CN113161530A - Bismuth-based nano material and preparation method and application thereof - Google Patents

Bismuth-based nano material and preparation method and application thereof Download PDF

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CN113161530A
CN113161530A CN202110261796.6A CN202110261796A CN113161530A CN 113161530 A CN113161530 A CN 113161530A CN 202110261796 A CN202110261796 A CN 202110261796A CN 113161530 A CN113161530 A CN 113161530A
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bismuth
nitrogen
nano material
based nanomaterial
based nano
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周凯
郭欣颖
牛利
韩冬雪
王昊宇
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Guangzhou 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M10/24—Alkaline accumulators
    • 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
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a bismuth-based nano material and a preparation method and application thereof, wherein the bismuth-based nano material comprises bismuth nano particles and nitrogen-doped porous carbon fibers, and the bismuth nano particles are wrapped by the nitrogen-doped porous carbon fibers, and the preparation method comprises the following steps: dissolving a carbon source, a bismuth source and a nitrogen-containing pore-forming agent in a solvent to obtain a precursor solution, and preparing a fiber material by taking the precursor solution as a raw material; and (3) pre-oxidizing the fiber material, and calcining in a protective atmosphere to obtain the bismuth-based nano material. The bismuth-based nano material prepared by the invention has excellent electrochemical performance, especially ultra-long cycle stability, is superior to bismuth-based cathode materials reported in the related technology, and has wide application prospect in alkaline batteries.

Description

Bismuth-based nano material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a bismuth-based nano material and a preparation method and application thereof.
Background
With the development of social science and technology, people can not support clothes and live without energy sources. Small articles such as mobile phones and tablet computers and large articles such as electric vehicles and smart power grids become essential parts in life. However, the traditional energy reserves are limited, and the higher and higher exploitation cost becomes a problem which cannot be ignored in the current society. The use of new energy sources such as solar energy and wind energy has strong dependence on the environment at that time, so that the development of efficient and environment-friendly energy sources is urgently needed.
Batteries are mainly used in three major industries, namely electric vehicles, energy storage and consumer electronics. Around these three directions, especially the rapid development in the field of electric vehicles and energy storage in recent years has prompted people to pay more attention to the development of safe, environmentally friendly and efficient energy storage technologies. In recent years, scientists have conducted a great deal of research into batteries, such as conventional lead-acid batteries, nickel-cadmium batteries, alkaline batteries (e.g., Ni/Bi batteries and Zn/Mn batteries), lithium ion batteries with high practicability, and sodium ion batteries. Compared with other batteries, alkaline batteries are favored by people because of their advantages of environmental friendliness, safety, low cost, high energy density, and the like. Unfortunately, most of the electrode materials of the currently used aqueous rechargeable batteries are metal oxides or hydroxides, and the compounds have the defect of poor conductivity, so that the rate performance of the batteries is poor. The positive pole of the alkaline battery mainly comprises manganese base, nickel base and cobalt base, and the negative pole material mainly comprises bismuth base, zinc base, iron base and the like. The cathode material is used as an important component of the alkaline battery and has the characteristics of safety, no toxicity, low cost, excellent electrochemical performance and the like. The metal bismuth is used as the cathode of the alkaline battery to generate highly reversible oxidation-reduction reaction in aqueous solution, and has a proper negative potential working interval, so that the bismuth is expected to be developed into an electrode material with high performance in aqueous solution. However, the cycle stability of the metal bismuth electrode is poor, and further development of the electrode is severely restricted.
