CN115498192A - Flexible cathode of sodium ion battery and preparation method thereof - Google Patents
Flexible cathode of sodium ion battery and preparation method thereof Download PDFInfo
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- CN115498192A CN115498192A CN202211150607.9A CN202211150607A CN115498192A CN 115498192 A CN115498192 A CN 115498192A CN 202211150607 A CN202211150607 A CN 202211150607A CN 115498192 A CN115498192 A CN 115498192A
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- tin
- sodium
- ion battery
- negative electrode
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009713 electroplating Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- 235000002906 tartaric acid Nutrition 0.000 claims description 11
- 239000011975 tartaric acid Substances 0.000 claims description 11
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 11
- 229940038773 trisodium citrate Drugs 0.000 claims description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 4
- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
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
- H01M4/13—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
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- 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
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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 belongs to the technical field of materials, and particularly relates to a flexible negative electrode of a sodium-ion battery and a preparation method thereof. The method comprises the following steps: and (3) placing the MXene film in electroplating liquid, electroplating the tin-zinc alloy on the MXene film by adopting an electrodeposition method, and washing and drying to obtain the flexible tin-zinc alloy. The invention adopts the electrodeposition method to prepare the tin-zinc alloy, the preparation process is simple and easy to implement, and the cost is low; the amount of the tin-zinc alloy can be controlled by adjusting the current, the voltage, the time and the like in the electrodeposition process; the ratio of tin to zinc in the alloy can be controlled by adjusting the ratio of tin salt to zinc salt in the product; the prepared flexible zinc-tin alloy cathode material has good flexibility, can buffer the volume change in the circulation process, and obtains better sodium storage performance; the high-conductivity MXene material can improve the conductivity of the whole electrode and obtain better rate performance.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a flexible negative electrode of a sodium-ion battery and a preparation method thereof.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Sodium ion batteries are widely concerned due to their unique advantages, such as abundant sodium source reserves, low price, rapid charge and discharge capability, and the fact that the negative current collector can be made of aluminum foil. However, the negative electrode graphite material of the lithium ion battery which is commercialized at present can hardly store sodium. Therefore, the exploration of the cathode material with excellent performance has important significance in promoting the development of the sodium-ion battery.
The tin-based material has the advantages of high theoretical capacity, abundant reserves, low cost and the like, and becomes one of the most potential cathode materials, and particularly, the tin-based alloy draws attention in the sodium ion battery in recent years. However, during the sodium storage process, the volume of the tin alloy electrode expands, which causes the electrochemical performance to be attenuated. In addition, the electrode has poor conductivity, which limits its rate capability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a flexible tin-zinc alloy negative electrode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a flexible negative electrode for a sodium-ion battery, comprising:
MXene film;
and the MXene film is loaded with a tin-zinc alloy.
MXene is a novel two-dimensional material and has the advantages of high conductivity, good flexibility and low density, so that the battery assembled by the composite material has higher energy density and longer endurance; in addition, from the material perspective, MXene @ tin-zinc alloy is a novel material.
In a second aspect of the present invention, a method for preparing a flexible negative electrode of a sodium ion battery is provided, including:
placing the MXene film in an electroplating solution, electroplating a tin-zinc alloy on the MXene film by adopting an electrodeposition method, washing and drying to obtain the MXene film;
the electroplating solution is a water/glycol solution containing zinc chloride, stannic chloride, trisodium citrate and tartaric acid.
In a third aspect of the invention, the application of the flexible negative electrode of the sodium-ion battery in preparing a sodium battery or other secondary batteries is provided.
The invention has the advantages of
(1) The invention adopts the electrodeposition method to prepare the tin-zinc alloy, and the preparation process is simple and easy to implement and has low cost.
(2) The amount of tin-zinc alloy can be controlled by adjusting the current, voltage, time and the like in the electrodeposition process.
(3) The ratio of tin and zinc in the alloy can be controlled by adjusting the ratio of tin salt and zinc salt in the product.
(4) The prepared flexible zinc-tin alloy cathode material has good flexibility, can buffer the volume change in the circulation process, and obtains better sodium storage performance.
(5) The high-conductivity MXene material can improve the conductivity of the whole electrode and obtain better rate performance.
(6) The MXene film adopted by the invention is of a two-dimensional stacked structure and has a rich layered structure, so that electrodeposition liquid can enter the interlayer, and compared with a metal substrate, the MXene film can obtain a material with higher loading capacity.
(7) The preparation method is simple, strong in practicability and easy to popularize.
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.
FIG. 1 is a photographic image of blank MXene and MXene @ ZnSn materials.
FIG. 2 is a low power SEM image of MXene @ ZnSn.
FIG. 3 is a high magnification SEM image of MXene @ ZnSn.
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.
As introduced by the background technology, aiming at the defects in the prior art, the invention provides a flexible MXene @ ZnSn material and a preparation method thereof.
A preparation method of a flexible tin-zinc alloy negative electrode material comprises the following steps:
and (3) placing the MXene film in electroplating liquid, electroplating the tin-zinc alloy on the MXene film by adopting an electrodeposition method, and washing and drying to obtain the flexible tin-zinc alloy.
The electroplating solution comprises a water/glycol solution of zinc chloride, tin chloride, trisodium citrate and tartaric acid;
the concentration of the tin chloride and the zinc chloride is 0.05-0.2mol L -1 ；
The concentration of the trisodium citrate is 0.1-0.5mol L -1 ；
The concentration of the tartaric acid is 0.05-0.5mol L -1 ；
The volume ratio of the water to the glycol is 1.5-1;
the electrodeposition parameters are as follows: constant current discharge with discharge current of 10-100 mA cm -2 The time is 60 s-60 min.
The electrodeposition parameters are as follows: constant voltage discharge is carried out, the discharge voltage is-1.2 to-1.4V, and the discharge time is 60s to 60min.
The invention also provides a flexible tin-zinc alloy prepared by the method.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
A flexible mxene @ znsn material:
electroplating solution: 0.06M SnCl 4 +0.06M ZnCl 2 +0.12M trisodium citrate +0.1M tartaric acid
Mixing Ti 3 C 2 MXene membrane deviceIn the above plating solution, the constant current discharge current was 10mA cm -2 And the time is 20min, and the flexible MXene @ ZnSn material can be obtained after washing and drying.
Example 2
A flexible MXene @ ZnSn material:
electroplating solution: 0.06M SnCl 4 +0.06M ZnCl 2 +0.12M trisodium citrate +0.1M tartaric acid
Mixing Ti 3 C 2 Placing MXene film in the above electroplating solution, discharging at-1.5V for 10min, and washing and drying to obtain flexible MXene @ ZnSn material.
Example 3
A flexible MXene @ ZnSn material:
electroplating solution: 0.05M SnCl 4 +0.06M ZnCl 2 +0.12M trisodium citrate +0.1M tartaric acid
Mixing Ti 3 C 2 MXene film was placed in the above plating solution with a constant current discharge current of 15mA cm -2 The time is 10min, and the flexible MXene @ ZnSn material can be obtained after washing and drying.
Example 4
A flexible MXene @ ZnSn material:
electroplating solution: 0.04M SnCl 4 +0.06M ZnCl 2 +0.12M trisodium citrate +0.1M tartaric acid
Mixing Ti 3 C 2 Placing MXene film in the above electroplating solution, discharging at constant voltage of-1.5V for 30min, and washing and drying to obtain flexible MXene @ ZnSn material.
Example 5
A flexible mxene @ znsn material:
electroplating solution: 0.06M SnCl 4 +0.03M ZnCl 2 +0.12M trisodium citrate +0.1M tartaric acid
Mixing Ti 3 C 2 MXene film was placed in the above plating solution with a constant current discharge current of 10mA cm -2 And the time is 40min, and the flexible MXene @ ZnSn material can be obtained after washing and drying.
Example 6
A flexible mxene @ znsn material:
electroplating solution: 0.06M SnCl 4 +0.04M ZnCl 2 +0.12M trisodium citrate +0.1M tartaric acid
Mixing Ti 3 C 2 And (3) placing the MXene film in the electroplating solution, wherein the constant voltage discharge voltage is-1.5V, the time is 60min, and washing and drying to obtain the flexible MXene @ ZnSn material.
The strength density of the composite material prepared in the above example was tested and the results show that: compared with a metal substrate, the composite material prepared by the flexible MXene film can obviously improve the energy density.
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 flexible negative electrode for a sodium-ion battery, comprising:
an MXene film;
and the MXene film is loaded with a tin-zinc alloy.
2. A preparation method of a flexible negative electrode of a sodium-ion battery is characterized by comprising the following steps:
placing the MXene film in electroplating liquid, electroplating the MXene film with a tin-zinc alloy by an electrodeposition method, washing and drying to obtain the tin-zinc alloy electroplating solution;
the electroplating solution is a water/glycol solution containing zinc chloride, stannic chloride, trisodium citrate and tartaric acid.
3. The method for preparing a flexible negative electrode for a sodium-ion battery according to claim 1, wherein the concentrations of tin chloride and zinc chloride in the plating solution are 0.05 to 0.2mol L, respectively -1 。
4. The method of claim 1The preparation method of the flexible negative electrode of the sodium ion battery is characterized in that the concentration of trisodium citrate is 0.1-0.5mol L -1 。
5. The method for producing a flexible negative electrode for a sodium-ion battery according to claim 1, wherein the concentration of tartaric acid in the plating solution is 0.05 to 0.5mol L -1 。
6. The method for producing a flexible negative electrode for a sodium-ion battery according to claim 1, wherein the volume ratio of water to ethylene glycol in the plating solution is 1.
7. The method of claim 1, wherein the electrodeposition is performed using constant current discharge.
8. The method for preparing the flexible negative electrode of the sodium-ion battery according to claim 1, wherein the specific conditions of the electrodeposition are as follows: the discharge voltage is-1.2 to-1.4V, and the discharge current is 10 to 100mA cm -2 The time is 60 s-60 min.
9. A flexible negative electrode for a sodium ion battery prepared by the method of any one of claims 2 to 8.
10. Use of a flexible negative electrode of a sodium-ion battery as claimed in claim 1 or 9 in the manufacture of a sodium battery or other secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211150607.9A CN115498192A (en) | 2022-09-21 | 2022-09-21 | Flexible cathode of sodium ion battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211150607.9A CN115498192A (en) | 2022-09-21 | 2022-09-21 | Flexible cathode of sodium ion battery and preparation method thereof |
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| CN115498192A true CN115498192A (en) | 2022-12-20 |
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Citations (9)
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|---|---|---|---|---|
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| CN104409707A (en) * | 2014-10-15 | 2015-03-11 | 河南师范大学 | Tin-based alloy flexible thin film electrode and preparation method thereof |
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| CN114420917A (en) * | 2022-01-18 | 2022-04-29 | 山东大学深圳研究院 | Flexible zinc-antimony composite material and preparation method and application thereof |
| CN114927677A (en) * | 2022-05-31 | 2022-08-19 | 山东大学 | Flexible sodium battery negative electrode material and green preparation method and application thereof |
-
2022
- 2022-09-21 CN CN202211150607.9A patent/CN115498192A/en active Pending
Patent Citations (9)
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| JP2002198091A (en) * | 2000-12-27 | 2002-07-12 | Hyogo Prefecture | Negative electrode for lithium secondary cell and lithium secondary cell using the same |
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| CN114927677A (en) * | 2022-05-31 | 2022-08-19 | 山东大学 | Flexible sodium battery negative electrode material and green preparation method and application thereof |
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