CN115020700B - Zinc sodium phosphate/zinc metal anode and preparation method thereof - Google Patents
Zinc sodium phosphate/zinc metal anode and preparation method thereof Download PDFInfo
- Publication number
- CN115020700B CN115020700B CN202210075843.2A CN202210075843A CN115020700B CN 115020700 B CN115020700 B CN 115020700B CN 202210075843 A CN202210075843 A CN 202210075843A CN 115020700 B CN115020700 B CN 115020700B
- Authority
- CN
- China
- Prior art keywords
- zinc
- sodium phosphate
- particles
- foil
- anode
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/134—Electrodes based on metals, Si 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
- H01M4/13—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
-
- 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
- H01M4/42—Alloys based on zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a zinc metal battery anode. The anode sequentially comprises a zinc metal substrate and a zinc sodium phosphate layer growing on the surface of the zinc metal substrate, wherein the particle size of the zinc sodium phosphate layer is 1-12 mu m, and the zinc sodium phosphate layer comprises Na 6 Zn 6 (PO 4 ) 6 •8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 And O particles. In the invention, zinc sodium phosphate is constructed on the surface of zinc metal in situ as an artificial interface layer to improve the cycling stability of the zinc metal anode; the prepared zinc sodium phosphate/zinc foil has a cycle life which is improved by 12 times compared with a pure zinc foil.
Description
Technical Field
The invention belongs to the field of new generation energy storage, and particularly relates to a zinc metal anode and a preparation method thereof.
Background
In recent years, lithium Ion Batteries (LIBs) have achieved great success in portable electronic products and electric vehicles. Lithium ion batteries have been an important energy storage system in recent years, and their inherent disadvantages, including high price, poor lithium resources, toxic electrolytes, and safety issues, have severely hampered their further large-scale energy storage applications. The rechargeable water-based zinc metal battery has the remarkable advantages of high safety, high ion conductivity, low cost, high energy density and the like as an important energy storage system. However, zinc metal is susceptible to zinc dendrite formation (which tends to short-circuit the cell) and side reactions (corrosion, water splitting) during repeated deposition/stripping processes, which greatly prevent the large-scale application of zinc metal cells.
An effective way to date to inhibit the growth of dendrites and side reactions of zinc metal anodes has been to increase the coulombic efficiency of zinc metal anodes. For example, designing eutectic zinc alloys, developing new or high concentration electrolytes, and introducing different electrolyte additives. Although these methods have hindered zinc dendrite growth to some extent, there are still strong side reactions, which make it impossible to satisfy practical industrial applications. The construction of an artificial solid interface layer is a good choice, which can not only inhibit zinc dendrite growth, but also prevent side reactions. However, the most common method of constructing artificial interfacial layers is currently achieved by painting. However, the artificial interface layer constructed by the method has risks of uneven distribution, easy falling off in the circulation process and the like. Thus, the in situ development of a dense, uniform, strong adhesion artificial interfacial layer remains a challenge for zinc metal anodes.
In order to inhibit the growth of zinc dendrites and the side reaction process, an artificial interface layer-zinc sodium phosphate is constructed on the surface of a zinc metal anode in situ by an electrodeposition method. PO (Positive oxide) 4 3- Ions and Zn 2+ The interaction between the zinc and the metal can effectively adjust the charge distribution of the zinc metal surface, further cause the uneven charge distribution of the artificial interface layer, thereby accelerating Zn 2+ The diffusion speed to the artificial interface layer is improved, and the binding force between the artificial interface layer and zinc metal is also improved. In addition, the zinc sodium phosphate can obviously reduce Zn in the process of stripping/electroplating zinc metal 2+ The deposited energy barrier is favorable for Zn 2+ The uniform deposition of zinc dendrites is hindered and the cycle life of the zinc metal battery is greatly improved.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a zinc sodium phosphate/zinc metal anode and a preparation method thereof, which aims at constructing an artificial interface layer on the surface of the zinc metal anode in situ to slow down zinc goldZinc dendrites and side reactions are formed during repeated deposition/stripping processes, thereby increasing the cycle life of the metallic zinc cell. In order to achieve the above object, according to one aspect of the present invention, there is provided an anode comprising a zinc substrate and a zinc sodium phosphate layer grown on the surface of the zinc substrate, the zinc sodium phosphate having a particle diameter of 1 μm to 12 μm, the zinc sodium phosphate particles being composed of Na 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 O particles, wherein the mass ratio of the zinc sodium phosphate layer to the substrate is 1: 100-1: 1000.
preferably, the zinc substrate is zinc foil, zinc wire, zinc-copper alloy or zinc-nickel alloy.