The main methods for reasonably designing and optimizing the bismuth anode material are reported to be structural design, surface modification and the like. For example, 4-dibenzooxazinyl diphenyl disulfide is used as a precursor, and the N, S double-doped porous carbon material is prepared as alpha-Bi by thermal cracking2O3A carrier of, with alpha-Bi2O3The nanofiber-loaded carbon nanotube is compounded to be used as an electrode material of the super capacitor. With BiCl3And PAN is used as a raw material to prepare Bi/C one-dimensional nanofiber serving as a cathode of a lithium ion battery or a sodium ion battery by using an electrostatic spinning method. Zeng et al prepared a 3D porous Bi nanoparticle/carbon composite material (P-B-C) by a simple in-situ activation method realized high mass loading capacity and high energy density, provided a rapid charge transfer and ion diffusion channel, and had good wettability. The high-load P-B-C electrode is at 6mA/cm2Has a capacity of 2.11mAh/cm at a current density of2(166 mAh/g). Synthesizing a precursor by using a room temperature liquid phase method, then realizing carbon coating by using dopamine molecular polymerization, and finally carrying out low-temperature carbonization treatment to obtain a carbon-coated metal nano hollow bismuth simple substance, wherein the carbon-coated metal nano hollow bismuth simple substance is applied to an alkaline battery. A bismuth/nickel hydroxide secondary alkaline battery using a metal Bi powder having a particle diameter of 0.005 to 5 μm as a negative electrode material. Preparation of bismuth oxide/reduced graphene oxide (Bi) by solvothermal method2O3@ rGO) nanocomposite, single-crystal Bi 5nm in size2O3The nanoparticles are immobilized and uniformly dispersed on the reduced graphene oxide sheets. The nano-structure enables Bi to be2O3The @ rGO serving as the lithium ion battery cathode maintains the capacity of 347.3mAh/g after 100 electrochemical cycles under 600mA/g, and the capacity retention rate is 79%. Zeng prepared a layered bismuth structure with single crystal properties on a flexible carbon cloth by a simple electrodeposition method, and then annealed in a nitrogen atmosphere at 200 ℃. The three-dimensional Bi multilevel nano structure with single crystal property can show that the fishbone-like Bi nano structure uniformly grows on the surface of the carbon fiber under a scanning electron microscope, and the morphology is not changed after calcination, so that the structure provides larger surface area and more active sitesAnd (4) point. At a high current density of 4.5A/g, the capacity was 96.2mAh/g, and when the current density was increased to 45A/g, more than 94% of the capacity was retained.
Although the preparation methods and the varieties of the bismuth-based negative electrode materials are various, the capacity and the durability of the currently reported bismuth-based negative electrode materials still need to be improved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a bismuth-based nano material which can be used as a negative electrode material of an alkaline battery and has ultra-long cycle stability.
Meanwhile, the invention also relates to a preparation method and application of the bismuth-based nano material.
Specifically, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a bismuth-based nanomaterial, wherein the bismuth-based nanomaterial comprises bismuth nanoparticles and nitrogen-doped porous carbon fibers, and the bismuth nanoparticles are wrapped by the nitrogen-doped porous carbon fibers.
The diameter of the nitrogen-doped porous carbon fiber is 150-250 nm.
The particle size of the bismuth nanoparticles is 10-25 nm.
The specific surface area of the bismuth-based nano material is 150-200 m2/g。
The volume of the micro pores of the bismuth-based nano material is 0.05-0.1 cm3(ii) a total pore volume of 0.05 to 0.2cm3/g。
The second aspect of the invention provides a preparation method of a bismuth-based nano material, which comprises the following steps:
dissolving a carbon source, a bismuth source and a nitrogen-containing pore-forming agent in a solvent to obtain a precursor solution, and preparing a fiber material by taking the precursor solution as a raw material;
and (3) pre-oxidizing the fiber material, and calcining in a protective atmosphere to obtain the bismuth-based nano material.
The preparation method of the fiber material specifically comprises the steps of taking the precursor solution as a raw material, carrying out electrostatic spinning, and collecting to obtain the fiber material.
The voltage adopted in the electrostatic spinning process is 10-20 kV, and the inner diameter of the used needle head is 0.4-1 mm.
The carbon source is a high molecular polymer, and may include any one of Polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) or a combination of two of them, for example.
The bismuth source comprises soluble bismuth salt and hydrate thereof, and for example, any one or more of bismuth nitrate and hydrate thereof, bismuth chloride and hydrate thereof can be included.
The nitrogen-containing pore-forming agent comprises one or more of dicyandiamide, urea and polymethyl methacrylate (PMMA).
The solvent is a highly polar organic solvent, and may include, for example, any one or a combination of two of N, N-dimethylformamide and N, N-dimethylacetamide.
The mass ratio of the carbon source, the bismuth source and the nitrogen-containing pore-forming agent is (0.5-1) to (0.1-0.5).
