CN114614027A - Preparation method of CoFe-S @3D-S-NCNT electrode and quasi-solid zinc-air battery - Google Patents

Preparation method of CoFe-S @3D-S-NCNT electrode and quasi-solid zinc-air battery Download PDF

Info

Publication number
CN114614027A
CN114614027A CN202210150723.4A CN202210150723A CN114614027A CN 114614027 A CN114614027 A CN 114614027A CN 202210150723 A CN202210150723 A CN 202210150723A CN 114614027 A CN114614027 A CN 114614027A
Authority
CN
China
Prior art keywords
cofe
ncnt
micro
preparation
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210150723.4A
Other languages
Chinese (zh)
Other versions
CN114614027B (en
Inventor
孙小华
赵大福
刘秋恒
孙盼盼
吕小伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Three Gorges University CTGU
Original Assignee
China Three Gorges University CTGU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Three Gorges University CTGU filed Critical China Three Gorges University CTGU
Priority to CN202210150723.4A priority Critical patent/CN114614027B/en
Publication of CN114614027A publication Critical patent/CN114614027A/en
Application granted granted Critical
Publication of CN114614027B publication Critical patent/CN114614027B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inert Electrodes (AREA)

Abstract

A preparation method of a CoFe-S @3D-S-NCNT electrode and a quasi-solid zinc-air battery. The invention relates to the technical field of chargeable and dischargeable quasi-solid zinc-air batteries, in particular to a preparation method of an electrode and a quasi-solid zinc-air battery comprising the electrode. By taking cobalt salt, ferric salt and 2-methylimidazole as reaction raw materials, growing at room temperature to obtain CoFe-MOF nanosheets, and then carrying out CVD annealing carbonization to obtain CoFe @3D-NCNT micro/nano materials; and then carrying out hydrothermal reaction in a sodium sulfide solution to obtain a CoFe-S @3D-S-NCNT micro/nano composite material with a 3D micro/nano hierarchical structure, high catalytic activity and better hydrophobicity. The prepared CoFe-S @3D-S-NCNT composite material is used as a cathode, a zinc anode and a quasi-solid stateThe electrolyte is assembled into a quasi-solid zinc-air battery with a sandwich structure. The battery has ideal charge and discharge performance, the open circuit voltage is up to 1.479V, and the discharge peak power density is up to 460mW/cm2Has excellent charge and discharge stability, and can be cycled for more than 225 weeks.

Description

Preparation method of CoFe-S @3D-S-NCNT electrode and quasi-solid zinc-air battery
Technical Field
The invention relates to the technical field of preparation of quasi-solid rechargeable zinc-air batteries, and particularly relates to the technical field of preparation of new energy materials on the side of an air cathode.
Background
The quasi-solid zinc-air battery has the advantages of high energy density, portability, small volume, low cost, safety, environmental protection and the like, and has good application prospect. However, the quasi-solid zinc-air battery has low peak power density and poor stability, and the realization of practical application is still a great challenge. The air electrode is used as a core component of a quasi-solid zinc-air battery, and has important influence on the energy storage density, the discharge peak power density and the cycle life of the battery. Therefore, the development of cathode electro-catalytic materials and air electrodes with high catalytic activity, high stability and high reaction kinetics has important significance in promoting the practical application of high-performance quasi-solid zinc-air batteries, and can also generate obvious economic value and social benefit. The development of current wearable electronic devices has attracted attention to quasi-solid state zinc-air batteries, which require portability while maintaining high performance, and thus the design of batteries requires attention to both electrochemical performance and structural stability.
Platinum carbon, ruthenium oxide, iridium oxide are by far the most effective electrocatalysts for ORR and OER. However, such noble metal materials are expensive and also have poor immunity to fuel oxidizing molecules. And the prepared integrated electrode material cannot have high dual-functional activity, and the performance of the assembled quasi-solid zinc-air battery is insufficient. In spite of the challenges faced, it is important to develop an efficient, durable electrocatalyst. Therefore, the cathode material aims to prepare an economic and efficient bifunctional electrocatalyst, namely, the vulcanized cobalt-iron alloy nano particles are coated on the nitrogen-doped carbon nano tube material, wherein the cobalt-iron sulfide plays a role in catalyzing Oxygen Evolution Reaction (OER) and the nitrogen-doped carbon nano tube catalyzes ORR reaction, and in addition, the morphological structure, the electric conduction capability and the surface component defects of the carbon nano tube structure material can also mutually cooperate to promote the catalytic reaction. The prepared cathode catalyst, zinc anode and electrolyte form a quasi-solid zinc-air battery with a sandwich structure. The powder air electrode material prepared by the simple method and having high bifunctional activity, high power density and excellent stability is not reported to be applied to quasi-solid zinc-air batteries.
Disclosure of Invention
In order to solve the problems, the invention provides a CoFe-S @3D-S-NCNT micro-nano composite material and a preparation method and application thereof. The material has high dual-function activity, and has excellent peak power density and better cycle stability with a quasi-solid zinc-air battery with a sandwich structure assembled by a zinc anode and an electrolyte.
One of the technical schemes of the invention is a CoFe-S @3D-S-NCNT micro-nano composite material which is a material with a 3D micro-nano composite structure and is formed by in-situ growth of CoFe alloy carbon nano tubes on a three-dimensional carbon substrate. The CoFe-S @3D-S-NCN micro-nano composite material has a 3D micro-nano hierarchical structure and good hydrophobicity, and a quasi-solid zinc-air battery with a sandwich structure is formed by an air cathode, a zinc anode and a quasi-solid electrolyte which are prepared from the CoFe-S @3D-S-NCNT micro-nano composite material, and has high peak power density and high cycle stability.
According to the second technical scheme, the preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material comprises the following steps: taking cobalt salt, ferric salt and 2-methylimidazole as reaction raw materials to obtain CoFe-MOF nanosheets, and then carrying out CVD annealing carbonization to obtain CoFe @3D-NCNT micro/nano materials; and then carrying out hydrothermal reaction in a sodium sulfide aqueous solution to obtain the CoFe-S @3D-S-NCNT micro-nano composite material with the surface of CoFe @3D-NCNT covered with cobalt sulfide and cobalt iron sulfide.
Further, the method specifically comprises the following steps:
(1) preparation of CoFe-MOF nanosheets: aging a mixed solution composed of cobalt salt, a ferric salt aqueous solution and a 2-methylimidazole aqueous solution, and then centrifugally cleaning and drying to obtain CoFe-MOF;
(2) preparation of CoFe @ 3D-NCNT: annealing CoFe-MOF nanosheets in a hydrogen-mixed atmosphere in the presence of melamine to obtain a CoFe @3D-NCNT nanomaterial;
(3) preparation of CoFe-S @ 3D-S-NCNT: and immersing the CoFe @3D-NCNT nano material in a sodium sulfide solution for hydrothermal reaction, and washing and drying to obtain CoFe-S @ 3D-S-NCNT.
Further, in the step (1), the cobalt salt can be cobalt nitrate, cobalt chloride or cobalt acetate, the concentration of the aqueous solution is 5-20g/L, the ferric salt can be ferric chloride, ferric nitrate or ferric acetate, the concentration of the aqueous solution is 0.5-2g/L, and the concentration of the aqueous solution of 2-methylimidazole is 20-50 g/L; stirring for 2-6h, drying at 60 deg.C for 10 h.
Further, the step (2) specifically includes: placing CoFe-MOF nanosheets at the downstream of a tube type atmosphere furnace tube, placing melamine at the upstream, placing the tube type atmosphere furnace tube in an argon and hydrogen atmosphere for calcining, raising the temperature to 700-900 ℃ within 0.5-2 hours, continuing to preserve heat for 1-2 hours, and naturally cooling to obtain CoFe @ 3D-NCNT;
in the mixed atmosphere of argon and hydrogen, the content of argon is 85-95% and the content of hydrogen is 5-15%. The preferable scheme is that in the mixed atmosphere of argon and hydrogen, the content of argon is 95 percent, and the content of hydrogen is 5 percent.
The mass ratio of melamine to cobalt salt and iron salt is 0.05-0.2: 5-20: 5-20. Under high-temperature atmosphere, ammonium ions in melamine have reducibility with a small amount of hydrogen in the atmosphere, metal ions in CoFe-MOF can be reduced into metal alloy, and the metal alloy is catalyzed and grown into carbon nano tubes in the presence of a carbon source.
Further, in the step (3): the concentration of the sodium sulfide solution is 10-20 g/L; the hydrothermal reaction temperature is 100 ℃ and 140 ℃, and the hydrothermal reaction time is 6-18 h.
The sulfur ions in the sodium sulfide solution form sulfides with partial metal particles in the three-dimensional carbon skeleton under the hydrothermal environment, and also form sulfides with partial alloy in the carbon nano tube, so that the catalytic performance of the catalyst is remarkably improved.