Preferably, the Na 6 Zn 6 (PO 4 ) 6 ·8H 2 The particle diameter of the O particles is 1-8 mu m, and the Na is 12 [Zn 12 P 12 O 48 ]·12H 2 The particle diameter of the O particles is 3-12 μm.
Preferably, the mass ratio of the zinc sodium phosphate layer to the substrate is 1:300 to 1:500.
according to another aspect of the present invention, there is also provided a method for preparing the above anode, comprising the steps of:
S1.Na 3 PO 4 preparing an electrolyte: preparing 0.1M-8M NaOH solution, then adding proper quantity of H 3 PO 4 The pH of the solution is adjusted to 6-8.
S2, respectively taking polished zinc foil as a working electrode, pt as a counter electrode and saturated calomel as a reference electrode, and Na 3 PO 4 As electrolyte, electrodepositing for 100-500 s under the voltage of-1-0V to obtain a zinc sodium phosphate protective layer on the surface of the zinc foil, wherein the zinc sodium phosphate particles are made of Na 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 And O particles.
Preferably, the concentration of the NaOH solution is 0.5-2M.
Preferably, the deposition voltage is-0.3 to-0.5V.
In general, compared with the prior art, the above technical scheme contemplated by the invention can obtain the following beneficial effects by in-situ construction of sodium/zinc phosphate as anode material:
1. the invention selects Na to overcome the defects of zinc dendrite formation (easy cell short circuit) and side reaction (corrosion and water decomposition) in the repeated electroplating/stripping process of the current zinc metal cell anode 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 The zinc sodium phosphate compound composed of O particles is covered on the surface of zinc metal to be used as an artificial interface layer, and the cycle life of the zinc sodium phosphate compound is proved to be improved by 12 times compared with that of pure zinc foil without the artificial interface layer.
2. And constructing a zinc sodium phosphate interface layer on the surface of the zinc substrate in situ by an electrodeposition method, and combining the zinc substrate with the zinc substrate instead of a smearing method. The method has the advantages of uniform artificial interface layer constructed on the zinc metal surface, strong adhesive force, simplicity and realization of industrial application.
3. At the interface of sodium zinc phosphate and zinc metal, PO is present 4 3- The interaction of ions and zinc atoms aggravates the uneven charge distribution on the surface of the metallic zinc, thereby enhancing Zn 2+ And the diffusion at the interface also increases the adhesion of the zinc sodium phosphate film to the zinc surface.
The 4-sodium zinc phosphate layer is highly stable in the water electrolyte, and can obviously reduce Zn in the process of stripping/electroplating zinc metal 2+ The deposited energy barrier enhances the reversibility of zinc metal electroplating/stripping and improves the cycle life of the zinc metal battery.
Drawings
FIG. 1 is an optical photograph of example 1 of the present invention, (a) zinc foil after polishing; (b) sodium zinc phosphate/zinc foil.
FIG. 2 is an X-ray diffraction pattern of examples 1-4 of the present invention.
FIG. 3 is a scanning electron microscope image of examples 1-4 of the present invention, (a) electrodeposited 100s zinc sodium phosphate/zinc foil; (b) electrodepositing a 200s zinc sodium phosphate/zinc foil; (c) electrodepositing 300s of zinc sodium phosphate/zinc foil; (d) electrodepositing 500s of zinc sodium phosphate/zinc foil.
FIG. 4 is a cycle life chart of examples 1-4 of the present invention.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention provides a zinc metal battery and an anode for the battery, which comprises a zinc substrate and a zinc sodium phosphate layer growing on the surface of the zinc substrate, wherein the mass ratio of the zinc sodium phosphate layer to the substrate is 1: 100-1: 1000, and preferably 1:300 to 1:500. when the mass ratio of the zinc sodium phosphate layer to the substrate is too small, the electrolyte cannot be effectively prevented from being in direct contact with zinc metal, and side reactions (corrosion and water decomposition) of the zinc metal are not prevented; when the mass ratio of the zinc sodium phosphate layer to the substrate is too large, zn in the electrolyte is completely blocked 2+ Plating/stripping reactions occur on the zinc metal surface and the cycle life will be reduced.
