CN112928243A - Self-supporting nickel sulfide electrode and preparation and application thereof - Google Patents
Self-supporting nickel sulfide electrode and preparation and application thereof Download PDFInfo
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- 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
- H01M4/24—Electrodes for alkaline accumulators
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- H01M4/28—Precipitating active material on the carrier
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/30—Nickel accumulators
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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
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- H01M4/24—Electrodes for alkaline accumulators
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention relates to a preparation method of a self-supporting nickel anode and application of the self-supporting nickel anode in a zinc-nickel battery. Has the advantages that: 1) the electrode is a self-supporting electrode, a current collector, a binder and external conductive carbon are not needed, and electrons can be rapidly conducted between a carbon network and an active substance; 2) the intrinsic conductivity and the structural stability of the anode material are improved; 3) introducing nickel sulfide on a polymer framework, and after calcination, uniformly dispersing the nickel sulfide material with a specific crystal form in a continuous highly graphitized three-dimensional conductive carbon network to provide a rapid transmission channel for electron transmission; 4) and carbonizing at high temperature to obtain the membrane electrode with a porous structure. Abundant pore structures ensure the full infiltration of electrolyte and provide a rapid diffusion channel for the diffusion of the electric balance ions; 5) after the polymer is carbonized, the polymer is uniformly coated on the surface of the active substance, so that the volume change of the active substance in the circulation process is inhibited, and the good structural stability can be kept in the long-term circulation process; 6) simple process and low energy consumption.
Description
Technical Field
The invention relates to the technical field of zinc-nickel batteries, in particular to a preparation method of a self-supporting nickel sulfide positive electrode and application of the self-supporting nickel sulfide positive electrode in a zinc-nickel battery.
Background
With the improvement of living standard of people, automobiles have gone into thousands of households as common vehicles, and at present, automobile fuels mainly come from non-renewable energy sources such as petroleum and the like, so that environmental pollution and energy depletion are caused. Environmental problems and energy crisis caused by the great popularization of fuel automobiles are more and more attracting attention of people, electric automobiles as an environment-friendly vehicle attract attention of all countries in the world, and all countries in the world are investing a great amount of manpower and material resources to develop the electric automobiles. Increasing the energy density of a battery while ensuring the safety of the battery is an important research subject at present. The lead-acid battery has a series of problems of low energy density utilization rate, capacity attenuation and environmental pollution caused by incomplete conversion of active substances and the like, and becomes the largest restriction factor for entering the electric automobile market. Lithium ion batteries occupy a large portion of the electric vehicle market due to their high energy density, but with the frequent occurrence of fire events, their safety issues have once been a concern.
The emerging high specific energy zinc-nickel battery has the obvious advantages of high working voltage, high energy density, high safety of water system electrolyte, no environmental pollution, low production cost, abundant electrode material resources and the like, and is a rechargeable secondary battery with great potential. But poor cycle stability is the biggest bottleneck limiting the development of high specific energy zinc-nickel batteries. The factors influencing the cycling stability of the zinc-nickel battery mainly comprise the following two factors: firstly, the intrinsic electronic conductivity of the positive electrode material nickel hydroxide is low, and the layered structure is easy to expand and contract in volume during the charging and discharging processes so as to cause the collapse of the structure, thereby reducing the cycle life of the battery, which is attributed to the intrinsic structure defects of the material; secondly, the preparation method of the electrode is not enough, and the specific preparation process is that nickel hydroxide, a binder and a conductive agent are mixed to prepare slurry, and then the slurry is coated on a current collector such as foamed nickel and the like to prepare the electrode.
In order to solve the problem of poor cycle stability of the high specific energy zinc-nickel battery, the invention provides a preparation method of a self-supporting nickel anode, and a high-performance self-supporting electrode without a current collector, a binder and conductive carbon is prepared. The process has the following advantages: 1) the electrode is a self-supporting electrode, a current collector, a binder and additional conductive carbon are not needed, the binding force of the whole electrode is improved, and electrons can be rapidly conducted between a carbon network and an active substance; 2) the nickel sulfide material with excellent conductivity is used for replacing a nickel hydroxide material, so that the intrinsic conductivity and the structural stability of the anode material are improved; 3) uniformly introducing nickel sulfide on a polymer framework by a hydrothermal method, and uniformly dispersing the nickel sulfide material with a specific crystal form in a continuous highly graphitized three-dimensional conductive carbon network after high-temperature calcination to provide a rapid transmission channel for electron transmission; 4) and (3) carbonizing at high temperature to obtain the membrane electrode with a porous structure, wherein the size of pores is about 100-500 nm. The abundant pore structure can ensure the full infiltration of the electrolyte and provide a rapid diffusion channel for the diffusion of the electric balance ions; 5) after the polymer is carbonized, the polymer can be uniformly coated on the surface of the active substance, so that the volume change of the active substance in the circulation process can be inhibited, and the good structural stability can be kept in the long-term circulation process; 6) compared with the traditional electrode preparation method, the process is simpler, the flow is shorter, the energy consumption is lower, and the method is more suitable for large-scale production.
