CN114883669A - Water system nickel-iron battery and preparation method thereof - Google Patents

Water system nickel-iron battery and preparation method thereof Download PDF

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CN114883669A
CN114883669A CN202210384815.9A CN202210384815A CN114883669A CN 114883669 A CN114883669 A CN 114883669A CN 202210384815 A CN202210384815 A CN 202210384815A CN 114883669 A CN114883669 A CN 114883669A
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nickel
electrode
printing
hours
solution
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徐茜
江睿奕
官操
李晨
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Northwestern Polytechnical University
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    • H—ELECTRICITY
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    • H01M10/30—Nickel accumulators
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    • B22—CASTING; POWDER METALLURGY
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    • B22F3/10—Sintering only
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract

The invention relates to a water system nickel-iron battery and a preparation method thereof, belonging to the field of batteries; the battery comprises Fe 2 O 3 @3DFe positive electrode, NiCo 2 S 4 @3DNi negative electrode and potassium hydroxide solution electrolyte; the preparation method comprises the steps of designing an F-KS structure template through software, and preparing NiCo by respectively adopting a nickel sulfate template and a ferric sulfate substrate 2 S 4 @3DNi electrode and Fe 2 O 3 The @3DFe electrode, the last two electrodes combined with electrolyte assembly yielded an aqueous nickel-iron battery. According to the invention, the water system nickel-iron battery composed of the porous metal structure electrode prepared by 3D printing of the recoverable metal salt is adopted, and the ordered electron/ion transmission path is deterministically manufactured by reasonably designing the three-dimensional periodic porous structure electrode, so that the problem of low random disordered electron/ion transmission rate of the traditional 3D porous structure is solved. Meanwhile, the raw materials of the process are easy to recover, and the process is a good choice for realizing sustainable production.

Description

Water system nickel-iron battery and preparation method thereof
Technical Field
The invention belongs to the field of batteries, and particularly relates to a water-system nickel-iron battery and a preparation method thereof.
Background
The ever-increasing demand for portable devices in the day ahead society has required electrochemical storage devices with higher power densities, higher energy densities and longer cycle lives. Over the past few decades, rapid development of nanostructured electrode materials has enabled superior energy or power densities. However, its good performance is usually achieved by using a catalyst with a low mass loading (. ltoreq.1 mg cm) -2 ) But such electrodes are difficult to commercialize.
The thick electrode design is a method which can effectively improve the electrode active material load, thereby improving the energy density of the device. However, in conventional electrode structures such as sandwich structures, increasing the electrode thickness limits ion diffusion, resulting in high resistance, slower kinetics and poor rate performance. However, 3D structured electrodes can overcome these limitations. The interconnected network of channels, in combination with the graded pores, ensures efficient charge transport throughout the electrode volume, thereby enabling rapid and high capacity energy storage.
Numerous strategies for producing porous metals have been developed, such as directed self-assembly of chemical routes, gas injection, dealloying, and investment casting. These methods are of great importance in the commercialization of metal products, but suffer from drawbacks such as cumbersome procedures, low yields, uncontrollable feature sizes, and poor strength for producing complex geometries. In addition, there is an increasing concern about the sustainability of recovery techniques and processes. Electrodes/catalysts with scrap metals/metal compounds are currently being recycled in a non-safe and non-environmentally friendly manner, so great efforts are currently being made by the parties to address this limitation to achieve sustainability in the closed-loop manufacturing of batteries.
