preparation of ZHS @ Zn-1 electrode: assembling the precursor in the step (2) into a symmetrical battery at 2mA cm -2 Electrically driving for 5min under the current density to obtain the ZHS @ Zn-1 electrode material.
A symmetrical cell assembled using the ZHS @ Zn-1 electrode material prepared in example 2 was operated at 2mA cm -2 The current density of the capacitor is kept for 200h, and no short circuit phenomenon occurs.
Example 3:
(1) Surface treatment of pure zinc plates: a zinc plate with a thickness of 0.1mm was immersed in 0.1mol hydrochloric acid solution for 3min, followed by being placed in ethanol: acetone: ultrasonic treatment is carried out in a container with water =1
(2) Preparing a ZIF-L @ Zn precursor: respectively adding 2.90g of zinc acetate and 3.38g of imidazole into a 100mL beaker containing 30mL of water at room temperature, mixing the two solutions, stirring to completely dissolve the two solutions, adding the zinc plate treated in the step (1), reacting for 6h at 60 ℃, washing the zinc plate with deionized water after the reaction is finished, and naturally airing.
(3) Preparation of ZHS @ Zn-2 electrode: assembling the precursors in the step (2) into a symmetrical battery at 2mA cm -2 Electrically driving for 5min under the current density to obtain the ZHS @ Zn-2 electrode material.
A symmetrical cell assembled using the ZHS @ Zn-2 electrode material prepared in example 3 was operated at 2mA cm -2 The current density of (2) is kept for 150h without short circuit phenomenon.
Example 4:
(1) Surface treatment of pure zinc plates: a zinc plate with a thickness of 0.1mm was immersed in 0.1mol hydrochloric acid solution for 3min, followed by being placed in ethanol: acetone: ultrasonic treatment is carried out in a container with water =1
(2) Preparing a ZIF-L @ Zn precursor: respectively adding 2.90g of zinc sulfate hexahydrate and 3.38g of imidazole into a 100mL beaker containing 30mL of water at room temperature, mixing the two solutions, stirring to completely dissolve the two solutions, adding the zinc plate treated in the step (1), reacting for 12 hours at 60 ℃, washing the zinc plate with deionized water after the reaction is finished, and naturally airing the zinc plate.
(3) Preparation of ZHS @ Zn-3 electrode: assembling the precursors in the step (2) into a symmetrical battery at 5mA cm -2 Electrically driving for 5min under the current density to obtain the ZHS @ Zn-3 electrode material.
A symmetrical cell assembled using the ZHS @ Zn-3 electrode material prepared in example 4 was operated at 2mA cm -2 Current density of (2) for 100hA short circuit phenomenon occurs.
Example 5:
(1) Surface treatment of pure zinc plates: a zinc plate with a thickness of 0.1mm was immersed in 0.1mol hydrochloric acid solution for 3min, followed by being placed in ethanol: acetone: ultrasonic treatment is carried out in a container with water =1
(2) Preparing a ZIF-L @ Zn precursor: respectively adding 5.80g of zinc sulfate hexahydrate and 3.38g of imidazole into a 100mL beaker containing 30mL of water at room temperature, mixing the two solutions, stirring to completely dissolve the two solutions, adding the zinc plate treated in the step (1), reacting for 12 hours at 60 ℃, washing the zinc plate clean by deionized water after the reaction is finished, and naturally airing the zinc plate.
(3) Preparation of ZHS @ Zn-4 electrode: assembling the precursors in the step (2) into a symmetrical battery at 5mA cm -2 Electrically driving for 5min under the current density to obtain the ZHS @ Zn-4 electrode material.
Symmetric cells assembled using the ZHS @ Zn-4 electrode material prepared in example 5 were at 2mA cm -2 The current density of (2) is kept for 80h without short circuit phenomenon.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the scope of the present invention as set forth in the claims.
Claims (6)
1. A preparation method of a zinc-based battery negative electrode material is characterized by comprising the following steps:
(1) Mixing a metal salt solution and an organic ligand solution, immersing a zinc plate in the mixed solution, reacting at 20-80 ℃ for 0.5-6.0 h, taking out, washing and drying to obtain the zinc plate with the precursor ZIF-L growing on the surface;
the metal salt is zinc nitrate, zinc chloride, zinc acetate or zinc sulfate;
the organic ligand is methylimidazole or 2-methylimidazole;
(2) Growing a precursor ZIF-L on the surface of the zinc plate group obtained in the step (1)Assembled into symmetrical cells with ZnSO 4 As an electrolyte, electrically converting a precursor ZIF-L on the surface of a zinc plate into basic zinc sulfate by electric drive to obtain a zinc-based battery negative electrode material with a basic zinc sulfate protective layer on the surface;
the electric drive time is 5min, and the current density is set to be 1-5 mA-cm -2 。
2. The method for preparing a negative electrode material for a zinc-based battery according to claim 1, wherein, in the step (1), the thickness of the zinc plate is 0.01 to 0.2mm.
3. The method for preparing a negative electrode material for a zinc-based battery according to claim 1, wherein, in the step (1), the zinc sheet is pretreated before use as follows: soaking the zinc plate in 0.1mol/L hydrochloric acid solution for 3min, then taking out and placing in ethanol: acetone: the volume ratio of water is 1:1:1 for 5min, then washing with deionized water, naturally drying, and polishing with 1000-mesh abrasive paper until the surface is smooth for later use.
4. The method for preparing a negative electrode material for a zinc-based battery according to claim 1, wherein the concentration of the metal salt solution is 0.01 to 10mol/L and the solvent is deionized water in the step (1).
5. The method for preparing a negative electrode material of a zinc-based battery according to claim 1, wherein in the step (1), the concentration of the organic ligand solution is 0.01 to 10mol/L, and the solvent is deionized water.
6. The method for preparing a negative electrode material for a zinc-based battery according to claim 1, wherein the volume ratio of the metal salt solution to the organic ligand solution in the step (1) is 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111297849.6A CN114050261B (en) | 2021-11-04 | 2021-11-04 | Preparation method of zinc-based battery negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111297849.6A CN114050261B (en) | 2021-11-04 | 2021-11-04 | Preparation method of zinc-based battery negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114050261A CN114050261A (en) | 2022-02-15 |
| CN114050261B true CN114050261B (en) | 2023-03-31 |
Family
ID=80207053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111297849.6A Active CN114050261B (en) | 2021-11-04 | 2021-11-04 | Preparation method of zinc-based battery negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114050261B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824152B (en) * | 2022-03-30 | 2023-02-03 | 南京工业大学 | Preparation method and application of zinc cathode modified by metal complex |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108288695A (en) * | 2018-01-11 | 2018-07-17 | 中南大学 | A kind of zinc-based secondary battery cathode material and preparation method thereof |
| CN110492088A (en) * | 2019-09-16 | 2019-11-22 | 安徽师范大学 | A kind of ZIF-8@redox graphene sulfur loaded composite material and preparation method and lithium-sulphur cell positive electrode and lithium-sulfur cell |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW557596B (en) * | 2002-06-03 | 2003-10-11 | Ming Chi Inst Of Technology | The method of preparing the solid-state polymer Zn-air battery |
| CN104393300B (en) * | 2014-10-14 | 2017-09-29 | 中国科学院宁波材料技术与工程研究所 | The electrode material of lithium ion battery and its application in lithium ion battery |
| CN105355890B (en) * | 2015-12-01 | 2017-09-26 | 天津师范大学 | The preparation method and application of negative electrode of lithium ion battery zinc sulphide graphene composite material |
| CN108767263B (en) * | 2018-07-16 | 2021-01-01 | 哈尔滨工业大学 | Preparation method and application of modified metal lithium negative electrode copper foil current collector |