Disclosure of Invention
The invention relates to a preparation method of a self-supporting electrode and application of the self-supporting electrode in a zinc-nickel battery. The composition of the self-supporting electrode is Ni3S4@3DPC(Ni3S4: active material, 3 DPC: three-dimensional porous carbon);
1) the preparation steps of the self-supporting electrode comprise: dissolving a certain amount of nickel salt and weak base in deionized water, and stirring for 0.5-1 h to obtain a mixed solution A. The molar ratio of the nickel salt to the weak base is 1: 5-1: 30, preferably 1: 10-1: 20, and the concentration of nickel ions is 0.01-0.06M, preferably 0.02-0.04M;
2) and immersing the polyolefin porous membrane into the mixed solution A, controlling the temperature of the solution to be 30-100 ℃, preferably 60-80 ℃, continuously stirring and heating for 12-72 h, taking out the polyolefin porous membrane, sequentially washing with ethanol and deionized water, and drying at room temperature to obtain the nickel silicate porous membrane. The stirring speed is 200-600 rpm, the polyolefin porous membrane is one or two of a Polyethylene (PE) porous membrane with embedded silica particles and a polypropylene (PP) porous membrane, the thickness of the polyolefin porous membrane is 200-900 mu m, the pore diameter is 50-500 nm, the porosity is 30-60%, the particle diameter of the embedded silica particles is 10-30 nm, and the mass content of the embedded silica particles in the polyolefin porous membrane is 40-60%;
3) and (3) soaking the nickel silicate base porous membrane prepared in the step (2) in an alkaline solution to remove silicon dioxide particles to obtain the hollow nickel silicate base porous membrane. The alkali liquor is NaOH or KOH aqueous solution, and the concentration is 3-6mol/L, preferably 4 mol/L;
4) calcining the hollow nickel silicate-based porous membrane obtained in the step (3) at 500-900 ℃ for 1-5h, preferably 600-800-2 h, in an inert gas atmosphere to obtain a self-supporting electrode NiO @3 DPC;
5) dissolving a certain amount of a vulcanizing agent in deionized water, wherein the concentration is 2-20 g/L, preferably 10g/L, and stirring for 0.5-1 h to obtain a solution B.
6) Placing the NiO @3DPC electrode prepared in the step (4) in the solution B, and carrying out hydrothermal reaction for 2-24 h at 100-200 ℃, preferably 150-180 ℃, and-0-12 h to obtain Ni3S4@3DPC self-supporting electrode;
7) the prepared NiSx @3DPC self-supporting electrode is used as a working electrode, a metal zinc sheet is used as a negative electrode, a glass fiber membrane is used as a diaphragm, electrolyte is 0.4mol/L ZnO and 4mol/L KOH aqueous solution, and a zinc-nickel battery is assembled by sequentially stacking and compressing a CR2025 button type shell according to the sequence of a negative electrode shell, a negative electrode, the electrolyte, the diaphragm, the electrolyte, a positive electrode and a positive electrode shell.
Based on the technical scheme, preferably, the nickel salt is nickel chloride, nickel nitrate, nickel acetate and nickel sulfate, and the weak base is urea, ammonia water and hexamethylenetetramine.
Based on the technical scheme, preferably, the vulcanizing agent can be one or more of thioacetamide, thiourea and sodium sulfide.