The zinc substrate is a conductive substrate containing zinc metal, and the zinc substrate is made of zinc foil, zinc wires, zinc-copper alloy and zinc-nickel alloy. Because of the high zinc content of the zinc foil, the zinc foil has better flexibility (strong mechanical binding force of sodium zinc phosphate), so that the zinc foil is preferable as a base material.
The zinc sodium phosphate particles are used as an artificial interface layer to be attached to the surface of zinc metal and are made of Na 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 O particle composition, wherein Na 6 Zn 6 (PO 4 ) 6 ·8H 2 The particle diameter of the O particles is 1-8 mu m, and the Na is 12 [Zn 12 P 12 O 48 ]·12H 2 The particle diameter of the O particles is 3-12 μm.
The preparation method of the anode comprises the following steps:
S1.Na 3 PO 4 preparing an electrolyte: preparing 0.1M-8M NaOH solution, then adding proper quantity of H 3 PO 4 The pH value of the solution is regulated to 6-8; during the same electrodeposition time, the concentration of NaOH is too high, and the zinc sodium phosphate is deposited too thick on the surface of the zinc foil, resulting in Zn in the electrolyte 2+ It is difficult to perform an electroplating/stripping reaction on the zinc metal surface, thereby reducing the cycle life of the zinc metal anode; the concentration of NaOH is too low, and zinc sodium phosphate can be deposited on the surface of zinc foil too thin to well prevent electrolyte from directly contacting zinc metal (corrosion and water decomposition reaction are easy to occur), so that the cycle life of the zinc metal anode is reduced.
S2, respectively taking polished zinc foil as a working electrode, pt as a counter electrode and saturated calomel as a reference electrode, and Na 3 PO 4 And (3) electrodepositing the zinc foil serving as electrolyte for 100-500 seconds under the voltage of-1-0V to obtain the zinc sodium phosphate protective layer on the surface of the zinc foil.
During the same electrodeposition time, the deposition voltage is too negative, and the zinc sodium phosphate is too thick deposited on the surface of the zinc foil, resulting in Zn in the electrolyte 2+ It is difficult to perform an electroplating/stripping reaction on the zinc metal surface, thereby reducing the cycle life of the zinc metal anode; the deposition voltage is too positive, and the zinc sodium phosphate is too thin to well prevent the electrolyte from being in direct contact with zinc metal on the surface of the zinc foil, so that the cycle life of the zinc metal anode is reduced, and therefore, the deposition voltage is preferably-0.3 to-0.5V.
The following are specific examples:
example 1
S1, a piece of zinc foil is taken and polished by sand paper to remove an oxide layer, and is wiped by acetone and ethanol in sequence, and finally the zinc foil is cut into the area of 4 multiplied by 4cm. Na (Na) 3 PO 4 Preparing an electrolyte: preparing 1M NaOH solution, and then adding a proper amount of H 3 PO 4 The pH of the solution is adjusted to 6-8.
S2, respectively taking polished zinc foil as a working electrode, pt as a counter electrode and saturated calomel as a reference electrode, and Na 3 PO 4 Electrodepositing 100 as an electrolyte at a voltage of-0.4Vs, the zinc sodium phosphate/zinc foil can be obtained. And washing the zinc sodium phosphate/zinc foil with deionized water, and baking at 60 ℃ for 12 hours to obtain the anode.
For simplicity of description, the preparation conditions of example 2 to example 11 are listed as table 1.
TABLE 1
Analysis of experimental results
FIG. 1 is an optical photograph of example 1 of the present invention; it can be seen that the polished zinc foil surface presents a bright white metallic luster and has obvious polishing scratches. And the surface of the zinc sodium phosphate/zinc foil presents a compact light gray protective film.
FIG. 2 is an X-ray diffraction pattern (JCPCDS 49-0621 and JCPCDS 47-0246) for examples 1-4; it can be seen that Na grows on the surface of the zinc metal 6 Zn 6 (PO 4 ) 6 ·8H 2 O (JCPLDS 47-0246) and Na 12 [Zn 12 P 12 O 48 ]·12H 2 O(JCPDS49-0621)。
FIG. 3 is a scanning electron microscope image of examples 1-4; it can be seen that the zinc foil surface grows with a number of irregular triangular and circular materials (zinc sodium phosphate), the more zinc sodium phosphate and the particle size of the zinc sodium phosphate is 1 μm to 12 μm as the deposition time increases. The Na is 6 Zn 6 (PO 4 ) 6 ·8H 2 The particle diameter of the O particles is 1-8 mu m, and the Na is 12 [Zn 12 P 12 O 48 ]·12H 2 The particle diameter of the O particles is 3-12 μm.
FIG. 4 shows the results of examples 1 to 4 according to the invention at 1mA/cm 2 、0.25mAh/cm 2 A lower cycle charge-discharge life chart; it can be seen that the zinc sodium phosphate/zinc foil has a longer cycle time than the zinc foil, and that the zinc sodium phosphate/zinc foil has the longest cycle time (1200 hours, 12 times higher than the zinc metal electrode) when deposited for 300 s.
The above-mentioned tests were carried out in examples 5 to 11, and similar results to those in examples 1 to 4 were obtainedThe method comprises the steps of carrying out a first treatment on the surface of the It can also be seen that the anode obtained in examples 1-11 comprises, in order from the bottom surface to the top surface, a zinc substrate and a zinc sodium phosphate layer having a particle diameter of 1 μm to 12 μm, wherein the zinc sodium phosphate particles are composed of Na 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 O particles, wherein the mass ratio of the zinc sodium phosphate layer to the substrate is 1: 100-1: 1000, na 6 Zn 6 (PO 4 ) 6 ·8H 2 The particle diameter of the O particles is 1-8 mu m, and the Na is 12 [Zn 12 P 12 O 48 ]·12H 2 The particle diameter of the O particles is 3-12 mu m, and the mass ratio of the zinc sodium phosphate layer to the zinc substrate is 1:300 to 1: at 500, the cycle times of the examples all perform well.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. An anode for zinc metal battery is characterized by comprising a zinc substrate and a zinc sodium phosphate layer growing on the surface of the zinc substrate, wherein the particle size of the zinc sodium phosphate is 1-12 mu m, and the zinc sodium phosphate particles are made of Na 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 O particles, wherein the mass ratio of the zinc sodium phosphate layer to the zinc substrate is 1: 100-1: 1000, wherein the zinc substrate is zinc foil, and the preparation method of the anode comprises the following steps:
S1.Na 3 PO 4 preparing an electrolyte: preparing 0.1-8M NaOH solution, then adding proper quantity of H 3 PO 4 The pH value of the solution is regulated to 6-8;
s2, respectively taking polished zinc foil as a working electrode, platinum as a counter electrode and a saturated calomel electrode as a reference electrode, and Na 3 PO 4 Is electrolyte, and is at electricity of-1 to 0VAnd electrodepositing for 100-500 s under reduced pressure to obtain the zinc sodium phosphate protective layer on the surface of the zinc foil.
2. The anode of claim 1, wherein the Na 6 Zn 6 (PO 4 ) 6 ·8H 2 The particle diameter of the O particles is 1-8 mu m, and the Na is 12 [Zn 12 P 12 O 48 ]·12H 2 The particle diameter of the O particles is 3-12 μm.
3. The anode of claim 1, wherein the mass ratio of the zinc sodium phosphate layer to the zinc substrate is 1:300 to 1:500.
4. a method of preparing an anode according to any one of claims 1 to 3, comprising the steps of:
S1.Na 3 PO 4 preparing an electrolyte: preparing 0.1-8M NaOH solution, then adding proper quantity of H 3 PO 4 The pH value of the solution is regulated to 6-8;
s2, respectively taking polished zinc foil as a working electrode, platinum as a counter electrode and a saturated calomel electrode as a reference electrode, and Na 3 PO 4 As electrolyte, electrodepositing for 100-500 s under the voltage of-1-0V to obtain a zinc sodium phosphate protective layer on the surface of the zinc foil, wherein the zinc sodium phosphate particles are made of Na 6 Zn 6 (PO 4 ) 6 ·8H 2 O particles and Na 12 [Zn 12 P 12 O 48 ]·12H 2 And O particles.
5. The method according to claim 4, wherein the concentration of the NaOH solution is 0.5-2M and the deposition voltage is-0.3 to-0.5V.