The pre-oxidation is specifically to carry out heat treatment on the fiber material in air at 200-300 ℃, wherein the heat treatment time is 1-3 h.
The calcination temperature is 600-800 ℃, and the calcination time is 1-3 h.
The protective atmosphere refers to an inert atmosphere containing no oxygen, and may be, for example, a nitrogen atmosphere, an argon atmosphere, or the like. Calcining in a protective atmosphere, and reducing the bismuth oxide generated by preoxidation into a bismuth simple substance by using a carbothermic reduction reaction at a high temperature.
The third aspect of the invention is to provide the application of the bismuth-based nano material.
Specifically, the invention provides an electrode which comprises a substrate, wherein the bismuth-based nano material is coated on the substrate.
The substrate can be a general conductive substrate, such as carbon, copper, titanium, nickel, stainless steel, and the like.
Meanwhile, the invention also provides an alkaline battery comprising the electrode, and the electrode can be used as a negative electrode of the alkaline battery.
The invention has the following beneficial effects:
according to the invention, the nitrogen-containing pore-forming agent is added into the precursor solution, and the nitrogen-containing pore-forming agent becomes gas to escape in the calcining process, so that a large number of pores are formed in the material, a rich and directional ion/electron transmission channel is provided for the material, and meanwhile, the bismuth-based nano material contains a microporous structure which is beneficial to effectively wrapping bismuth nano particles, so that the loss of the bismuth-based nano material in the circulating process is avoided, the stability of the material is improved, and the electrochemical circulating performance of the material is improved; and the nitrogen-containing pore-forming agent enables the nano material to be successfully doped with nitrogen in the calcining process, the nitrogen doping improves the electronic conductivity of the material, and meanwhile, more active sites can be provided, and the electrochemical performance of the material is improved.
The bismuth-based nano material prepared by the invention has excellent electrochemical performance, especially ultra-long cycle stability, is superior to bismuth-based cathode materials reported in the related technology, and has wide application prospect in alkaline batteries.
Drawings
FIG. 1 is a schematic illustration of electrospinning;
FIG. 2 is a TEM image of Bi @ NPCF;
FIG. 3 is an XRD pattern of Bi @ NPCF;
FIG. 4 is an XPS plot of Bi @ NPCF;
FIG. 5 is a nitrogen isothermal sorption desorption curve and pore size distribution plot of Bi @ NPCF;
FIG. 6 is a graph of comparative constant current charge and discharge for Bi @ PCF, Bi @ NPCF, HD-Bi @ NPCF at a current density of 8A/g;
FIG. 7 shows the results of constant current charge and discharge measurements of Bi @ NPCF at different current densities;
FIG. 8 is a graph of the cycle performance of Bi @ NPCF;
FIG. 9 is a TEM image of Bi @ NPCF cycling 10000 cycles later.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Example 1
0.5g PAN was added to 6mL DMF and stirred for 12h to give solution A.
0.49g of bismuth nitrate pentahydrate, 0.1g of dicyandiamide and 1.2mL of DMF are added into a centrifuge tube, stirred until the mixture is clear and transparent, added into the solution A for mixing, and simultaneously 0.2mL of DMF is used for cleaning the centrifuge tube and the cleaning solutions are added into the solution A together. Then, the mixture was stirred in a water bath at 35 ℃ for 35min (1000rpm) to obtain a precursor solution.
Electrospinning was performed using the precursor solution. Specific electrospinning procedure as shown in fig. 1, the precursor solution was drawn up using a 1mL syringe and a flat needle gauge of 20G was used, then the syringe was placed in a micro syringe pump and a layer of aluminum foil was laid on a roller as a collector. Applying a voltage of 10kV to the needle, wherein the distance between the needle point and the receiver is 12.5cm, and collecting the fiber material after the completion.
Taking the fiber material down in a porcelain boat, heating to 250 ℃ in a muffle furnace at a heating rate of 2 ℃/min, carrying out heat preservation and calcination for 2h for pre-oxidation, cooling to room temperature, and taking out. And (3) placing the pre-oxidized material in a tubular furnace, introducing nitrogen, heating to 700 ℃ at a heating rate of 5 ℃/min, keeping the temperature, calcining for 2h, cooling to room temperature, and taking out to obtain the bismuth-based nano material, wherein the label is Bi @ NPCF.
As shown in FIG. 2, the appearance of Bi @ NPCF is a one-dimensional nanofiber through TEM test, and nanoparticles with the particle size distribution of about 20nm are uniformly wrapped in the fiber with the diameter of 150-250 nm. According to the preparation raw materials and the preparation method, the nano-fiber should be nitrogen-doped carbon nano-fiber, and the nano-particles wrapped inside the nano-fiber should be bismuth nano-particles.
The XRD pattern of Bi @ NPCF as shown in fig. 3 confirms the presence of elemental metal Bi; as further reflected in the XPS plot of Bi @ NPCF shown in fig. 4, Bi @ NPCF contains N, C and Bi elements, indicating successful doping of the material with nitrogen.
The nitrogen isothermal adsorption-desorption curve and the pore size distribution diagram of the Bi @ NPCF are shown in FIG. 5, and the BET specific surface area of the Bi @ NPCF is 153.05m2Per g, micropore volume of 0.07cm3(ii)/g, total pore volume of 0.084cm3(ii) in terms of/g. The material has high micropore content, is more beneficial to effectively wrapping the bismuth nano-particles, and avoids the loss of the bismuth nano-particles in the circulating process caused by overlarge pore diameter. Therefore, it can be presumed that Bi @ NPCF should have a high micropore content based on the content of Bi @ NPCFAnd (4) cycling stability.
Example 2
This example provides a bismuth-based nanomaterial whose preparation method is different from that of example 1 only in that the mass of dicyanodiamide is adjusted to 0.2 g.
The preparation method comprises the following steps:
0.5g PAN was added to 6mL DMF and stirred for 12h to give solution A.
0.49g of bismuth nitrate pentahydrate, 0.2g of dicyandiamide and 1.2mL of DMF are added into a centrifuge tube, stirred until the mixture is clear and transparent, added into the solution A for mixing, and simultaneously 0.2mL of DMF is used for cleaning the centrifuge tube and the cleaning solutions are added into the solution A together. Then, the mixture was stirred in a water bath at 35 ℃ for 35min (1000rpm) to obtain a precursor solution.
Electrospinning was performed using the precursor solution. Specific electrospinning procedure as shown in fig. 1, the precursor solution was drawn up using a 1mL syringe and a flat needle gauge of 20G was used, and the syringe was then placed in a micro syringe pump. And laying a layer of aluminum foil on the roller as a collector, applying a voltage of 10kV to the needle head, enabling the distance between the needle head and the receiver to be 12.5cm, and collecting the fiber material after spinning is finished.
Taking the fiber material down in a porcelain boat, heating to 250 ℃ in a muffle furnace at a heating rate of 2 ℃/min, carrying out heat preservation and calcination for 2h for pre-oxidation, cooling to room temperature, and taking out. And (3) placing the pre-oxidized material in a tubular furnace, introducing nitrogen, heating to 700 ℃ at a heating rate of 5 ℃/min, carrying out heat preservation calcination for 2h, cooling to room temperature, and taking out to obtain the bismuth-based nano material, wherein the mark is HD-Bi @ NPCF.
Comparative example 1
This comparative example provides a bismuth-based nanomaterial whose preparation method differs from that of example 1 only in that dicyanodiamine is not added to the precursor solution.
The preparation method comprises the following steps:
0.5g PAN was added to 6mL DMF and stirred for 12h to give solution A.
0.49g of bismuth nitrate pentahydrate and 1.2mL of DMF are added to a centrifuge tube, stirred until clear and transparent, added to solution A and mixed, and simultaneously the centrifuge tube is washed with 0.2mL of DMF and the washing solutions are added together to solution A. Then, the mixture was stirred in a water bath at 35 ℃ for 35min (1000rpm) to obtain a precursor solution.
Electrospinning was performed using the precursor solution. Specific electrospinning procedure as shown in fig. 1, the precursor solution was drawn up using a 1mL syringe and a flat needle gauge of 20G was used, and the syringe was then placed in a micro syringe pump. And laying a layer of aluminum foil on the roller as a collector, applying a voltage of 10kV to the needle head, enabling the distance between the needle head and the receiver to be 12.5cm, and collecting the fiber material after spinning is finished.