Advances in Additive Manufacturing (AM), also known as 3D printing technology, offer new possibilities to address these challenges in metal processing. Due to the randomness of the conventional 3D porous metal structure, it is still unsatisfactory in terms of electron/ion transport rate. In sharp contrast, 3D printed metallic structures allow for the defined, fine fabrication of ordered electron/ion transport paths. The physical structure of the electrode structure is designed and optimized, and the aim of directly improving the load of the active material can be realized, so that better electrochemical performance is obtained. Currently, the most mature metal 3D printing technologies are the Selective Laser Melting (SLM) and Electron Beam Melting (EBM) methods, but these technologies are cost prohibitive and still have limited resolution. Digital Light Processing (DLP) is a powerful and widely used 3D printing method that uses photopolymerization for 3D printing, can be built much faster than conventional stereolithography equipment, and can achieve high resolution, complex geometry printing. The printing device is low in cost, simple to operate, high in manufacturing speed, high in material use efficiency and high in resolution, and can print complex 3D structures. If the energy storage material is properly utilized in the field of energy storage, the energy storage material has great prospect. However, DLP processes produce samples that are typically polymers. Common methods for obtaining a conductive metal substrate by DLP include: using the printed polymer part as a template, and metalizing the sample by Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), chemical plating or electrodeposition and the like.
In this work, we report a process for producing fully metallic structures with high resolution and layered porosity by DLP without the need for metallization. By using metal salts as precursors, the material limitations of DLP metal printing are reduced by a simple chemical process (acid/salt assisted reaction) followed. The raw materials of the process have the advantages of cost effectiveness, easy recovery and sustainable production.
Disclosure of Invention
The technical problem to be solved is as follows:
in order to avoid the defects of the prior art, the invention provides the water-based nickel-iron battery and the preparation method thereof, the water-based nickel-iron battery is formed by adopting the porous metal structure electrode prepared by 3D printing of the recoverable metal salt, the ordered electron/ion transmission path is deterministically manufactured by reasonably designing the electrode with the three-dimensional periodic porous structure, and the problem of low random disordered electron/ion transmission rate of the traditional 3D porous structure is solved. Meanwhile, the raw materials of the process are easy to recover, and the process is a good choice for realizing sustainable production.
The technical scheme of the invention is as follows: an aqueous ferronickel battery comprises a positive electrode, a negative electrode and an electrolyte; the method is characterized in that: the positive electrode is Fe 2 O 3 @3DFe with NiCo as negative electrode 2 S 4 @3DNi, the electrolyte is potassium hydroxide solution.
The further technical scheme of the invention is as follows: the anode and the cathode are layered porous 3D metal nickel electrodes.
A preparation method of a water system nickel-iron battery is characterized by comprising the following specific steps:
the method comprises the following steps: designing an F-KS structural template through software;
mixing, stirring and grinding nickel sulfate powder, Variquat CC42NS and light-cured resin according to a certain proportion to obtain resin, and printing by adopting the resin; after printing, taking the printed structure off the printing platform, carrying out ultrasonic cleaning for multiple times, and drying at room temperature to obtain a nickel sulfate template;
mixing, stirring and grinding ferric sulfate powder, Variquat CC42NS and light-cured resin according to a certain proportion to obtain resin, and printing by adopting the resin; after printing, taking the printed structure off the printing platform, carrying out ultrasonic cleaning for multiple times, and drying at room temperature to obtain a ferric sulfate substrate;
step two: placing the nickel sulfate template/ferric sulfate substrate obtained in the step one in a muffle furnace for degreasing and sintering, transferring the degreased nickel oxide structure/ferric oxide structure into a PECVD furnace, and heating and reducing in an argon-hydrogen mixed atmosphere to obtain a 3D printing metal nickel structure/3D printing metal iron structure;
step three: dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and hexamethylenetetramine in certain mass in methanol, and stirring to form a transparent pink red solution; transferring the solution into an autoclave lined with polytetrafluoroethylene, suspending the 3D printed metal nickel structure obtained in the step two in the solution, and heating to synthesize Ni-Co LDH; cleaning with deionized water for several times, and drying in a vacuum oven to obtain Ni-Co LDH @3 DNi;
step four: adding a certain mass of sodium sulfide nonahydrate into deionized water, and stirring until the mixture is transparent; then putting the Ni-Co LDH @3DNi sample prepared in the third step into the transparent solution to obtain a mixture; then, the obtained mixture is transferred into an autoclave lined with polytetrafluoroethylene, heated and reacted, the product is taken out, washed by deionized water and dried to obtain NiCo 2 S 4 The @3DNi electrode;
step five: mixing a certain mass of sodium hydroxide, ammonium persulfate, deionized water and an ammonium fluoride solution, and transferring the mixture into a high-pressure kettle lined with polytetrafluoroethylene; immersing a 3D printed metallic iron structure into the solution of the autoclave in the step; taking out after heating reaction, washing with deionized water and drying in a vacuum oven; heating and maintaining the prepared substrate in Ar atmosphere to obtain Fe 2 O 3 The @3DFe electrode;
step six: with Fe 2 O 3 @3DFe being positive electrode, NiCo 2 S 4 And @3DNi is a negative electrode, and 6M potassium hydroxide is an electrolyte, and the water-based nickel-iron battery is assembled.
The further technical scheme of the invention is as follows: in the first step, 20-60g of metal salt, 1-10mL of murariquat CC42NS and 30mL of light-cured resin are mixed in an amber bottle, stirred for 1-3 hours in a magnetic stirrer at room temperature and then ground by a planetary ball mill; the light-cured resin is prepared by mixing E-HDDA and E-TMPTA in a ratio of 3:22 and adding 2 wt.% of TPO.
The further technical scheme of the invention is as follows: in the second step, the sintering temperature of the degreasing sintering process is 200-1000 ℃, and the sintering time is 1-5 hours; the reduction step is carried out for 1-5 hours in an argon-hydrogen mixed atmosphere at 400-900 ℃.
The further technical scheme of the invention is as follows: in the third step, 0.03-0.1g of cobalt nitrate hexahydrate, 0.01-0.5g of nickel nitrate hexahydrate, 0.05-0.1g of hexamethylenetetramine and 20-50mL of methanol are used; the temperature of the high-pressure kettle is 150-; the vacuum drying temperature is 40-80 deg.C, and the drying time is 10-20 hr.
The further technical scheme of the invention is as follows: in the fourth step, 0.5-1.0g of sodium sulfide nonahydrate, 10-50mL of deionized water, 100-150 ℃ of high-pressure kettle, 5-10 hours of reaction time, 40-80 ℃ of drying temperature and 10-20 hours of drying time.
The further technical scheme of the invention is as follows: in the fifth step, 0.1-0.5g of sodium hydroxide, 0.2-0.6g of ammonium persulfate, 10-40mL of deionized water, 1.0-6.0mL of 50mM ammonium fluoride solution, 200 ℃ of the autoclave, 10-20 hours of reaction time, 400 ℃ of vacuum drying temperature, 1 ℃/min of heating rate and 2-6 hours of keeping in Ar atmosphere.
The further technical scheme of the invention is as follows: in the sixth step, Fe 2 O 3 @3DFe and NiCo 2 S 4 The @3DNi electrode is soaked in electrolyte, placed at room temperature, assembled face to face and immersed in solution to obtain the water-based nickel-iron battery.
Advantageous effects
The invention has the beneficial effects that: the invention provides a water system nickel-iron battery consisting of porous metal structure electrodes prepared by adopting 3D printing of recyclable metal salt and a preparation method thereof, and the water system nickel-iron battery firstly combines a Digital Light Processing (DLP) technology (a 3D printing technology with the layer resolution of 27 mu m) with post-treatment and heat treatment to obtain an orderly graded porous 3D metal substrate. The 3D metal structure with the ordered internal structure increases the specific surface area, makes an ordered electron/ion transmission path and improves the electrochemical performance.
Excellent mechanical properties: through finite element analysis and quasi-static compression test of the system, the compressive strength of the metallic nickel structure prepared by 3D printing can reach 13.52MPa, and the compressive strength of the foamed nickel can only reach 0.414 MPa.
Excellent electrochemical performance: compared with the traditional foamed nickel and foamed iron, the 3D printed nickel and iron substrate has lower resistivity. On the basis of 3D printing of a metallic nickel structure, the material with high active material mass loading capacity (18.38 mg/cm under the thickness of 4 mm) is prepared 2 ) High area capacity (44.85mA cm) -2 7.327mAh cm under current density -2 ) The current density is from 42.9mA cm -2 Increased to 171.4mA cm -2 NiCo, which also retains 57.28% of rate capability 2 S 4 @3DNi electrode, based on 3D printing of metallic iron structure, prepared at 16.02mA cm -2 Has 10.87mAh cm at current density -2 Area capacity of Fe 2 O 3 @3DFe electrode, and an asymmetric water system ferronickel battery is assembled at 16.02mA cm -2 An impressive current density of 10.87mAh cm -2 Area capacity.