6. A zinc metal battery comprising an anode according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210075843.2A CN115020700B (en) | 2022-01-23 | 2022-01-23 | Zinc sodium phosphate/zinc metal anode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210075843.2A CN115020700B (en) | 2022-01-23 | 2022-01-23 | Zinc sodium phosphate/zinc metal anode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115020700A CN115020700A (en) | 2022-09-06 |
| CN115020700B true CN115020700B (en) | 2023-05-09 |
Family
ID=83067715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210075843.2A Active CN115020700B (en) | 2022-01-23 | 2022-01-23 | Zinc sodium phosphate/zinc metal anode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115020700B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104300122A (en) * | 2014-10-19 | 2015-01-21 | 桂林理工大学 | Preparation method of negative material of nickel-zinc battery |
| CN104810419A (en) * | 2015-04-29 | 2015-07-29 | 天津理工大学 | Copper zinc tin selenium solar cell device and preparing method thereof |
| JP2020093968A (en) * | 2018-12-06 | 2020-06-18 | 曙ブレーキ工業株式会社 | Snow crystal-like zinc carbonate salt particle, snow crystal-like composite particle and method for producing the same |
| CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
-
2022
- 2022-01-23 CN CN202210075843.2A patent/CN115020700B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104300122A (en) * | 2014-10-19 | 2015-01-21 | 桂林理工大学 | Preparation method of negative material of nickel-zinc battery |
| CN104810419A (en) * | 2015-04-29 | 2015-07-29 | 天津理工大学 | Copper zinc tin selenium solar cell device and preparing method thereof |
| JP2020093968A (en) * | 2018-12-06 | 2020-06-18 | 曙ブレーキ工業株式会社 | Snow crystal-like zinc carbonate salt particle, snow crystal-like composite particle and method for producing the same |
| CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115020700A (en) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1613159A (en) | Current collector structure and methods to improve the performance of a lead-acid battery | |
| CN111916744B (en) | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof | |
| CN111668493A (en) | Three-dimensional current collector for inhibiting dendritic crystal of lithium metal negative electrode and application of three-dimensional current collector in metal lithium battery | |
| CN103477477A (en) | Negative electrode active material for a lithium secondary battery, and method for preparing same | |
| CN113013418A (en) | Alloy framework supported zinc metal cathode and preparation method and application thereof | |
| CN114883670A (en) | Water-based zinc ion battery electrolyte taking wheat straw extract as biomass organic salt additive and application thereof | |
| CN115799512A (en) | Preparation and application of cathode material of water-based zinc ion battery capable of inhibiting dendritic crystal growth | |
| EP2419952B1 (en) | Electrically rechargeable battery with zn electrode, and method for manufacturing said battery | |
| CN115020700B (en) | Zinc sodium phosphate/zinc metal anode and preparation method thereof | |
| CN110350146B (en) | Modified three-dimensional porous antimony electrode, preparation method and application | |
| CN116111068A (en) | Zinc cathode material modified by three-dimensional antimony/antimony oxide composite layer and preparation method and application thereof | |
| CN113571710B (en) | Copper current collector for lithium metal battery and surface modification method and application thereof | |
| KR20230080868A (en) | Zinc metal anode for aqueous secondary battery, preparation method thereof and aqueous secondary battery comprising the zinc metal anode | |
| CN114243019A (en) | Zinc cathode material with double modification layers on surface, preparation method thereof and application of zinc cathode material in water-based zinc ion battery | |
| Yao et al. | Effect of Composite Additives on the Zinc Anode of Zinc-Nickel Single-Flow Batteries | |
| CN108660484A (en) | A method of preparing zinc indium alloy powder using electrochemical co-deposition | |
| Xie et al. | Effect of K2SnO3 in Electrolyte on the Property of Single-Flow Zinc-Nickel Battery | |
| CN117542948B (en) | Water-based zinc ion battery negative electrode material, preparation method and zinc ion battery | |
| CN117637974A (en) | Three-dimensional composite zinc cathode and preparation method and application thereof | |
| CN117594884A (en) | Water-based zinc ion battery electrolyte and preparation method and application thereof | |
| CN117276707A (en) | Aqueous zinc ion battery dual-additive electrolyte and preparation method and application thereof | |
| CN117071004A (en) | Preparation method of metallic zinc with certain crystal plane orientation by amphiphilic small organic molecule electrodeposition | |
| CN115692706A (en) | Double-layer protective layer of metal lithium and interface modification method of metal lithium cathode | |
| CN117936683A (en) | High-utilization-rate dendrite-free zinc electrodeposited/stripped bismuth functional layer and construction method and application thereof | |
| CN112103476A (en) | Lithium-free negative electrode material of dual-ion battery, preparation method and dual-ion battery |
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 |