| KR20210001662A (en) * | 2019-06-28 | 2021-01-06 | 주식회사 엘지화학 | Metal organic framework, porous carbon structure comprising the same and method for preparing the same |
| CN110492069B (en) * | 2019-08-11 | 2022-07-19 | 中山市华舜科技有限责任公司 | Synthesis method of Zn @ metal organic framework composite electrode material |
| CN110642236B (en) * | 2019-09-02 | 2022-10-11 | 吉首大学 | Zinc-based aqueous battery negative electrode material and preparation method thereof |
| CN111293300B (en) * | 2020-02-28 | 2022-04-22 | 中南大学 | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof |
| KR102572952B1 (en) * | 2020-03-03 | 2023-09-01 | 기초과학연구원 | Fabrication Method of Anode for Zinc-Ion Battery and Anode for Zinc-Ion Battery manufactured Therefrom and Aqueous Zinc-Ion Battery comprising the Same |
| CN111900388B (en) * | 2020-05-26 | 2021-12-07 | 北京理工大学 | Zinc ion battery negative electrode material, preparation and application thereof |
| CN112072087B (en) * | 2020-08-25 | 2022-02-18 | 浙江工业大学 | Preparation method and application of zinc ion battery negative electrode composite material |
| CN112582578B (en) * | 2020-12-28 | 2022-07-05 | 安阳师范学院 | Zinc cathode with protective layer and preparation method and application thereof |
-
2021
- 2021-11-04 CN CN202111297849.6A patent/CN114050261B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108288695A (en) * | 2018-01-11 | 2018-07-17 | 中南大学 | A kind of zinc-based secondary battery cathode material and preparation method thereof |
| CN110492088A (en) * | 2019-09-16 | 2019-11-22 | 安徽师范大学 | A kind of ZIF-8@redox graphene sulfur loaded composite material and preparation method and lithium-sulphur cell positive electrode and lithium-sulfur cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114050261A (en) | 2022-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106654221B (en) | Three-dimensional porous carbon coating selenizing Zinc material and preparation method thereof for negative electrode of lithium ion battery | |
| CN110642236B (en) | Zinc-based aqueous battery negative electrode material and preparation method thereof | |
| CN110492069B (en) | Synthesis method of Zn @ metal organic framework composite electrode material | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN104538604B (en) | Surface modifying method for lithium nickel manganese oxide positive electrode material | |
| CN108258241A (en) | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials | |
| CN113410453B (en) | Preparation method of metal-organic coordination film modified zinc cathode | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN113258070A (en) | Metal zinc cathode interface modification method for water-based zinc ion battery | |
| CN111313111A (en) | Heteroatom-doped carbon/CoS based on metal organic framework derivation2Functional material and application thereof | |
| CN112331933A (en) | Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN100353594C (en) | Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology | |
| CN114050261B (en) | Preparation method of zinc-based battery negative electrode material | |
| CN114792775A (en) | Polymer coating modified zinc cathode and preparation method and application thereof | |
| CN112421115A (en) | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof | |
| CN112234175B (en) | Preparation method of high-reversible aqueous zinc ion battery negative electrode material | |
| CN115064651A (en) | Bifunctional protective layer modified zinc cathode and preparation method thereof | |
| CN114551883A (en) | Aqueous zinc ion battery coating, cathode and battery | |
| CN112820876B (en) | Na2Ti3O7@Fe2O3Composite material, preparation method thereof and application thereof in sodium-ion battery | |
| CN114520302B (en) | Aqueous metal battery and modified anode thereof | |
| CN114649508B (en) | Antimony-based integrated electrode and preparation method and application thereof | |
| CN115020683B (en) | Preparation method of TAP/Ti3C2Tx electrode material | |
| CN116741922A (en) | Preparation method of water-based zinc ion battery zinc cathode material with surface in-situ constructed manganese-doped metal-organic framework layer | |
| CN117174816A (en) | Preparation method of fluorinated zinc oxide metal composite foil anode Zn@F-ZnO and energy storage application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |