CN111276672A - Preparation and application of electrode containing tin array structure - Google Patents

Preparation and application of electrode containing tin array structure Download PDF

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CN111276672A
CN111276672A CN202010093550.8A CN202010093550A CN111276672A CN 111276672 A CN111276672 A CN 111276672A CN 202010093550 A CN202010093550 A CN 202010093550A CN 111276672 A CN111276672 A CN 111276672A
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tin
electrode
array structure
copper substrate
preparation
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CN111276672B (en
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倪江锋
朱晓翠
孙梦雷
李亮
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Suzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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 relates to a preparation method of an electrode with a high-performance tin-containing array structure for a sodium ion battery, which comprises the following steps: taking a cleaned copper substrate as a working electrode, taking a solution containing tin ions and a template agent as an electrolyte, and adopting a three-electrode system to perform constant-current electrodeposition so as to form a tin array structure on the surface of the copper substrate; and annealing the substrate subjected to the treatment in vacuum or non-oxidizing gas at the temperature of 80-230 ℃ to obtain the electrode with the tin-containing array structure. The preparation method has simple process and convenient operation, and the prepared electrode can be directly used for the cathode of the sodium-ion battery and shows higher specific capacity, good cycling stability and excellent rate charge-discharge characteristics.

Description

Preparation and application of electrode containing tin array structure
Technical Field
The invention relates to the technical field of electrode preparation, in particular to preparation and application of an electrode with a tin-containing array structure.
Background
In recent years, rapid development of lithium ion batteries in the fields of large-scale energy storage and vehicle-mounted power accelerates the consumption of lithium resources in the world, and causes the problem of possible exhaustion of the lithium resources. In addition, the recycling of lithium resources is still a worldwide technical problem. Therefore, the search for new and alternative energy storage battery systems is an urgent issue to be solved. The sodium ion battery has the characteristics of rich resources, low price, higher safety and the like, thereby being a potential choice. Despite the many potential performance and cost advantages of sodium ion batteries, practical use in energy storage devices still faces a number of problems. One of the important problems is the lack of a stable high capacity anode material, which is associated with a large sodium ion radius and a high standard reduction potential.
Alloy-based negative electrode materials such as metallic tin (Sn) having a g of up to 847mAh-1The sodium storage capacity and the average sodium storage potential of about 0.2V are achieved, so that the sodium storage device has a good application prospect. The volume expansion of the tin material is higher to 420 percent after the tin material is completely embedded with sodium, so that the cracking of electrode particles is easily caused. On one hand, the cracked particles can be separated from the current collector to be in electric contact with the current collector, and the electrochemical activity is lost; on the other hand, the generated new interface consumes sodium ions to form a solid electrolyte interface film, and capacity is reduced in the circulation process. The conventional approach to solving the cycling stability of Sn electrodes is to disperse tin in conductive carbon or to compound it with other materials to mitigate the volume expansion during sodium storage. However, the method is complicated in process and is not ideal in effect. For example, Chinese patent (application No. 201910225161.3) prepares a Zn-Sn-O nanoparticle and carbon fiber composite material, and only 280mAh g is kept after 200 charge-discharge cycles1The capacity of (c). Chinese patent application No. 201910089476.X grows monomeric tin directly on carbon cloth, but the material has not high practical capacity and needs to use hydrazine hydrate, a highly toxic reducing agent.
Some other metal alloy negative electrode materials have been proposed, for example, Chinese patent (application No. 201510957261.7) discloses a sodium ionThe preparation method of the titanium oxide cathode of the sub-battery comprises the step of obtaining TiO on a metal titanium substrate by utilizing electrochemical anodic oxidation2Nano array, sulfurizing the obtained titanium oxide nano array to obtain sulfur-doped TiO2The capacity of the nanometer cathode needs to be improved. Chinese patent application No. 201910206983.7 discloses a zinc-metal composite electrode with an array structure and a preparation method thereof, wherein the composite electrode is composed of metal zinc and composite components thereof, and has a vertical array structure, the vertical array is arranged in an array of zinc-tin-zinc, and the capacity of the composite electrode needs to be improved.
Disclosure of Invention
In order to solve the problems of low capacity and poor cycling stability of the cathode obtained by the existing method, the invention aims to provide preparation and application of the electrode with the tin-containing array structure.