Drawings
Fig. 1 is a scanning electron microscope image of a 3D printed metallic nickel substrate.
FIG. 2 shows NiCo 2 S 4 Scanning electron micrograph of @3D Ni electrode.
Fig. 3 is a scanning electron microscope image of a 3D printed metallic iron substrate.
FIG. 4 is Fe 2 O 3 Scanning electron micrographs of the @3DFe electrode.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The embodiment of the invention adopts recyclable metal salt as a raw material and is prepared by 3D printingThe water system nickel-iron battery assembled by the metal electrodes with the 3D structures comprises a positive electrode, a negative electrode and electrolyte; the positive electrode is Fe 2 O 3 @3DFe with NiCo as negative electrode 2 S 4 @3DNi, the electrolyte is potassium hydroxide solution; the anode and the cathode are layered porous 3D metal nickel electrodes.
The embodiment of the invention discloses a preparation method of a water system nickel-iron battery assembled by 3D structure metal electrodes which are prepared by 3D printing by adopting recyclable metal salt as a raw material, which comprises the following specific steps:
the method comprises the following steps: designing an F-KS structure template through MS Lattice software;
mixing nickel sulfate powder, Variquat CC42NS and light-cured resin according to a certain proportion, stirring and grinding. The resulting resin was printed by an Asiga MAX X27 UV printer (UV wavelength 385nm, layer resolution 27 μm); after printing, taking down the printed structure from the printing platform, immersing the printed structure into IPA (isopropyl alcohol) for ultrasonic cleaning for 3 times, and drying at room temperature to obtain a nickel sulfate template;
mixing, stirring and grinding ferric sulfate powder, Variquat CC42NS and light-cured resin according to a certain proportion to obtain resin, and printing by adopting the resin; after printing, taking the printed structure off the printing platform, carrying out ultrasonic cleaning for multiple times, and drying at room temperature to obtain a ferric sulfate substrate;
step two: placing the nickel sulfate template/ferric sulfate substrate in the first step into a muffle furnace (carbide AAF 1700) for sintering, then transferring the degreased nickel oxide structure/ferric oxide structure into a PECVD furnace, and heating and reducing in an argon-hydrogen mixed atmosphere to obtain a 3D printed metal nickel structure;
step three: dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and hexamethylenetetramine in methanol by certain mass, and stirring to form a transparent pink red solution. And (4) transferring the solution into an autoclave lined with polytetrafluoroethylene, suspending the 3D printed metal nickel sample obtained in the step two in the solution by using an aramid fiber wire, and heating to synthesize Ni-Co LDH. Washing with deionized water for several times, and drying in a vacuum oven to obtain Ni-Co LDH @3 DNi;
step four: will be oneAdding the sodium sulfide nonahydrate into deionized water according to the mass, and stirring until the mixture is transparent. Then the Ni-Co LDH @3DNi sample prepared in step three was placed in the above solution. Subsequently, the mixture was transferred to a 50mL autoclave lined with polytetrafluoroethylene and the reaction was heated. Taking out the product, washing with deionized water, and drying to obtain NiCo 2 S 4 The @3DNi electrode;
step five: mixing a certain mass of sodium hydroxide, ammonium persulfate, deionized water and ammonium fluoride solution, and transferring the mixture into a polytetrafluoroethylene lining autoclave with the volume of 50 mL. Will have a size of 2 * 3 * A 1.44mm 3D metallic iron substrate was immersed in the autoclave solution. The reaction was heated, taken out, rinsed with deionized water and dried in a vacuum oven. Heating and maintaining the prepared substrate in Ar atmosphere to obtain Fe 2 O 3 The @3DFe electrode;
step six: fe2O3@3DFe is used as a positive electrode, NiCo 2 S 4 And @3DNi is a negative electrode, and 6M potassium hydroxide is an electrolyte, and the water-based nickel-iron battery is assembled and prepared.
Preferably: in the first step, 20-60g of metal salt, 1-10mL of LVariquat CC42NS and 30mL of light-cured resin (prepared by adding 2 wt.% of TPO into E-HDDA and E-TMPTA according to the proportion of 3: 22) are mixed in an amber bottle, stirred for 1-3 hours in a magnetic stirrer at room temperature and then ground by a planetary ball mill.
Preferably: in the second step, the sintering temperature of the degreasing sintering process is 200-1000 ℃, and the sintering time is 1-5 hours. The reduction step is carried out in an argon-hydrogen mixed atmosphere of 400-900-.
Preferably: in the third step, 0.03-0.1g of cobalt nitrate hexahydrate, 0.01-0.5g of nickel nitrate hexahydrate, 0.05-0.1g of hexamethylenetetramine and 20-50mL of methanol are added; the temperature of the high-pressure kettle is 150-; the vacuum drying temperature is 40-80 deg.C, and the drying time is 10-20 hr.
Preferably: in the fourth step, 0.5-1.0g of sodium sulfide nonahydrate, 10-50mL of deionized water, 100-150 ℃ of high-pressure kettle, 5-10 hours of reaction time, 40-80 ℃ of drying temperature and 10-20 hours of drying time.
Preferably: in the fifth step, 0.1-0.5g of sodium hydroxide, 0.2-0.6g of ammonium persulfate, 10-40mL of deionized water, 1.0-6.0mL of 50mM ammonium fluoride solution, 200 ℃ of the autoclave, 10-20 hours of reaction time, and 400 ℃ of vacuum drying temperature (1 ℃/min heating rate) and 2-6 hours of vacuum drying temperature in Ar atmosphere.
Preferably: in the sixth step, Fe 2 O 3 @3DFe and NiCo 2 S 4 The @3DNi electrode is soaked in electrolyte, placed at room temperature, assembled face to face and immersed in the solution to assemble and prepare the water-based nickel-iron battery.
Example (b):
1. and preparing the 3D printing metal nickel substrate. 58g of nickel sulfate powder, 5mL of Variquat CC42NS and 30mL of a photocurable resin (consisting of E-HDDA and E-TMPTA in a ratio of 3:22 and 2 wt.% TPO) were mixed, stirred at room temperature for 1-3 hours, and then ground with a planetary ball mill to make the nickel sulfate powder finer in the resin. And then, printing the substrate by using a Digital Light Processing (DLP) technology to obtain a 3D printed nickel sulfate substrate. Then, the mixture was degreased and sintered in a muffle furnace (at 200, 400, and 600 ℃ for 2 hours, and at 840 and 1000 ℃ for 3 hours, respectively). Thereafter, the degreased nickel oxide structure was then transferred to a PECVD furnace and reduced in an argon-hydrogen mixed atmosphere at 600 ℃ for 10 hours, resulting in a 3D printed metallic nickel structure.
2. Preparation of NiCo 2 S 4 @3DNi electrode. First, Ni-Co LDH was prepared. 0.036g of cobalt nitrate hexahydrate, 0.018g of nickel nitrate hexahydrate and 0.075g of hexamethylenetetramine were dissolved in 30mL of methanol and stirred to form a clear pink solution which was transferred to a polytetrafluoroethylene-lined autoclave. To make the active growth more uniform, the samples were suspended in solution using aramid yarn. After heating at 180 ℃ for 12 hours, Ni-Co LDH was synthesized, then washed several times with deionized water, and dried in a vacuum oven at 60 ℃ for 12 hours. Then preparing NiCo 2 S 4 @3 DNi. 0.70g of sodium sulfide nonahydrate was added to 30mL of deionized water and stirred to form a clear solution, and the prepared Ni-Co LDH @3DNi sample was placed in the solution and then transferred to a 50mL polytetrafluoroethylene-lined autoclave at 120 deg.CThe reaction was carried out for 8 hours. Finally, taking out the product, washing the product by deionized water, and drying the product for 12 hours at the temperature of 60 ℃ to obtain NiCo 2 S 4 @3DNi。
3. And preparing the 3D printing metal iron substrate. 56g of iron sulfate powder, 5mL of Variquat CC42NS and 30mL of a photocurable resin (consisting of E-HDDA and E-TMPTA in a ratio of 3:22 with 2 wt.% TPO) were mixed, then stirred at room temperature for 1-3 hours, and then ground with a planetary ball mill to make the iron sulfate powder finer in the resin. And then, printing the substrate by using a Digital Light Processing (DLP) technology to obtain a 3D printed ferric sulfate substrate. Then, the mixture was degreased and sintered in a muffle furnace (at 200 ℃ C. for 3 hours, 400 ℃ C., 480 ℃ C., 600 ℃ C. for 6 hours, and 800 ℃ C. for two hours, respectively). Thereafter, the degreased iron oxide structure was then transferred to a PECVD furnace and reduced in an argon-hydrogen mixed atmosphere at 800 ℃ for 10 hours, resulting in a 3D printed metallic iron structure.
4. An Fe2O3@3DFe electrode was prepared. 0.2g of sodium hydroxide, 0.457g of ammonium persulfate, 27mL of deionized water, and 3.0mL of a 50mM ammonium fluoride solution were mixed, and then the solution was transferred to a Teflon-lined autoclave having a volume of 50mL, and the 3D metallic nickel substrate was immersed in the solution in the autoclave. The reaction was carried out at 180 ℃ for 12 hours, and the substrate covered with brick-red iron trioxide was taken out, rinsed with deionized water and dried in a vacuum oven. The prepared substrate was heated to 350 ℃ (at a ramp rate of 1 ℃/min) and kept in an Ar atmosphere for 4 hours
5. And fourthly, assembling the water system nickel-iron battery. With Fe 2 O 3 @3DFe being positive electrode, NiCo 2 S 4 @3DNi as negative electrode, 6M potassium hydroxide as electrolyte, Fe 2 O 3 @3DFe and NiCo 2 S 4 The @3DNi electrode is soaked in electrolyte, placed at room temperature, assembled face to face and immersed in the solution to prepare the water-based nickel-iron battery.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.

Claims (9)

1. An aqueous ferronickel battery comprises a positive electrode, a negative electrode and an electrolyte; the method is characterized in that: the positive electrode is Fe 2 O 3 @3DFe with NiCo as negative electrode 2 S 4 @3DNi, the electrolyte is potassium hydroxide solution.
2. The aqueous ferronickel battery according to claim 1, characterized in that: the anode and the cathode are layered porous 3D metal nickel electrodes.
3. A preparation method of the water-based nickel-iron battery of claim 1 is characterized by comprising the following specific steps:
the method comprises the following steps: designing an F-KS structural template through software;
mixing, stirring and grinding nickel sulfate powder, Variquat CC42NS and light-cured resin according to a certain proportion to obtain resin, and printing by adopting the resin; after printing, taking the printed structure off the printing platform, carrying out ultrasonic cleaning for multiple times, and drying at room temperature to obtain a nickel sulfate template;
mixing, stirring and grinding ferric sulfate powder, Variquat CC42NS and light-cured resin according to a certain proportion to obtain resin, and printing by adopting the resin; after printing, taking the printed structure off the printing platform, carrying out ultrasonic cleaning for multiple times, and drying at room temperature to obtain a ferric sulfate substrate;
step two: placing the nickel sulfate template/ferric sulfate substrate obtained in the step one in a muffle furnace for degreasing and sintering, transferring the degreased nickel oxide structure/ferric oxide structure into a PECVD furnace, and heating and reducing in an argon-hydrogen mixed atmosphere to obtain a 3D printing metal nickel structure/3D printing metal iron structure;
step three: dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and hexamethylenetetramine in certain mass in methanol, and stirring to form a transparent pink red solution; transferring the solution into an autoclave lined with polytetrafluoroethylene, suspending the 3D printed metal nickel structure obtained in the step two in the solution, and heating to synthesize Ni-Co LDH; cleaning with deionized water for several times, and drying in a vacuum oven to obtain Ni-Co LDH @3 DNi;
step four: adding a certain mass of sodium sulfide nonahydrate into deionized water, and stirring until the mixture is transparent; then putting the Ni-Co LDH @3DNi sample prepared in the third step into the transparent solution to obtain a mixture; then, the mixture is transferred into an autoclave lined with polytetrafluoroethylene, heated and reacted, the product is taken out, washed by deionized water and dried to obtain NiCo 2 S 4 The @3DNi electrode;
step five: mixing a certain mass of sodium hydroxide, ammonium persulfate, deionized water and an ammonium fluoride solution, and transferring the mixture into a high-pressure kettle lined with polytetrafluoroethylene; immersing a 3D printed metallic iron structure into the solution of the autoclave in the step; taking out after heating reaction, washing with deionized water and drying in a vacuum oven; heating and maintaining the prepared substrate in Ar atmosphere to obtain Fe 2 O 3 The @3DFe electrode;
step six: with Fe 2 O 3 @3DFe being positive electrode, NiCo 2 S 4 And @3DNi is a negative electrode, and 6M potassium hydroxide is an electrolyte, and the water-based nickel-iron battery is assembled.
4. The method for producing an aqueous ferronickel battery according to claim 3, characterized in that: in the first step, 20-60g of metal salt, 1-10mL of chlorariquat CC42NS and 30mL of light-cured resin are mixed in an amber bottle, stirred for 1-3 hours in a magnetic stirrer at room temperature and then ground by a planetary ball mill; the light-cured resin is prepared by mixing E-HDDA and E-TMPTA in a ratio of 3:22 and adding 2 wt.% of TPO.
5. The method for producing an aqueous ferronickel battery according to claim 3, characterized in that: in the second step, the sintering temperature of the degreasing sintering process is 200-1000 ℃, and the sintering time is 1-5 hours; the reduction step is carried out for 1-5 hours in an argon-hydrogen mixed atmosphere at 400-900 ℃.
6. The method for producing an aqueous ferronickel battery according to claim 3, characterized in that: in the third step, 0.03-0.1g of cobalt nitrate hexahydrate, 0.01-0.5g of nickel nitrate hexahydrate, 0.05-0.1g of hexamethylenetetramine and 20-50mL of methanol are used; the temperature of the high-pressure kettle is 150-; the vacuum drying temperature is 40-80 deg.C, and the drying time is 10-20 hr.
7. The method for producing an aqueous ferronickel battery according to claim 3, characterized in that: in the fourth step, 0.5-1.0g of sodium sulfide nonahydrate, 10-50mL of deionized water, 100-150 ℃ of high-pressure kettle, 5-10 hours of reaction time, 40-80 ℃ of drying temperature and 10-20 hours of drying time.
8. The method for producing an aqueous ferronickel battery according to claim 3, characterized in that: in the fifth step, 0.1-0.5g of sodium hydroxide, 0.2-0.6g of ammonium persulfate, 10-40mL of deionized water, 1.0-6.0mL of 50mM ammonium fluoride solution, 200 ℃ of the autoclave, 10-20 hours of reaction time, 400 ℃ of vacuum drying temperature, 1 ℃/min of heating rate and 2-6 hours of keeping in Ar atmosphere.
9. The method for producing an aqueous ferronickel battery according to claim 3, characterized in that: in the sixth step, Fe 2 O 3 @3DFe and NiCo 2 S 4 The @3DNi electrode is soaked in electrolyte, placed at room temperature, assembled face to face and immersed in solution to obtain the water-based nickel-iron battery.
CN202210384815.9A 2022-04-13 2022-04-13 Water system nickel-iron battery and preparation method thereof Pending CN114883669A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115513406A (en) * 2022-09-30 2022-12-23 华中科技大学 Zinc ion battery cathode, preparation method thereof and zinc ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115513406A (en) * 2022-09-30 2022-12-23 华中科技大学 Zinc ion battery cathode, preparation method thereof and zinc ion battery

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