According to the third technical scheme, the CoFe-S @3D-S-NCNT micro-nano composite material is applied to an air electrode of a quasi-solid zinc-air battery.
According to the fourth technical scheme, the quasi-solid zinc-air battery air electrode is prepared by adding ethanol and naphthol solution into the CoFe-S @3D-S-NCNT micro-nano composite material in a ratio of (800-1000 mu L): (40-100 mu L), ultrasonically mixing for 40-80 min to obtain catalyst ink, dripping the catalyst ink on carbon paper or carbon cloth, and drying at 50 ℃ to obtain the quasi-solid rechargeable zinc-air battery air electrode.
In the fifth technical scheme of the invention, the quasi-solid zinc-air battery anode material is one of zinc sheets, zinc foils, zinc strips, carbon cloth carbon paper and the like which are plated with zinc in situ.
In the sixth technical scheme of the invention, the quasi-solid electrolyte material of the quasi-solid zinc-air battery is one of PVA electrolyte, PaNa electrolyte, biological cellulose membrane electrolyte and acrylic acid gel electrolyte.
Seventhly, the quasi-solid zinc-air battery is prepared by taking carbon paper of the CoFe-S @3D-S-NCNT nano composite material as a cathode electrode, a zinc anode electrode and electrolyte gel, and the quasi-solid zinc-air battery of the CoFe-S @3D-S-NCNT nano composite material is obtained.
Compared with the prior art, the invention has the beneficial effects that:
the CoFe-S @3D-S-NCNT three-dimensional micro-nano composite material has a composite structure that the carbon nano tube grows on a three-dimensional carbon skeleton in situ, the product appearance is uniform, the microstructure has certain hydrophobicity, the cobalt iron sulfide has better OER performance, the ORR performance of the carbon nano tube is excellent, and the composite material combines the advantages of the three and has high difunctional activity. Due to the improvement of hydrophobicity, more air can be contacted in the electrolyte, so that the discharge polarization of the electrolyte is obviously improved, and the power density of the material is further improved.
The preparation method of the CoFe-S @3D-S-NCNT three-dimensional micro-nano composite material air electrode has the advantages of high repeatability, simple synthesis process, easiness in control and the like. The quasi-solid zinc-air battery formed by using the prepared CoFe-S @3D-S-NCNT micro-nano composite material as a cathode, a zinc anode and a quasi-solid electrolyte material has high bifunctional activity, high power density and high stability; applied to the air electrode of a rechargeable quasi-solid zinc-air battery with the power density of 460mWcm2Long term stability of 225 cycles.
Drawings
Figure 1 is the XRD pattern of the product prepared in example 1, where: the abscissa X is the diffraction angle (2 θ), and the ordinate Y is the relative diffraction intensity.
FIG. 2 is a TEM image of the product prepared in example 1, with Co as the object image in the image of a9S8Co and amorphous carbon material, the object image in the b picture is Co8FeS8And Co7Fe3。
FIG. 3 is a morphology chart (5 μm) of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
FIG. 4 is a morphology chart (2 μm) of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
FIG. 5 is a morphology chart of CoFe @3D-NCNT material prepared in step (2) of example 1.
FIG. 6 is a hydrophobicity chart of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
FIG. 7 is an ORR performance diagram of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
FIG. 8 is an OER performance graph of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
FIG. 9 is an ORR stability test performance diagram of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
Fig. 10 is a diagram of a PaNa quasi-solid electrolyte prepared in example 1.
FIG. 11 is a graph of the open circuit voltage of a rechargeable zinc-air cell of example 1 with CoFe-S @3D-S-NCN micro T nanocomposites.
FIG. 12 is the discharge polarization curve performance results for a zinc-rechargeable air cell of CoFe-S @3D-S-NCN micro T nanocomposite prepared in example 1.
FIG. 13 shows the cycle performance results of the rechargeable zinc-air battery made of the CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
FIG. 14 is a diagram of a rechargeable zinc-free battery lighting LED lamp made of CoFe-S @3D-S-NCNT micro-nano composite material prepared in example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO)3)2·6H2O) and 0.06g of ferrous chloride tetrahydrate (FeCl)2·4H2O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, deionized water and ethanol were subjected to centrifugal washing several times at 6500 rpm for a purple solution, and dried at 80 ℃ for 12 hours.
(2) Preparation of CoFe @3D-NCNT
Placing the prepared purple CoFe-MOF powder at the downstream of a porcelain boat, placing melamine at the upstream, placing the porcelain boat in a tube furnace for calcination, wherein the calcination atmosphere is 95% argon and 5% hydrogen, the calcination temperature is 800 ℃, the temperature rise time is 176 minutes, the heat preservation time is 1 hour, and after the tube furnace is naturally cooled, obtaining the CoFe @3D-NCNT nano material.
(3) Preparation of CoFe-S @3D-S-NCNT
And (2) ultrasonically dissolving 0.7g of sodium sulfide in 40mL of deionized water, transferring the deionized water to a reaction kettle, immersing the CoFe @3D-NCNT black powder synthesized in the step (2) into the solution, carrying out hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, carrying out centrifugal washing on deionized water and ethanol for several times at the rotating speed of 6500 revolutions, and drying at 80 ℃ to obtain the final product CoFe-S @3D-S-NCNT nano composite material.
XRD test results for this example show that: as shown in FIG. 1, the X axis of the abscissa is the diffraction angle (2. theta.), and the Y axis of the ordinate is the relative diffraction intensity, and the diffraction peaks thereof correspond to the C peak, the Co peak, and the CoFe alloy peak. As for the absence of sulfide, it was not found because the degree of sulfide in water was weak and the detectivity of XRD was limited.
The TEM test results for this example show that: as shown in FIG. 2, Co is found in TEM9S8Co, amorphous C material, Co7Fe3And Co8FeS8It was demonstrated that hydrothermal vulcanization work results in transformation of the alloy to sulfide
The nanocomposite prepared in the present example was analyzed by a field emission scanning electron microscope, and the obtained electron micrographs are shown in fig. 3 to 5; wherein, FIGS. 3-4 are morphology diagrams of the prepared CoFe-S @3D-S-NCNT micro-nano composite material at a ratio of 5 μm and 3 μm respectively, and FIG. 5 is a morphology diagram of the CoFe @3D-NCNT micro-nano material prepared in the step (2); as can be seen, the CoFe-S @3D-S-NCNT micro-nano composite material prepared by the embodiment has uniform appearance and a typical hydrophobic structure.
Taking the CoFe-S @3D-S-NCNT micro-nano composite material prepared in the embodiment, fully grinding, and then sequentially adding ethanol and naphthol solution in a ratio (800-1000 mu L): (40-100 mu L), ultrasonically mixing for 40-80 min to obtain catalyst ink, dripping the catalyst ink on carbon paper or carbon cloth with the area of 1 square centimeter, and drying at 50 ℃ to obtain the quasi-solid rechargeable zinc-air battery air electrode.
The prepared CoFe-S @3D-S-NCNT micro/nano composite material is subjected to hydrophobicity test, and carbon paper loaded with the CoFe-S @3D-S-NCNT micro/nano composite material is directly tested, as shown in FIG. 6, the hydrophobic angle is 151 degrees, which proves that the CoFe-S @3D-S-NCNT micro/nano composite material is excellent in hydrophobicity, and the material with good hydrophobicity has advantages in discharge polarization because the discharge polarization needs a large amount of oxygen to enable the reaction to be carried out in the forward direction.
ORR performance test is carried out on the prepared CoFe-S @3D-S-NCNT micro-nano composite material, as shown in figure 7, the prepared CoFe-S @3D-S-NCNT micro-nano composite material has a higher half-wave potential of 0.855V, which is close to 6mA/cm2The limiting current density of (a), indicates that it has excellent ORR activity.
OER performance test is carried out on the prepared CoFe-S @3D-S-NCNT micro-nano composite material, as shown in figure 8, it can be seen that the OER performance is 10mA/cm2Only a small overpotential of 310mV is sufficient to demonstrate excellent OER performance.
ORR stability test is carried out on the prepared CoFe-S @3D-S-NCNT micro-nano composite material, as shown in figure 9, it can be seen that after the stability test of 7200S, the current density can still be kept at 96% of the initial current, and the good stability is proved.
And (3) aligning the solid-state battery for assembly, and assembling the quasi-solid-state zinc-air battery with a sandwich structure by taking the polished zinc sheet as an anode, taking a PaNa (sodium polyacrylate) electrolyte and taking carbon paper loaded with a CoFe-S @3D-S-NCNT micro-nano composite material as a cathode.
Fig. 10 shows a PaNa electrolyte, which is a jelly-like gel.
The discharge polarization performance test is carried out on the quasi-solid zinc-air battery of the prepared CoFe-S @3D-S-NCNT micro-nano composite material, and the result is shown in figure 12, so that the open-circuit voltage can be stabilized at 1.479V within the test time, and the open-circuit voltage is relatively high.
The discharge polarization performance test is carried out on the quasi-solid zinc-air battery of the prepared CoFe-S @3D-S-NCNT micro-nano composite material, the result is shown in figure 13, the discharge function is normal, and the maximum power density is 460mW/cm2Showing C prepared by the process of the present inventionThe quasi-solid zinc-air battery with the sandwich structure assembled by the oFe-S @3D-S-NCNT micro-nano composite material has higher energy conversion efficiency.
The quasi-solid zinc-air battery made of the CoFe-S @3D-S-NCNT micro/nano composite material is subjected to cycle performance detection and is subjected to cycle charge and discharge, and the result is shown in figure 13, the battery performance is still stable before 225 cycles of continuous work, and the rechargeable zinc-air battery assembled by the CoFe-S @3D-S-NCNT micro/nano composite material made by the method has good battery cycle stability.
As shown in fig. 14, it can be seen that the LED (3V) lamp can be lighted by the quasi-solid zinc-air battery made of the quasi-solid zinc-air battery composed of two quasi-solid zinc-air batteries including the cathode material of CoFe-S @3D-S-NCNT micro/nano composite material, the PaNa electrolyte and the zinc sheet.
Example 2
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO)3)2·6H2O) and 0.06g of ferrous chloride tetrahydrate (FeCl)2·4H2O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, deionized water and ethanol were subjected to centrifugal washing several times at 6500 rpm for a purple solution, and dried at 80 ℃ for 12 hours.
(2) Preparation of CoFe @3D-NCNT
Placing the prepared purple powder of the CoFe-MOF at the downstream of a porcelain boat, placing melamine at the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is 95% argon and 5% hydrogen, the calcination temperature is 800 ℃, the temperature rise time is 176 minutes, the heat preservation time is 1 hour, and after the tube furnace naturally cools down, obtaining the CoFe @3D-NCNT nano material.
(3) Preparation of CoFe-S @3D-S-NCNT
And (2) ultrasonically dissolving 0.7g of sodium sulfide in 40mL of deionized water, transferring the deionized water to a reaction kettle, immersing the CoFe @3D-NCNT black powder synthesized in the step (2) into the solution, carrying out hydrothermal reaction for 5 hours at 120 ℃, cooling to room temperature, carrying out centrifugal washing on deionized water and ethanol for several times at the rotating speed of 6500 revolutions, and drying at 80 ℃ to obtain the final product CoFe-S @3D-S-NCNT nano composite material.
Example 3
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO)3)2·6H2O) and 0.06g of ferrous chloride tetrahydrate (FeCl)2·4H2O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, deionized water and ethanol were subjected to centrifugal washing several times at 6500 rpm for a purple solution, and dried at 80 ℃ for 12 hours.
(2) Preparation of CoFe @3D-NCNT
Placing the prepared purple CoFe-MOF powder at the downstream of a porcelain boat, placing melamine at the upstream, placing the porcelain boat in a tube furnace for calcination, wherein the calcination atmosphere is 95% argon and 5% hydrogen, the calcination temperature is 800 ℃, the temperature rise time is 176 minutes, the heat preservation time is 1 hour, and after the tube furnace is naturally cooled, obtaining the CoFe @3D-NCNT micro-nano material.
(3) Preparation of CoFe-S @3D-S-NCNT
And (2) ultrasonically dissolving 0.7g of sodium sulfide in 40mL of deionized water, transferring the deionized water to a reaction kettle, immersing the CoFe @3D-NCNT black powder synthesized in the step (2) into the solution, carrying out hydrothermal reaction for 15 hours at 120 ℃, cooling to room temperature, carrying out centrifugal washing on deionized water and ethanol for several times at the rotating speed of 6500 revolutions, and drying at 80 ℃ to obtain the final product CoFe-S @3D-S-NCNT micro-nano composite material.
The nanocomposite materials prepared in examples 2 to 3 were subjected to performance verification, the nanocomposite material prepared in example 2 had an ORR half-wave potential of 0.84V and an OER overpotential of 350mV, and the nanocomposite material prepared in example 3 had an ORR half-wave potential of 0.83V and an OER overpotential of 330mV, and as a result, it was found that the product prepared with a hydrothermal time of 10 hours had more excellent bifunctional activity.
Example 4
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO)3)2·6H2O) and 0.06g of ferrous chloride tetrahydrate (FeCl)2·4H2O) was dissolved in 40mL of deionized water, and the resulting solution was mixed with water1.32g of 2-methylimidazole (2-MIM) in 40mL of deionized water are mixed and aged for 4 hours at room temperature, and the purple solution is deionized water and ethanol are centrifugally washed for several times at a rotation speed of 6500 revolutions and dried for 12 hours at 80 ℃.
(2) Preparation of CoFe @3D-NCNT
Placing the prepared purple CoFe-MOF powder at the downstream of a porcelain boat, placing melamine at the upstream, placing the porcelain boat in a tube furnace for calcination, wherein the calcination atmosphere is 95% argon and 5% hydrogen, the calcination temperature is 700 ℃, the temperature rise time is 176 minutes, the heat preservation time is 1 hour, and after the tube furnace is naturally cooled, obtaining the CoFe @3D-NCNT nano material.
(3) Preparation of CoFe-S @3D-S-NCNT
And (2) ultrasonically dissolving 0.7g of sodium sulfide in 40mL of deionized water, transferring the deionized water to a reaction kettle, immersing the CoFe @3D-NCNT black powder synthesized in the step (2) into the solution, carrying out hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, carrying out centrifugal washing on deionized water and ethanol for several times at the rotating speed of 6500 revolutions, and drying at 80 ℃ to obtain the final product CoFe-S @3D-S-NCNT nano composite material.
Example 5
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO)3)2·6H2O) and 0.06g of ferrous chloride tetrahydrate (FeCl)2·4H2O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, deionized water and ethanol were subjected to centrifugal washing several times at 6500 rpm for a purple solution, and dried at 80 ℃ for 12 hours.
(2) Preparation of CoFe @3D-NCNT
Placing the prepared purple CoFe-MOF powder at the downstream of a porcelain boat, placing melamine at the upstream, placing the porcelain boat in a tube furnace for calcination, wherein the calcination atmosphere is 95% argon and 5% hydrogen, the calcination temperature is 900 ℃, the temperature rise time is 176 minutes, the heat preservation time is 1 hour, and after the tube furnace is naturally cooled, obtaining the CoFe @3D-NCNT nano material.
(3) Preparation of CoFe-S @3D-S-NCNT
And (2) ultrasonically dissolving 0.7g of sodium sulfide in 40mL of deionized water, transferring the deionized water to a reaction kettle, immersing the CoFe @3D-NCNT black powder synthesized in the step (2) into the solution, carrying out hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, carrying out centrifugal washing on deionized water and ethanol for several times at the rotating speed of 6500 revolutions, and drying at 80 ℃ to obtain the final product CoFe-S @3D-S-NCNT nano composite material.
Example 6
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO)3)2·6H2O) and 0.06g of ferrous chloride tetrahydrate (FeCl)2·4H2O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, deionized water and ethanol were subjected to centrifugal washing several times at 6500 rpm for a purple solution, and dried at 80 ℃ for 12 hours.
(2) Preparation of CoFe @3D-NCNT
Placing the prepared purple powder of the CoFe-MOF at the downstream of a porcelain boat, placing melamine at the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is argon, the calcination temperature is 800 ℃, the temperature rise time is 176 minutes, the heat preservation time is 1 hour, and obtaining the CoFe @3D-NCNT nano material after the tube furnace naturally cools down.
(3) Preparation of CoFe-S @3D-S-NCNT
And (2) ultrasonically dissolving 0.7g of sodium sulfide in 40mL of deionized water, transferring the deionized water to a reaction kettle, immersing the CoFe @3D-NCNT black powder synthesized in the step (2) into the solution, carrying out hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, carrying out centrifugal washing on deionized water and ethanol for several times at the rotating speed of 6500 revolutions, and drying at 80 ℃ to obtain the final product CoFe-S @3D-S-NCNT nano composite material.
The same experiment verification as that of the example 1 shows that when the material prepared in the example 2 is used for preparing the electrode of the rechargeable zinc-air battery, the peak power density is 360 mW/cm2The cycling stability is more than 180 weeks; when the material prepared in example 3 is used for preparing the electrode of the rechargeable zinc-air battery, the peak power density is 380 mW/cm2The cycle stability is more than 150 weeks; when the material prepared in example 4 is used for preparing the electrode of the rechargeable zinc-air battery, the peak power density is 240 mW/cm2The cycling stability is more than 110 weeks; when the material prepared in example 5 is used for preparing the electrode of the rechargeable zinc-air battery, the peak power density is 240 mW/cm2The cycle stability is over 140 weeks; when the material prepared in example 6 is used for preparing the electrode of the rechargeable zinc-air battery, the peak power density is 120 mW/cm2The cycling stability is more than 100 weeks, and the materials prepared in examples 2-6 have better power density and better cycling stability when used for preparing the electrode of the rechargeable zinc-air battery.
Comparative example 1
The difference from example 1 is that no iron element was introduced in step (1), but only pure Co-MOF.
The prepared material is subjected to catalytic activity test and discharge polarization test, the ORR half-wave potential is 0.82V, the OER overpotential is 390mV, and the peak power density is 375 mW/cm2The results show that: after annealing and sulfurizing, the electrochemical performance of the pure Co-MOF is reduced.
Comparative example 2
The difference from example 1 is that the calcination process in step (2) is carried out without introducing melamine as a carbon source and the temperature is raised to 800 ℃ and then the holding time is 1 hour.
The prepared material is subjected to morphology, circulation stability, catalytic activity test and discharge polarization test, the ORR half-wave potential is 0.73V, the OER overpotential is 430mV, and the peak power density is 140 mW/cm2The cycle stability was 85 weeks, and the results showed: after melamine is not introduced as a carbon source and calcined, carbon nanotubes cannot grow in situ on the CoFe-MOF nano-sheets, so that the electrochemical performance is reduced, and the power density of the assembled quasi-solid zinc-air battery is poor.
Comparative example 3
The difference from example 1 is that step (3) is omitted.
The prepared material is subjected to catalytic activity test, cycle stability and discharge polarization test, the ORR half-wave potential is 0.78V, the OER overpotential is 370mV, and the peak power density is 340 mW/cm2The cycling stability was 100 weeks, and the results showed: non-vulcanized product, dual-function activityAnd the power density of the assembled rechargeable zinc-air battery is lower.
The result shows that the CoFe-S @3D-S-NCNT nanocomposite prepared by the method has high bifunctional catalytic activity, and the material has excellent power density and good cycle stability when being applied to a quasi-solid zinc-air battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