The invention has the advantages of
1) The nickel sulfide material is used for replacing the traditional nickel hydroxide material, so that the intrinsic conductivity and the structural stability of the nickel anode material are improved;
2) the self-supporting electrode prepared by the process has a three-dimensional conductive carbon network and a porous structure, can ensure sufficient electrolyte infiltration, good contact between an active substance and a carbon material, rapid electron conduction and ion diffusion, and effectively improves the rate capability of the battery;
3) after the polymer is carbonized, the polymer is uniformly coated on the surface of the active substance, so that the volume change of the active substance in the circulation process can be inhibited, and the good structural stability can be kept in the long-term circulation process;
4) the preparation method of the self-supporting electrode simplifies the production process of the battery, has lower energy consumption and is more suitable for large-scale production.
Drawings
FIG. 1 is a photograph of examples and comparative examples 2 to 4.
Fig. 2 is an XRD pattern of examples and comparative examples 2 to 4.
Fig. 3 is a TGA profile of an example.
FIG. 4 is SEM images (scale 100nm in the figure) of examples and comparative example 4.
FIG. 5 is a graph comparing the properties of examples and comparative examples 1 to 4.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention. Comparative example 1: preparing a nickel anode from a commercial nickel hydroxide material by a traditional slurry coating method;
comparative example 2: in the hollow nickel silicate-based porous membrane obtained in the step 3, particles accumulated in the pores are in a nickel silicate shell structure, and after the membrane is calcined in argon at 600 ℃ for 2 hours, nickel silicate is dehydrated and changed into nickel oxide, so that a self-supporting electrode NiO @3DPC-600 is obtained;
comparative example 3: calcining the hollow nickel silicate-based porous membrane in argon at 700 ℃ for 2h to obtain a self-supporting electrode NiO @3 DPC-700;
comparative example 4: calcining the hollow nickel silicate-based porous membrane in argon at 800 ℃ for 2 hours to obtain a self-supporting electrode NiO @3 DPC-800;
example (b):
1) the polyethylene porous base membrane with embedded silica particles is taken, the thickness of the polyethylene porous base membrane is 200 mu m, the pore diameter is distributed between 50 nm and 200nm, the porosity is about 58 percent, and the mass content of the silica (the particle diameter of the particles is 10 nm to 30nm) is about 50 percent. The base film was cut to a size of 8cm × 8cm, and washed with ethanol and deionized water in this order. Dissolving 0.49g of nickel chloride hexahydrate and 2.4g of urea in 200mL of deionized water, magnetically stirring for about 30 minutes to obtain a clear solution, putting four pieces of base membranes into the solution, heating to 60 ℃, stirring for 24 hours at 500rmp, taking out the reacted membranes after reaction, sequentially washing with deionized water and ethanol, and naturally airing at room temperature to obtain the nickel silicate base porous membrane;
2) soaking the nickel silicate base porous membrane prepared in the step (1) in a 4mol/L KOH aqueous solution for 10 hours to remove silicon dioxide particles to obtain a hollow nickel silicate base porous membrane;
3) calcining the hollow nickel silicate-based porous membrane obtained in the step (2) for 2 hours at 800 ℃ in an argon atmosphere to obtain a self-supporting electrode NiO @3 DPC;
4) dissolving 1g of thioacetamide in 100mL of water, and stirring for 0.5-1 h to obtain a solution B. Placing the NiO @3DPC electrode prepared in the step (3) in the solution B, and carrying out hydrothermal reaction for 10h at 160 ℃ to prepare Ni3S4@3DPC self-supporting electrode;
the electrodes prepared in comparative examples 1 to 4 and examples were used as positive electrodes, zinc sheets (50 μm) were used as negative electrodes, glass fiber films were used as separators, and an electrolyte was an aqueous solution of 0.4mol/L ZnO and 4mol/L KOH, and a zinc-nickel battery was assembled by stacking and compressing the negative electrode case, the negative electrode, the electrolyte, the separator, the electrolyte, the positive electrode, and the positive electrode case in this order by a CR2025 button case.
Fig. 1 is a photograph of comparative examples 2-4 and examples, from which it can be seen that the overall morphology of the self-supporting electrode remained good during both the high temperature calcination and the hydrothermal reaction. As the calcining temperature is increased, the carbonization degree is increased, the size of the electrode sheet is reduced, but the size of the electrode is not basically changed after one-step vulcanization. As can be seen from the sectional topography of FIG. 2, the electrode sheet thickness size after vulcanization does not change much, but nickel sulfide particles are finer, and the porosity of the electrode structure is increased. Fig. 3 is an XRD pattern of comparative examples 2 to 4 and examples, in which only two peak positions of nickel oxide appear in the electrode after the base film is calcined at a high temperature, and the crystallinity increases as the calcination temperature increases. After hydrothermal sulfidation, the nickel oxide peak completely disappeared and a nickel sulfide peak (mainly Ni) appeared3S4) It was shown that the sulfidation reaction proceeded sufficiently to obtain a self-supporting electrode Ni3S4@3 DPC-800. The carbon content in the self-supporting nickel sulfide electrode is 16% as obtained by thermogravimetric testing (fig. 4), and the strong carbon skeleton network plays a key role in rapid electron conduction.