The invention relates to a preparation method of an electrode with a tin-containing array structure, which comprises the following steps:
(1) using a cleaned copper substrate as a working electrode and containing tin ions (Sn)4+And/or Sn2+) The solution of the template agent is used as electrolyte, and a three-electrode system is adopted for constant-current electrodeposition so as to form a nano-scale tin array structure on the surface of the copper substrate;
(2) and (2) cleaning the substrate treated in the step (1), annealing at 80-230 ℃ in vacuum or non-oxidizing gas to form a copper-tin alloy between the tin array structure and the copper substrate, and obtaining the electrode with the tin array structure after annealing.
Further, before the step (1), the copper substrate is ultrasonically cleaned by oxalic acid solution, deionized water and alcohol to remove an oxide layer and adsorbed impurities on the surface of the copper substrate so as to obtain a cleaned copper substrate.
Further, in the step (1), the three-electrode system uses a carbon electrode or a platinum electrode as a counter electrode; the three-electrode system uses an Ag/AgCl electrode or a calomel electrode as a reference electrode.
Further, in the step (1), the solvent in the solution containing tin ions and the additive includes an organic solvent and water. The volume ratio of the organic solvent to the water is 0.1-10: 1, preferably 0.3-2: 1. The organic solvent is one or more selected from ethylene glycol, diethylene glycol and glycerol.
Further, in the step (1), the concentration of tin ions is 0.01 to 0.2M, preferably 0.04 to 0.1M. The tin ions are derived from one or more of stannic chloride, stannous chloride and stannous oxalate. When the tin source is tin tetrachloride, the electrolyte contains Sn4+(ii) a When the tin source is stannous chloride, stannous oxalate or other stannous ion salt, the electrolyte contains Sn2+。
Further, in the step (1), the concentration ratio of the template to the tin ions is 0.5 to 5:1, preferably 1 to 2: 1. The template agent is one or more of trisodium citrate, ethylenediamine hydrochloride and polyvinylpyrrolidone. In the application, the template agent is used for complexing with tin ions, so that the tin ions are orderly stacked at fixed points on a copper substrate after obtaining electrons, and an ordered array is formed.
Further, in the step (1), the working current density of the constant current electrodeposition is 0.01-0.04A/cm2(ii) a The deposition time is 5-60 min, preferably 10-20 min.
Further, in the step (2), the non-oxidizing gas is one or more selected from other non-oxidizing gases such as argon, nitrogen, helium and the like.
Further, in the step (2), the annealing temperature is preferably 120 to 200 ℃.
Further, in the step (2), the annealing time is 0.1 to 24 hours, preferably 1 to 6 hours.
In the annealing process, the joint of the copper substrate and the tin array structure is converted into copper-tin alloy, the adhesion between the tin array structure and the copper substrate is stronger depending on the formed copper-tin alloy, and part of the copper-tin alloy extends from bottom to top along the growth direction of the tin array structure in the annealing process, so that the stability of the tin structure is obviously improved. Under the annealing condition of the invention, the prepared electrode containing the tin array structure can be ensured to have a large amount of tin array structures with enhanced copper-tin alloying.
The invention also discloses an electrode with a tin-containing array structure prepared by the preparation method, which comprises a copper substrate and the tin array structure positioned on the surface of the copper substrate, wherein a copper-tin alloy is formed between the copper substrate and the tin array structure.
Furthermore, the tin array structure has a size of nanometer, a height of 0.5-10 μm, preferably 2-10 μm, and is three-dimensional, such as a sheet or a cone. The invention has no requirement on the thickness of the copper substrate in the electrode with the tin array structure.
The invention adopts an electrochemical constant-current electrodeposition method to prepare the tin array electrode, and further forms copper-tin alloy by an annealing treatment method to enhance the electric contact between the tin array and the substrate. The preparation method has the advantages of simple operation, simple equipment and low manufacturing cost.
The invention also claims the application of the electrode containing the tin array structure prepared by the method as the negative electrode of the sodium-ion battery.
The electrode with the tin-containing array structure prepared by the invention can be directly used for the cathode of a sodium ion battery, shows higher specific capacity, good cycling stability and excellent rate charge-discharge characteristics, and is a sodium ion battery cathode material with very high application potential.
By the scheme, the invention at least has the following advantages:
(1) the tin array is directly grown on the metal copper substrate without adding a conductive agent and a binder, the electrode is simple and convenient to manufacture, and good contact is kept between the electrode and the substrate;
(2) the three-dimensional ordered tin array structure has sufficient gaps, provides a rapid channel for the transmission of sodium ions, can accommodate the volume expansion in the sodium storage process, and improves the cycling stability of the electrode;
(3) the copper-tin alloy is formed after annealing treatment, so that the adhesion force of the tin array and the substrate can be enhanced, the electric contact between the tin array and the substrate is further improved, the structural stability of tin is obviously improved, and the copper-tin alloy is prepared by the methodThe reversible sodium storage capacity of the tin cathode can reach 801mAh g -1100 cycles of charging and discharging at 2C, 591mAh g still remained-1The cycle capacity retention rate is more than 88%.
(4) The preparation method has the advantages of simple process, convenient operation, simple equipment, easy control and low cost, and can be used for large-scale industrial production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a scanning electron microscope photograph of the negative electrode of the tin array obtained in example 1;
FIG. 2 is an X-ray diffraction pattern of a tin-array negative electrode obtained in example 1;
FIG. 3 is a charge and discharge curve of a tin array negative electrode obtained in example 1;
fig. 4 is a charge-discharge cycle curve of a tin array negative electrode obtained in example 1;
FIG. 5 is a scanning electron microscope photograph of the negative electrode of the tin array obtained in example 2;
fig. 6 is a charge and discharge curve of a tin array negative electrode obtained in example 2;
FIG. 7 is a charge and discharge curve of a tin array negative electrode obtained in example 3;
FIG. 8 is a SEM picture of a tin array cathode obtained in example 4;
fig. 9 is a charge and discharge curve of the tin array negative electrode obtained in example 4.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples of the present invention, the sodium storage performance of the electrode having a tin-containing array structure was tested by the following steps:
electrode with tin-containing array structureThen used as a working electrode, a metal sodium sheet is used as a counter electrode, and NaPF with the concentration of 1M is used6The diglycol dimethyl ether solution is used as electrolyte to assemble a sodium ion battery, and then a charge-discharge test is carried out between 0.001 and 2V.
Example 1
A piece of copper sheet of 2cm x 0.5cm is taken and cleaned by ultrasonic in oxalic acid solution, deionized water and alcohol for 10min respectively. The cleaned copper sheet is used as a working electrode, a carbon electrode is used as a counter electrode, an electrolyte consists of 0.06M stannic chloride pentahydrate and 0.12M trisodium citrate solution, the electrolyte solvent is ethylene glycol and water (the volume ratio is 1: 1), and a three-electrode system is adopted and is 0.01A cm-2And electrodepositing for 20min under current density to deposit the tin array structure on the surface of the copper substrate. And annealing the copper substrate deposited with the tin array structure, wherein the used protective atmosphere is argon, the temperature is 180 ℃, and the time is 2 hours, so that the cathode with the tin array structure is obtained, and the height is about 3 mu m.
Sodium storage performance test is carried out on the cathode with the tin array structure (hereinafter referred to as tin array cathode) according to the method, and the result shows that the prepared tin array cathode shows 801mAh g-1The reversible sodium storage capacity of (2) can maintain 88% of the initial capacity after 100 cycles at a rate of 2C.
Example 2
A piece of copper sheet of 2cm x 0.5cm is taken and cleaned by ultrasonic in oxalic acid solution, deionized water and alcohol for 10min respectively. The cleaned copper sheet is used as a working electrode, the carbon electrode is used as a counter electrode, the electrolyte consists of 0.2M stannic chloride pentahydrate and 0.2M polyvinylpyrrolidone solution, the electrolyte solvent is ethylene glycol and water (the volume ratio is 1: 1), and a three-electrode system is adopted and is 0.01A cm-2Is deposited for 5min at a current density of (1) to deposit a tin array structure on the surface of the copper substrate. And (3) annealing the copper substrate deposited with the tin array structure for 2 hours at 220 ℃ under the protection of argon to obtain the tin array cathode with the height of about 5 mu m.
The tin array negative electrode is subjected to sodium storage performance test according to the method, and the result shows that the reversible sodium storage capacity of the obtained tin array negative electrode reaches 721mAh g-1The initial time can be kept after 100 cycles under the multiplying power of 2C80% of the initial capacity.