Taking the fiber material down in a porcelain boat, heating to 250 ℃ in a muffle furnace at a heating rate of 2 ℃/min, carrying out heat preservation and calcination for 2h for pre-oxidation, cooling to room temperature, and taking out. And (3) placing the pre-oxidized material in a tubular furnace, introducing nitrogen, heating to 700 ℃ at a heating rate of 5 ℃/min, carrying out heat preservation calcination for 2h, cooling to room temperature, and taking out to obtain the bismuth-based nano material, wherein the mark is Bi @ PCF.
And (3) electrochemical performance testing:
8mg of Bi @ NPCF (or HD-Bi @ NPCF, Bi @ PCF), 1mg of acetylene black and 1mg of PTFE are uniformly dispersed in a mortar by taking ethanol as a dispersing agent, coated on 1cm multiplied by 2cm of carbon cloth, dried for 12 hours in a common oven at 80 ℃ to prepare a corresponding working electrode, and electrochemical test is carried out in 6M KOH solution by taking Hg/HgO as a reference electrode and a platinum sheet as a counter electrode.
Constant current charge and discharge tests were performed on Bi @ PCF, Bi @ NPCF, HD-Bi @ NPCF at the same current density of 8A/g, and the results are shown in FIG. 6. From FIG. 6, it can be seen that Bi @ NPCF and HD-Bi @ NPCF have higher capacities than Bi @ PCF, where Bi @ NPCF has a capacity up to 140 mAh/g.
By performing constant current charge and discharge tests on the Bi @ NPCF at different current densities (3, 4, 5, 6, 8, 10, 20A/g), the results are shown in fig. 7, and the Bi @ NPCF can be found to have high capacity at different current densities.
As shown in FIG. 8, by performing a cycle stability test on Bi @ NPCF, it can be seen that Bi @ NPCF has no capacity attenuation after cycling for 10000 cycles at a current density of 20A/g, and has excellent cycle stability. The tested material was taken for TEM testing as shown in fig. 9, and the material remained unchanged in morphology of the one-dimensional fiber after cycling for 10000 cycles, demonstrating that the material structure was very stable.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A bismuth-based nanomaterial, characterized in that: the bismuth-based nano material comprises bismuth nano particles and nitrogen-doped porous carbon fibers, and the bismuth nano particles are wrapped by the nitrogen-doped porous carbon fibers.
2. The bismuth-based nanomaterial of claim 1, wherein: the diameter of the nitrogen-doped porous carbon fiber is 150-250 nm.
3. The bismuth-based nanomaterial according to claim 1 or 2, characterized in that: the particle size of the bismuth nanoparticles is 10-25 nm.
4. The bismuth-based nanomaterial of claim 3, wherein: the specific surface area of the bismuth-based nano material is 150-200 m2/g。
5. A method for preparing the bismuth-based nanomaterial of any one of claims 1 to 4, wherein the method comprises the following steps: the method comprises the following steps:
dissolving a carbon source, a bismuth source and a nitrogen-containing pore-forming agent in a solvent to obtain a precursor solution, and preparing a fiber material by taking the precursor solution as a raw material;
and (3) pre-oxidizing the fiber material, and calcining in a protective atmosphere to obtain the bismuth-based nano material.
6. The method for preparing the bismuth-based nanomaterial according to claim 5, characterized in that: the mass ratio of the carbon source, the bismuth source and the nitrogen-containing pore-forming agent is (0.5-1) to (0.1-0.5).
7. The method for preparing the bismuth-based nanomaterial according to claim 5, characterized in that: the pre-oxidation is specifically to carry out heat treatment on the fiber material in air at 200-300 ℃; preferably, the heat treatment time is 1-3 h.
8. The method for preparing the bismuth-based nanomaterial according to claim 5, characterized in that: the calcination temperature is 600-800 ℃; preferably, the calcination time is 1-3 h.
9. An electrode, characterized by: comprises a substrate, on which the bismuth-based nanomaterial of any one of claims 1 to 4 is coated.
10. An alkaline battery, characterized in that: comprising the electrode of claim 9.
CN202110261796.6A 2021-03-10 2021-03-10 Bismuth-based nano material and preparation method and application thereof Pending CN113161530A (en)

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