Fig. 5 shows the performance of the zinc-nickel batteries of examples and comparative examples 1 to 4, from which it can be seen that the capacity exertion of the unsulfided nickel oxide electrode (comparative examples 2 to 4) is very low, which may be due to the serious agglomeration of the active material, thereby affecting the capacity exertion, and the electrode after one-step sulfidation (example) is more sufficient for the contact of the active material with the electrolyte due to the increase of the porosity, thereby facilitating the better exertion of the capacity. Compared with a commercial nickel hydroxide material (comparative example 1), the nickel sulfide material has good structural stability, and meanwhile, the uniform carbon coating can also inhibit slight volume change of the nickel sulfide in the charging and discharging processes, so that the structural stability is further ensured, and the cycle performance of the material is improved. The nickel anode for the zinc-nickel battery is excellent in performance and simple in preparation process, and is a preparation method of the nickel anode for the zinc-nickel battery, which is very suitable for large-scale production.
Claims (6)
1. A preparation method of a self-supporting electrode is characterized by comprising the following steps:
the preparation steps of the self-supporting electrode comprise:
1) dissolving nickel salt and weak base in deionized water, and stirring for 0.5-1 h to obtain a mixed solution A; the molar ratio of the nickel salt to the weak base is 1: 5-1: 30, preferably 1: 10-1: 20, and the concentration of nickel ions is 0.01-0.06M, preferably 0.02-0.04M;
2) immersing the polyolefin porous membrane into the mixed solution A, controlling the temperature of the solution to be 30-100 ℃, preferably 60-80 ℃, continuously stirring and heating for 12-72 h, taking out the polyolefin porous membrane, sequentially washing with ethanol and deionized water, and drying at room temperature to obtain a nickel silicate base porous membrane; the stirring speed is 200-600 rpm,
the polyolefin porous membrane is one or two of Polyethylene (PE) and polypropylene (PP) porous membranes with embedded silica particles, the thickness of the polyolefin porous membrane is 200-900 micrometers, the pore diameter is 50-500 nm, and the porosity is 30-60%, wherein the particle size of the embedded silica particles is 10-30 nm, and the mass content of the embedded silica particles in the polyolefin porous membrane is 40-60%;
3) soaking the nickel silicate base porous membrane prepared in the step (2) in an alkaline solution to remove silicon dioxide particles to obtain a hollow nickel silicate base porous membrane; the alkali liquor is NaOH and/or KOH aqueous solution, and the concentration is 3-6mol/L, preferably 4 mol/L;
4) calcining the hollow nickel silicate-based porous membrane obtained in the step (3) at 500-900 ℃ in an inert gas atmosphere for 1-5h, preferably 600-800-2 h, and preparing a self-supporting electrode NiO @3 DPC;
5) dissolving a certain amount of a vulcanizing agent in deionized water, wherein the concentration is 2-20 g/L, preferably 10g/L, and stirring for 0.5-1 h to obtain a solution B; the sulfurizing reagent can be one or more of thioacetamide, thiourea and sodium sulfide;
6) placing the NiO @3DPC electrode prepared in the step (4) in the solution B, and carrying out hydrothermal reaction at the temperature of 100-200 ℃ for 2-24 h, preferably at the temperature of 150-180 ℃ for 10-12h to obtain Ni3S4@3DPC self-supporting electrode.
2. The method of claim 1, wherein: the nickel salt is nickel chloride, nickel nitrate, nickel acetate and nickel sulfate, and the weak base is one or more of urea, ammonia water and hexamethylenetetramine.
3. The method of claim 1, wherein: the inert atmosphere is argon and/or nitrogen.
4. A self-supporting electrode prepared by the preparation method according to any one of claims 1 to 3.
5. Use of the self-supporting electrode of claim 4 in a zinc-nickel battery.
6. Use according to claim 5, characterized in that: the self-supporting electrode is used as a positive electrode and applied to a zinc-nickel battery.
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