Example 3
A piece of copper sheet of 2cm multiplied by 1cm is taken and is respectively cleaned in oxalic acid solution, deionized water and alcohol for 10min by ultrasonic cleaning. The cleaned copper sheet is used as a working electrode, a carbon electrode is used as a counter electrode, an electrolyte consists of 0.1M of stannic chloride pentahydrate, 0.1M of stannous chloride and 0.4M of ethylenediamine hydrochloride, the electrolyte solvent is diethylene glycol and water (the volume ratio is 1:2), and a three-electrode system is adopted, wherein the three-electrode system is 0.04A cm-2And electrodepositing for 10min under current density to deposit the tin array structure on the surface of the copper substrate. And then carrying out vacuum annealing treatment on the copper substrate deposited with the tin array structure, wherein the annealing temperature is 200 ℃, and the annealing time is 30min, so as to obtain the tin array cathode, and the height is about 10 mu m.
The tin array negative electrode is subjected to sodium storage performance test according to the method, and the result shows that the reversible sodium storage capacity of the prepared tin array negative electrode reaches 790mAh g-1. 75% of the initial capacity can be maintained after 100 cycles at a rate of 2C.
Example 4
A piece of copper sheet of 2cm multiplied by 1cm is taken and is respectively cleaned in oxalic acid solution, deionized water and alcohol for 10min by ultrasonic cleaning. And taking the cleaned copper sheet as a working electrode. Then, the carbon electrode is taken as a counter electrode, the electrolyte consists of 0.01M stannic chloride pentahydrate, 0.05M stannous oxalate and 0.02M trisodium citrate solution, the electrolyte solvent is glycerol and water (the volume ratio is 1:4), and a three-electrode system is adopted to be 0.04Acm-2Electrodeposition was carried out for 40min at current density to deposit a pyramidal array of tin on the copper substrate surface, with a height of around 2 μm. Carrying out heat treatment on the copper substrate deposited with the cone-shaped tin array structure at 100 ℃ for 10 hours under nitrogen atmosphere to obtain a final tin array cathode, and carrying out sodium storage performance test according to the method, wherein the result shows that the cathode has 685mAh g-1The reversible sodium storage capacity of (c). 85% of the initial capacity can be maintained after 100 cycles at a rate of 2C.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of an electrode containing a tin array structure is characterized by comprising the following steps:
(1) taking a cleaned copper substrate as a working electrode, taking a solution containing tin ions and a template agent as an electrolyte, and adopting a three-electrode system to perform constant-current electrodeposition so as to form a tin array structure on the surface of the copper substrate;
(2) and (2) annealing the substrate treated in the step (1) at 80-230 ℃ in vacuum or non-oxidizing gas to obtain the electrode with the tin-containing array structure.
2. The method of claim 1, wherein: before the step (1), ultrasonically cleaning the copper substrate by oxalic acid solution, water and alcohol to obtain the cleaned copper substrate.
3. The method of claim 1, wherein: in the step (1), the three-electrode system uses a carbon electrode or a platinum electrode as a counter electrode; the three-electrode system takes an Ag/AgCl electrode or a calomel electrode as a reference electrode.
4. The method of claim 1, wherein: in the step (1), a solvent in the electrolyte comprises an organic solvent and water, and the volume ratio of the organic solvent to the water is 0.1-10: 1; the organic solvent is one or more selected from ethylene glycol, diethylene glycol and glycerol.
5. The method of claim 1, wherein: in the step (1), the concentration of the tin ions is 0.01-0.2M; the tin ions are derived from one or more of stannic chloride, stannous chloride and stannous oxalate.
6. The method of claim 1, wherein: in the step (1), the concentration ratio of the template to the tetravalent tin ions is 0.5-5: 1; the template agent is one or more of trisodium citrate, ethylenediamine hydrochloride and polyvinylpyrrolidone.
7. The method of claim 1, wherein: in the step (1), the working current density of the constant-current electrodeposition is 0.01-0.04A/cm2(ii) a The deposition time is 5-60 min.
8. The method of claim 1, wherein: in the step (2), the non-oxidizing gas is one or more selected from argon, nitrogen and helium.
9. An electrode containing a tin array structure prepared by the preparation method according to any one of claims 1 to 8, characterized in that: the tin-based composite material comprises a copper substrate and a tin array structure positioned on the surface of the copper substrate, wherein a copper-tin alloy is formed between the copper substrate and the tin array structure.
10. Use of the tin array structured electrode of claim 9 as a negative electrode in a sodium ion battery.
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CN114243027A (en) * 2021-12-17 2022-03-25 广东工业大学 Sodium ion battery negative current collector, preparation method thereof and sodium ion battery
CN114243027B (en) * 2021-12-17 2024-02-13 广东工业大学 Negative current collector of sodium ion battery, preparation method of negative current collector and sodium ion battery

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