  1. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material is characterized by comprising the following steps of:
    (1) preparation of CoFe-MOF nanosheets: aging a mixed solution composed of cobalt salt, a ferric salt aqueous solution and a 2-methylimidazole aqueous solution, and then centrifugally cleaning and drying to obtain CoFe-MOF;
    (2) preparation of CoFe @ 3D-NCNT: annealing CoFe-MOF micro-nano sheets in a mixed atmosphere of argon and hydrogen in the presence of melamine to obtain a CoFe @3D-NCNT micro-nano material;
    (3) preparation of CoFe-S @ 3D-S-NCNT: and immersing the CoFe @3D-NCNT micro-nano material in a sodium sulfide solution for hydrothermal reaction, and washing and drying to obtain CoFe-S @ 3D-S-NCNT.
  2. 2. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein in the step (1), the cobalt salt comprises cobalt nitrate, cobalt chloride or cobalt acetate, and the concentration of the aqueous solution is 5-20 g/L; the ferric salt comprises ferric chloride, ferric nitrate or ferric acetate, and the concentration of the aqueous solution of the ferric salt is 0.5-2 g/L; the concentration of the 2-methylimidazole aqueous solution is 20-50 g/L.
  3. 3. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein in the mixed atmosphere of argon and hydrogen, the content of argon is 85-95% and the content of hydrogen is 5-15%.
  4. 4. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein in the mixed atmosphere of argon and hydrogen, the content of argon is 95% and the content of hydrogen is 5%.
  5. 5. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein the mass ratio of melamine to cobalt salt and iron salt is 0.05-0.2: 5-20: 5-20.
  6. 6. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein in the step (2), CoFe-MOF nanosheets are placed at the downstream of a tube type atmosphere furnace tube, melamine is placed at the upstream of the tube type atmosphere furnace tube, the tube type atmosphere furnace tube is placed in an argon and hydrogen atmosphere, the temperature is raised to 700-900 ℃ within 0.5-2 hours, heat preservation is continued for 1-2 hours, and after natural cooling, CoFe @3D-NCNT is obtained.
  7. 7. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein in the step (3): the concentration of the sodium sulfide solution is 10-20 g/L.
  8. 8. The preparation method of the CoFe-S @3D-S-NCNT micro-nano composite material according to claim 1, wherein in the step (3): the hydrothermal reaction temperature is 100 ℃ and 140 ℃, and the hydrothermal reaction time is 6-18 h.
  9. 9. A quasi-solid chargeable zinc-air battery air electrode containing the CoFe-S @3D-S-NCNT micro/nano composite material of any one of claims 1 to 8, wherein ethanol and naphthol solution are added into the CoFe-S @3D-S-NCNT micro/nano composite material for ultrasonic dispersion to obtain catalyst ink, the catalyst ink is dripped onto carbon paper or carbon cloth, and drying is carried out to obtain the quasi-solid chargeable zinc-air battery air electrode.
  10. 10. A quasi-solid zinc-air battery comprising an air electrode prepared from the CoFe-S @3D-S-NCNT micro-nanocomposite material according to any one of claims 1 to 8 as a cathode electrode; any one of zinc electrodes deposited in situ by a zinc sheet, a zinc foil, a zinc strip, carbon cloth or carbon paper is taken as an anode electrode; and any one of PVA electrolyte, PaNa electrolyte, biological cellulose membrane electrolyte and acrylic acid gel electrolyte is used as the gel electrolyte to be assembled to obtain the quasi-solid zinc-air battery.
CN202210150723.4A 2022-02-18 2022-02-18 Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery Active CN114614027B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210150723.4A CN114614027B (en) 2022-02-18 2022-02-18 Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210150723.4A CN114614027B (en) 2022-02-18 2022-02-18 Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery

Publications (2)

Publication Number Publication Date
CN114614027A true CN114614027A (en) 2022-06-10
CN114614027B CN114614027B (en) 2024-03-15

Family

ID=81858547

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210150723.4A Active CN114614027B (en) 2022-02-18 2022-02-18 Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery

Country Status (1)

Country Link
CN (1) CN114614027B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023240891A1 (en) * 2022-06-14 2023-12-21 浙江大学 Cyano group-modified zr-fe mof, preparation method therefor, and zinc-based flow battery zinc negative electrode material

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108365230A (en) * 2018-01-04 2018-08-03 中国科学院大学 A kind of universality preparation method and application for the air electrode that active site is combined with electrode structure
CN109559898A (en) * 2018-11-09 2019-04-02 江苏大学 A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load
CN109585856A (en) * 2018-11-07 2019-04-05 三峡大学 A kind of preparation method of difunctional cobalt sulfide and sulphur, nitrogen-doped carbon In-situ reaction electrode
CN110350206A (en) * 2018-08-27 2019-10-18 哈尔滨工业大学 Vertical graphene-supported carbon nano-tube combination electrode material and preparation method thereof and the application in all solid state zinc-air battery
CN110518261A (en) * 2019-08-02 2019-11-29 三峡大学 The preparation method of nitrogen-phosphor codoping carbon nanotube cladding ferro-cobalt bimetallic alloy original position electrode
CN111082079A (en) * 2019-12-30 2020-04-28 上海交通大学 Bifunctional oxygen electrocatalyst material and preparation method and application thereof
CN111490257A (en) * 2020-04-03 2020-08-04 三峡大学 Preparation method of bifunctional Co-N-C electrocatalyst
CN111668453A (en) * 2020-07-14 2020-09-15 合肥工业大学 Flexible self-supporting positive electrode material and preparation method and application thereof
CN111744502A (en) * 2020-07-07 2020-10-09 东华大学 Magnesium-doped cobalt disulfide composite carbon nanotube material, preparation method and application
CN112090441A (en) * 2020-09-28 2020-12-18 浙江师范大学 Preparation method, product and application of cobalt-based carbon nano material
CN113113615A (en) * 2021-04-08 2021-07-13 浙江师范大学 NiFe-LDH/Co-CNTs nano composite material and preparation method and application thereof
CN113381030A (en) * 2021-05-13 2021-09-10 三峡大学 Co9S8Preparation method of-Co @ NCNTs composite electrode
CN113410475A (en) * 2020-03-17 2021-09-17 中国科学院化学研究所 Graphitized carbon layer coated transition metal nanoparticle catalyst and preparation method thereof
CN113540477A (en) * 2021-07-12 2021-10-22 浙江师范大学 Preparation method and application of multi-component carbon nano material
CN113675402A (en) * 2021-07-20 2021-11-19 华南理工大学 Metal-nitrogen doped porous carbon material and preparation method and application thereof
CN113764689A (en) * 2021-08-30 2021-12-07 江苏大学 Porous graphene supported cobalt-iron sulfide catalyst, and preparation method and application thereof
CN113936928A (en) * 2021-09-30 2022-01-14 江苏欧力特能源科技有限公司 Preparation method of composite electrode of Co-Ni-S composite sphere interconnection structure derived from CNTs interpenetrating MOF
US20220037675A1 (en) * 2020-08-03 2022-02-03 Nanyang Technological University Catalyst for rechargeable energy storage devices and method for making the same

