CN114927677A - Flexible sodium battery negative electrode material and green preparation method and application thereof - Google Patents
Flexible sodium battery negative electrode material and green preparation method and application thereof Download PDFInfo
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- CN114927677A CN114927677A CN202210608710.7A CN202210608710A CN114927677A CN 114927677 A CN114927677 A CN 114927677A CN 202210608710 A CN202210608710 A CN 202210608710A CN 114927677 A CN114927677 A CN 114927677A
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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
- H01M4/36—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
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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
- 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 flexible sodium battery cathode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing the flexible current collector in electroplating solution, depositing tin and zinc on the flexible current collector in an electrodeposition mode, and then charging to dissolve deposited zinc to obtain the flexible porous tin negative electrode material; the electroplating solution comprises zinc salt, tin salt, trisodium citrate and tartaric acid. The preparation method adopts the integrated technology of electro-deposition alloying and dealloying to prepare the porous tin anode material, has simple and easy preparation process, is green and environment-friendly, and is expected to realize large-scale production.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and particularly relates to a flexible sodium battery negative electrode material, and a green preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Among the alloy negative electrode materials of sodium batteries, the metallic tin negative electrode has high theoretical specific capacity (847mAh g) -1 ) And a lower reaction potential, and thus has great application potential. But during the circulation process, large volume expansion (420%) is generated, the structure of the electrode is damaged, and the electrode material is pulverized and broken to be concentratedShedding the fluid; in addition, a large volume change may form an unstable SEI film, thereby consuming electrolyte and sodium ions, resulting in rapid capacity fade.
The problem can be effectively solved by making the tin material porous, the porous structure has a large specific surface area, and the shell increases the contact area of the electrolyte; the pore structure can provide a channel for rapid diffusion of sodium ions; in addition, the volume change in the circulating process can be buffered, and the circulating stability of the material can be improved. The special porous structure can improve the electrochemical performance of the tin cathode to a certain extent.
The existing preparation method of the porous tin has the problems of complex process, harsh conditions, need of toxic substances and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a flexible sodium battery negative electrode material, and a green preparation method and application thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a flexible sodium battery negative electrode material, which comprises the following steps:
placing the flexible current collector in electroplating solution, depositing tin and zinc on the flexible current collector in an electrodeposition mode, and then charging to dissolve deposited zinc to obtain the flexible porous tin negative electrode material;
the electroplating solution comprises zinc salt, tin salt, trisodium citrate and tartaric acid.
In a second aspect, the invention provides a flexible sodium battery negative electrode material prepared by the preparation method.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
the preparation method adopts the integrated technology of electro-deposition alloying and dealloying to prepare the porous tin anode material, has simple and easy preparation process, is green and environment-friendly, and is expected to realize large-scale production.
The zinc obtained by dealloying in the invention can be recycled, the utilization rate of materials can be improved, and the production cost is further reduced.
The proportion of different metals in the zinc-tin alloy can be adjusted by adjusting parameters in the alloying process, so that the pore size and the distribution of the porous tin product can be regulated and controlled.
The porosity of the porous tin can be adjusted by adjusting parameters in the dealloying process.
The flexible porous tin material prepared by the invention has good mechanical property, can effectively buffer the volume change in the circulation process, keeps the stability of the structure and obtains good circulation performance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Figure 1 is an XRD pattern of the porous tin product of example 1.
Fig. 2 is a cyclic voltammogram of the product porous tin of example 1 as a negative electrode material for a sodium ion battery.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
In a first aspect, the invention provides a preparation method of a flexible sodium battery negative electrode material, which comprises the following steps:
placing the flexible current collector in electroplating solution, depositing tin and zinc on the flexible current collector in an electrodeposition mode, and then charging to dissolve deposited zinc to obtain the flexible porous tin negative electrode material;
the electroplating solution comprises zinc salt, tin salt, trisodium citrate and tartaric acid.
Trisodium citrate is used as a conductive salt to improve the conductivity of the electrolyte, and tartaric acid is used for stabilizing the pH value of the electroplating solution.
In some embodiments, the flexible current collector is selected from copper foil, aluminum foil, carbon-based materials, or mxeenes.
In some embodiments, the zinc salt is zinc chloride or zinc sulfate.
Preferably, the concentration of the zinc salt is 0.01-0.5 mol L -1 。
In some embodiments, the tin salt is tin chloride.
Preferably, the concentration of the stannic chloride is 0.01-0.5 mol L -1 。
Preferably, the concentration of trisodium citrate is 0.2-1.0 mol L -1 。
Preferably, the concentration of the tartaric acid is 0.05-0.5 mol L -1 。
Too high concentrations of zinc and tin salts can result in too large and uneven electrodeposited particles, and too low concentrations can result in too little active material being obtained by electrodeposition. Too low a concentration of trisodium citrate will result in too low an electrolyte conductivity and too high a solubility. Too high a concentration of tartaric acid causes the electrolyte to be slightly acidic, while too low a concentration may cause the solution to be slightly alkaline.
In some embodiments, the solvent of the electroplating solution is a mixed solution of water and ethylene glycol.
Preferably, the volume ratio of the water to the glycol is 3: 1-1: 3.
In some embodiments, the electrodeposition is constant current discharge with a current density of 10-50 mA cm -2 The time is 30 s-2 h.
Preferably, the charging is constant current charging, and the current density is 1-20 mA cm -2 The time is 300s-6 h.
In a second aspect, the invention provides a flexible porous tin anode material prepared by the preparation method.
The present invention will be further described with reference to the following examples.
Example 1
A flexible sodium battery negative electrode material and a preparation method thereof are disclosed:
electroplating solution: 0.2M SnCl 4 +0.2M ZnCl 2 +0.12M trisodium citrate +0.15M tartaric acid.
Placing the copper foil in the electroplating solution, and discharging at constant current of 10mA cm -2 The time is 3 min; then at 1mA cm -2 Charging for 32min under the current density, and washing and drying to obtain the flexible porous tin material with the pore size distribution of 500-600 nm.
Fig. 1 is an XRD pattern of the porous tin product of example 1, and characteristic peaks of tin are observed, and other miscellaneous peaks do not appear, indicating that a high-purity porous tin material is synthesized.
Fig. 2 is a cyclic voltammogram of the product porous tin of example 1 as a negative electrode material for a sodium ion battery. The characteristic peak of the tin material during sodium storage is shown, and in addition, the overlapped curve further shows that the synthesized porous tin material has good cycle performance.
Example 2
A flexible sodium battery negative electrode material and a preparation method thereof are disclosed:
electroplating solution: 0.15M SnCl 4 +0.15M ZnCl 2 +0.12M trisodium citrate +0.11M tartaric acid
Placing the copper foil in the electroplating solution, and discharging with constant current of 15mA cm -2 The time is 2 min; then at 2mA cm -2 Charging for 17min under the current density, and washing and drying to obtain the flexible porous tin material with the pore size distribution of 800-900 nm.
Example 3
A flexible sodium battery negative electrode material and a preparation method thereof are disclosed:
electroplating solution: 0.08M SnCl 4 +0.08M ZnCl 2 +0.12M trisodium citrate +0.15M tartaric acid
Placing the copper foil in the electroplating solution, and discharging at constant current of 18mA cm -2 The time is 2 min; then at 1mA cm -2 Charging for 40min under the current density, and washing and drying to obtain the flexible porous tin material with the pore size distribution of 900-950 nm.
Example 4
A flexible sodium battery negative electrode material and a preparation method thereof are disclosed:
electroplating solution: 0.2M SnCl 4 +0.2M ZnCl 2 +0.12M lemonTrisodium citrate +0.15M tartaric acid
Mixing Ti 3 C 2 The film was placed in the above-mentioned plating solution with a constant current discharge current of 10mA cm -2 The time is 3 min; then at 1mA cm -2 Charging for 32min under the current density, and washing and drying to obtain the flexible porous tin material with the pore size distribution of 600-650 nm.
Example 5
A flexible sodium battery negative electrode material and a preparation method thereof are disclosed:
electroplating solution: 0.15M SnCl 4 +0.15M ZnCl 2 +0.12M trisodium citrate +0.11M tartaric acid
Placing carbon cloth in the electroplating solution, and constant current discharging at 15mA cm -2 The time is 2 min; then at 2mA cm -2 Charging for 17min under the current density, washing and drying to obtain the flexible porous tin material, wherein the pore size distribution of the porous tin material is 750-900 nm.
Example 6
A flexible sodium battery negative electrode material and a preparation method thereof are disclosed:
electroplating solution: 0.08M SnCl 4 +0.08M ZnCl 2 +0.12M trisodium citrate +0.15M tartaric acid
Placing the carbon net in the electroplating solution, and discharging at constant current of 18mA cm ～2 The time is 2 min; then at 1mA cm -2 Charging for 40min under the current density, and washing and drying to obtain the flexible porous tin material with the pore size distribution of 900-950 nm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a flexible sodium battery negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
placing the flexible current collector in electroplating solution, depositing tin and zinc on the flexible current collector in an electrodeposition mode, and then charging to dissolve deposited zinc to obtain the flexible porous tin negative electrode material;
the electroplating solution comprises zinc salt, tin salt, trisodium citrate and tartaric acid.
2. The preparation method of the flexible sodium battery negative electrode material according to claim 1, characterized by comprising the following steps: the flexible current collector is selected from copper foil, aluminum foil, carbon-based materials or Mxenes.
3. The method for preparing the negative electrode material of the flexible sodium battery according to claim 1, wherein the method comprises the following steps: the zinc salt is zinc chloride or zinc sulfate; the concentration of the zinc salt is 0.01-0.5 mol L -1 。
4. The preparation method of the flexible sodium battery negative electrode material according to claim 1, characterized by comprising the following steps: the tin salt is tin chloride; the concentration of stannic chloride is 0.01-0.5 mol L -1 。
5. The preparation method of the flexible sodium battery negative electrode material according to claim 1, characterized by comprising the following steps: the concentration of trisodium citrate is 0.2-1.0 mol L -1 (ii) a The concentration of the tartaric acid is 0.05-0.5 mol L -1 。
6. The method for preparing the negative electrode material of the flexible sodium battery according to claim 1, wherein the method comprises the following steps: the solvent of the electroplating solution is a mixed solution of water and glycol.
7. The method for preparing a battery anode material according to claim 6, characterized in that: the volume ratio of the water to the ethylene glycol is 3: 1-1: 3.
8. The preparation method of the flexible sodium battery negative electrode material according to claim 1, characterized by comprising the following steps: the electrodeposition is constant current discharge with the current density of 10-50 mA cm -2 The time is 30 s-2 h.
9. The method for preparing the negative electrode material of the flexible sodium battery according to claim 1, wherein the method comprises the following steps: the charging is constant current charging, and the current density is 1-20 mA cm -2 The time is 300s-6 h.
10. A flexible sodium battery negative electrode material is characterized in that: the preparation method is used for preparing the compound.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115498192A (en) * | 2022-09-21 | 2022-12-20 | 山东大学 | Flexible cathode of sodium ion battery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752554A (en) * | 2010-01-04 | 2010-06-23 | 北京航空航天大学 | Method for preparing Sn-Zn alloy cathode material of lithium ion battery |
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- 2022-05-31 CN CN202210608710.7A patent/CN114927677A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752554A (en) * | 2010-01-04 | 2010-06-23 | 北京航空航天大学 | Method for preparing Sn-Zn alloy cathode material of lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| YONGLING AN等: "Dealloying: An effective method for scalable fabrication of 0D, 1D, 2D, 3D materials and its application in energy storage", 《NANO TODAY》, pages 1 - 53 * |
| 陈可茂: "Sn-Zn无铅钎料的电沉积工艺研究", 《工程科技Ⅰ辑》, pages 015 - 33 * |
| 陈可茂: "陈可茂 Sn-Zn无铅钎料的电沉积工艺研究", 《工程科技Ⅰ辑》, pages 015 - 33 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115498192A (en) * | 2022-09-21 | 2022-12-20 | 山东大学 | Flexible cathode of sodium ion battery and preparation method thereof |
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