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108365230A (en) * 2018-01-04 2018-08-03 中国科学院大学 A kind of universality preparation method and application for the air electrode that active site is combined with electrode structure
CN110350206A (en) * 2018-08-27 2019-10-18 哈尔滨工业大学 Vertical graphene-supported carbon nano-tube combination electrode material and preparation method thereof and the application in all solid state zinc-air battery
CN109585856A (en) * 2018-11-07 2019-04-05 三峡大学 A kind of preparation method of difunctional cobalt sulfide and sulphur, nitrogen-doped carbon In-situ reaction electrode
CN109559898A (en) * 2018-11-09 2019-04-02 江苏大学 A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load
CN110518261A (en) * 2019-08-02 2019-11-29 三峡大学 The preparation method of nitrogen-phosphor codoping carbon nanotube cladding ferro-cobalt bimetallic alloy original position electrode
CN111082079A (en) * 2019-12-30 2020-04-28 上海交通大学 Bifunctional oxygen electrocatalyst material and preparation method and application thereof
CN113410475A (en) * 2020-03-17 2021-09-17 中国科学院化学研究所 Graphitized carbon layer coated transition metal nanoparticle catalyst and preparation method thereof
CN111490257A (en) * 2020-04-03 2020-08-04 三峡大学 Preparation method of bifunctional Co-N-C electrocatalyst
CN111744502A (en) * 2020-07-07 2020-10-09 东华大学 Magnesium-doped cobalt disulfide composite carbon nanotube material, preparation method and application
CN111668453A (en) * 2020-07-14 2020-09-15 合肥工业大学 Flexible self-supporting positive electrode material and preparation method and application thereof
US20220037675A1 (en) * 2020-08-03 2022-02-03 Nanyang Technological University Catalyst for rechargeable energy storage devices and method for making the same
CN112090441A (en) * 2020-09-28 2020-12-18 浙江师范大学 Preparation method, product and application of cobalt-based carbon nano material
CN113113615A (en) * 2021-04-08 2021-07-13 浙江师范大学 NiFe-LDH/Co-CNTs nano composite material and preparation method and application thereof
CN113381030A (en) * 2021-05-13 2021-09-10 三峡大学 Co9S8Preparation method of-Co @ NCNTs composite electrode
CN113540477A (en) * 2021-07-12 2021-10-22 浙江师范大学 Preparation method and application of multi-component carbon nano material
CN113675402A (en) * 2021-07-20 2021-11-19 华南理工大学 Metal-nitrogen doped porous carbon material and preparation method and application thereof
CN113764689A (en) * 2021-08-30 2021-12-07 江苏大学 Porous graphene supported cobalt-iron sulfide catalyst, and preparation method and application thereof
CN113936928A (en) * 2021-09-30 2022-01-14 江苏欧力特能源科技有限公司 Preparation method of composite electrode of Co-Ni-S composite sphere interconnection structure derived from CNTs interpenetrating MOF

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUIJUN LIA ET AL.: "S, N co-doped carbon nanotubes coupled with CoFe nanoparticles as an efficient bifunctional ORR/OER electrocatalyst for rechargeable Zn-air batteries", CHEMICAL ENGINEERING JOURNAL, vol. 429, pages 1 - 8 *
ZHENXI SHANG ET AL.: "CoFe nanoalloy particles encapsulated in nitrogen-doped carbon layers as bifunctional oxygen catalyst derived from a Prussian blue analogue", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 740, pages 743 - 753, XP085413573, DOI: 10.1016/j.jallcom.2018.01.019 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023240891A1 (en) * 2022-06-14 2023-12-21 浙江大学 Cyano group-modified zr-fe mof, preparation method therefor, and zinc-based flow battery zinc negative electrode material

Also Published As

Publication number Publication date
CN114614027B (en) 2024-03-15

Similar Documents

Publication Publication Date Title
Wu et al. Role of flower-like ultrathin Co 3 O 4 nanosheets in water splitting and non-aqueous Li–O 2 batteries
CN105552393B (en) A kind of alkaline water system metal-air batteries bifunctional catalyst and preparation method thereof
CN110838588B (en) Rechargeable zinc-air battery bifunctional catalyst and preparation method and application thereof
CN108172799A (en) A kind of tertiary cathode material of nucleocapsid structure lithium ion battery and preparation method thereof
CN113388847B (en) Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof
Xu et al. Hollow bimetallic selenide derived from a hierarchical MOF-based Prussian blue analogue for urea electrolysis
CN107159297A (en) A kind of difunctional VPO catalysts cobalt/cobaltosic oxide/nitrogen carbon composite and preparation method thereof
CN106876828B (en) A kind of preparation method of lithium-air battery non-carbon anode, lithium-air battery
CN110451489B (en) Cobalt nitride embedded porous nitrogen-doped graphene material, and preparation method and application thereof
CN104157858B (en) Classifying porous ferroso-ferric oxide/graphene nano line and its preparation method and application
Martínez-Lázaro et al. Microfluidic water splitting cell using 3D NiFe2O4 hollow spheres
Wang et al. Elaborately tailored NiCo 2 O 4 for highly efficient overall water splitting and urea electrolysis
CN111001428A (en) Metal-free carbon-based electrocatalyst, preparation method and application
Li et al. Almond shell derived porous carbon for a high-performance anode of microbial fuel cells
CN111634954B (en) Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof
CN106807378A (en) A kind of hexagon nickel cobalt oxide oxygen-separating catalyst and its preparation method and application
CN111013631A (en) Novel three-dimensional grading porous composite material, preparation method and application thereof
CN109148859A (en) A kind of preparation method of double carbon-coating coated manganese oxide composite materials
CN113512737B (en) Nickel hydroxide electrocatalyst, preparation method, electrochemical activation method and application thereof
CN112886029B (en) Preparation and application of bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier
CN104201396B (en) Carbon electrode modified by cerium-zirconium oxide, preparation method and flow battery
CN109837559A (en) A kind of FeOOH-nickel-ferric spinel integrated electrode preparation method of hydro-thermal auxiliary
CN111933961A (en) Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof
CN114628696B (en) Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst
CN113540477A (en) Preparation method and application of multi-component carbon nano material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant