CN110052601B - Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating - Google Patents

Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating Download PDF

Info

Publication number
CN110052601B
CN110052601B CN201910357763.4A CN201910357763A CN110052601B CN 110052601 B CN110052601 B CN 110052601B CN 201910357763 A CN201910357763 A CN 201910357763A CN 110052601 B CN110052601 B CN 110052601B
Authority
CN
China
Prior art keywords
hydrogen storage
storage alloy
graphene
type hydrogen
silicon dioxide
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.)
Active
Application number
CN201910357763.4A
Other languages
Chinese (zh)
Other versions
CN110052601A (en
Inventor
张虎
钟喜春
龙克文
刘仲武
余红雅
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.)
Sanqiaohui Foshan New Material Co ltd
Original Assignee
Sanqiaohui Foshan New Material Co ltd
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 Sanqiaohui Foshan New Material Co ltd filed Critical Sanqiaohui Foshan New Material Co ltd
Priority to CN201910357763.4A priority Critical patent/CN110052601B/en
Publication of CN110052601A publication Critical patent/CN110052601A/en
Application granted granted Critical
Publication of CN110052601B publication Critical patent/CN110052601B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • H01M4/383—Hydrogen absorbing alloys
    • H01M4/385—Hydrogen absorbing alloys of the type LaNi5
    • 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)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Electrochemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for modifying AB5 type hydrogen storage alloy by silicon dioxide-graphene composite coating, which comprises the steps of preparing AB5 type hydrogen storage alloy powder by a vacuum induction melting method, plating by graphene-copper sulfate composite plating solution, and carrying out surface coating treatment on graphene-silicon dioxide composite sol to obtain the modified AB5 type hydrogen storage alloy by the silicon dioxide-graphene composite coating. The production method of the invention can play a role in surface coating protection of the hydrogen storage alloy and greatly improve the durability of the hydrogen storage alloy, thereby greatly improving the cycle stability of the hydrogen storage alloy, and also can give consideration to the electrode performance of the hydrogen storage alloy, so that the hydrogen storage alloy has excellent discharge capacity and high-rate discharge performance, thereby developing products with excellent comprehensive performance.

Description

Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating
Technical Field
The invention relates to the technical field of hydrogen storage alloys, in particular to a method for modifying an AB5 type hydrogen storage alloy by silicon dioxide-graphene composite coating.
Background
With the development of economy, the consumption of petrochemical energy sources such as coal, petroleum, natural gas and the like is continuously accelerated, and meanwhile, the environmental pollution is also intensified. The hydrogen energy is a green clean energy with wide source and abundant reserves, has a plurality of excellent characteristics, and the storage of the hydrogen energy is the key to the practicability of the hydrogen energy. The hydrogen storage alloy is a high-performance hydrogen storage material, refers to an intermetallic compound which can reversibly absorb, store and release a large amount of hydrogen at a certain temperature and pressure, and is used as a key material of a Ni-MH secondary battery, and plays a key role in the performance of the battery. In order to provide a Ni-MH secondary battery with high energy density, good discharge characteristics, and cycle life, it is of great importance to develop a high-performance hydrogen storage alloy.
Among various hydrogen storage alloys researched and developed at present, AB5 type hydrogen storage alloy has higher discharge capacity, and has been widely commercialized and applied as an important production material for the negative electrode of Ni-MH secondary batteries. However, the AB5 type hydrogen storage alloy has poor oxidation resistance, pulverization resistance and corrosion resistance, and is easy to degrade during repeated charging and discharging, and the cycle stability, cycle life and other properties of the alloy still need to be improved. The hydrogen storage alloy powder is subjected to surface coating treatment to form a protective layer on the surface, so that the durability of the alloy powder can be improved, and the method is an effective solution for improving the cycle stability of the alloy powder. For example, plating copper on the surface of the hydrogen storage alloy can act as a corrosion resistant protective layer, improving the cycling stability of the hydrogen storage alloy. However, since the copper plating layer is not stable enough in air, the discharge performance is significantly reduced after storage in air; and the copper plating process has higher requirement, and the rough copper plating layer can not play good corrosion resistance and electric conduction effects and can also reduce the discharge stability. In addition, the single surface-coated modified hydrogen storage alloy has great limitation, and not only the improvement of the cycle stability is limited, but also the electrochemical properties such as the discharge capacity, the high-rate discharge performance and the like of the hydrogen storage alloy are difficult to be comprehensively improved. Therefore, how to comprehensively improve the comprehensive performance of the hydrogen storage alloy is an important issue at present.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a method for modifying AB5 type hydrogen storage alloy by silicon dioxide-graphene composite coating, which can play a role in surface coating protection of the hydrogen storage alloy and greatly improve the durability of the hydrogen storage alloy, thereby greatly improving the cycle stability of the hydrogen storage alloy, and also can give consideration to the electrode performance of the hydrogen storage alloy, so that the hydrogen storage alloy has excellent discharge capacity and high-rate discharge performance, and a product with excellent comprehensive performance is developed.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating comprises the following steps:
(1) weighing raw material metal powder with the purity of more than 99 percent according to the chemical composition of the AB5 type hydrogen storage alloy, preparing the AB5 type hydrogen storage alloy by adopting a vacuum induction melting method under the protection of inert gas, and obtaining AB5 type hydrogen storage alloy powder by mechanical crushing, ball milling and screening;
(2) placing the AB5 type hydrogen storage alloy powder in the step (1) into graphene-copper sulfate composite plating solution for plating, filtering after plating, washing with deionized water and ethanol in sequence, and drying at 30-60 ℃ for 2-4h to obtain primary coated AB5 type hydrogen storage alloy powder;
(3) and (3) mixing the primary coated AB5 type hydrogen storage alloy powder obtained in the step (2) with the graphene-silicon dioxide composite sol, uniformly stirring, standing and aging for 24-48h, adding into a ball mill, placing the ball mill into a microwave generating device for microwave-assisted ball milling treatment, taking out, adding into a mixer for heating and mixing treatment, finally preserving heat at 200 ℃ for 300 ℃ for 2-4h, and cooling to obtain the silicon dioxide-graphene composite coated modified AB5 type hydrogen storage alloy.
Preferably, the AB5 type hydrogen storage alloy has a chemical composition of LaNi3.6Co0.7Mn0.4Al0.3。
Preferably, the AB5 type hydrogen storage alloy powder is 200-300 mesh.
Preferably, the graphene-copper sulfate composite plating solution is prepared from the following raw materials in parts by weight: 1-5 parts of copper sulfate, 0.1-1 part of graphene, 0.1-0.5 part of EDTA, and 1000 parts of deionized water 800-; the preparation method comprises the following steps: and sequentially dissolving EDTA and copper sulfate in deionized water, and then adding graphene to perform ultrasonic dispersion uniformly to obtain the graphene-copper sulfate composite plating solution.
Preferably, the mass ratio of the AB5 type hydrogen storage alloy powder to the graphene-copper sulfate composite plating solution is (0.5-1): (5-10).
Preferably, the plating is carried out under the ultrasonic treatment condition of 30-40kHz and the temperature is 20-25 ℃, and the plating time is 1-2 min.
Preferably, the graphene-silica composite sol is prepared from the following raw materials in parts by weight: 1-2 parts of ethyl orthosilicate, 0.05-0.1 part of graphene, 4-8 parts of ethanol and 4-8 parts of hydrochloric acid aqueous solution with the concentration of 0.05-0.1 mol/L; the preparation method comprises the following steps: adding ethyl orthosilicate into ethanol, uniformly mixing, adding graphene, performing ultrasonic dispersion, adding a hydrochloric acid aqueous solution, and stirring for 0.5-1h to obtain the graphene-silicon dioxide composite sol.
Preferably, the mass ratio of the primary coated AB5 type hydrogen storage alloy powder to the graphene-silica composite sol is (1-2): (5-10).
Preferably, the microwave-assisted ball milling treatment comprises the following specific steps: ball milling is carried out for 1-3min under the condition of 400-600W microwave treatment, then the microwave treatment is stopped, the ball milling is continued for 3-5min, and the steps are repeated for 2-5 times.
Preferably, the specific flow of the heating and mixing treatment is as follows: firstly, mixing materials for one time under the conditions that the rotating speed is 200-400r/min and the temperature is 40-60 ℃, wherein the time for mixing materials for one time is 5-10 min; after the first mixing, the second mixing is carried out at the rotation speed of 800-.
The invention has the advantages that:
according to the invention, a graphene-copper primary coating layer is formed on the surface of AB5 type hydrogen storage alloy powder by using a chemical composite plating method, copper in the coating layer has high catalytic activity and strong capacities of adsorbing electrons and transporting electrons, and can rapidly provide electrons reaching the surface of an electrode, promote the hydrogen storage reaction and improve the discharge capacity of the hydrogen storage alloy; the graphene in the coating layer has excellent conductivity, and can reduce the resistance of the hydrogen storage alloy electrode, so that the high-rate discharge performance is improved; by introducing the chemical composite plating method of the graphene into the plating solution, the chemical composite plating method not only plays a role in refining grains in the formation process of the plating layer, so that the structure of the copper plating layer is more compact, the surface is smoother, the quality of the copper plating layer is improved, the corrosion resistance and the air oxidation resistance of the copper plating layer are further improved, the circulation stability of the hydrogen storage alloy is improved, but also the combination effect of the graphene and the surface of the hydrogen storage alloy can be enhanced, the graphene is uniformly distributed in a coating layer, and the high-rate discharge performance of the battery is effectively improved.
In addition, a silicon dioxide-graphene secondary coating layer is formed on the surface of the primary coating layer by utilizing a sol-gel method, on one hand, the compact coating layer of the graphene-silicon dioxide can effectively inhibit the oxidation and pulverization of the composite coating layer, so that the hydrogen storage alloy is endowed with more excellent cycle stability, on the other hand, the surface coating of the silicon dioxide can cause the discharge performance such as the discharge capacity of the hydrogen storage alloy to be reduced, and the graphene can improve the discharge capacity and high-rate discharge performance of the hydrogen storage alloy, so that the adverse effect of the coating on the discharge performance is reduced, and the requirement of the discharge performance is met on the premise of further improving the cycle stability of the hydrogen storage alloy.
According to the invention, after the AB5 type hydrogen storage alloy powder coated once is mixed with the graphene-silicon dioxide composite sol, microwave-assisted ball milling treatment is firstly adopted, and then staged heating and mixing treatment is carried out, so that the composite sol is fully contacted with the alloy powder, and the secondary coating layer is uniformly heated in the process of forming the secondary coating layer, thereby improving the compactness and uniformity of the secondary coating layer and the binding force between the secondary coating layer and the primary coating layer, and ensuring that the coated hydrogen storage alloy has good surface quality, discharge performance and cycle stability.
In conclusion, the invention not only can greatly improve the cycle stability of the hydrogen storage alloy, but also can improve the discharge capacity and the high-rate discharge performance of the hydrogen storage alloy, thereby achieving the purpose of comprehensively improving the discharge capacity, the high-rate discharge performance and the cycle stability of the hydrogen storage alloy.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1
A method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating comprises the following steps:
(1) according to the chemical composition of LaNi3.6Co0.7Mn0.4Al0.3Weighing AB5 type hydrogen storage alloy raw material metal powder with the purity of more than 99 percent, preparing AB5 type hydrogen storage alloy by adopting a vacuum induction melting method under the protection of inert gas, and obtaining AB5 type hydrogen storage alloy powder with 200 meshes through mechanical crushing, ball milling and screening;
(2) placing the AB5 type hydrogen storage alloy powder in the step (1) into a graphene-copper sulfate composite plating solution, plating for 1min under the ultrasonic treatment conditions of 20 ℃ and 30kHz, filtering after plating, washing with deionized water and ethanol in sequence, and drying at 30 ℃ for 2h to obtain a primary coated AB5 type hydrogen storage alloy powder, wherein the graphene-copper sulfate composite plating solution is prepared from the following raw materials in parts by weight: 1 part of copper sulfate, 0.1 part of graphene, 0.1 part of EDTA and 800 parts of deionized water, and the preparation method comprises the following steps: sequentially dissolving EDTA and copper sulfate in deionized water, adding graphene, and performing ultrasonic dispersion to obtain a graphene-copper sulfate composite plating solution, wherein the mass ratio of the AB5 type hydrogen storage alloy powder to the graphene-copper sulfate composite plating solution is 0.5: 5;
(3) mixing the primary coated AB5 type hydrogen storage alloy powder obtained in the step (2) with graphene-silicon dioxide composite sol, uniformly stirring, standing and aging for 24h, adding into a ball mill, placing the ball mill into a microwave generating device, performing ball milling for 1min under the condition of 400W microwave treatment, stopping the microwave treatment, continuing ball milling for 3min, repeating the steps for 2 times, taking out, adding into a mixer, and performing primary mixing for 5min under the conditions that the rotating speed is 200r/min and the temperature is 40 ℃; after the first mixing, performing secondary mixing at the rotation speed of 800r/min and the temperature of 85 ℃, wherein the time for secondary mixing is 10min, and finally, keeping the temperature at 200 ℃ for 2h, and cooling to obtain the silica-graphene composite coated modified AB5 type hydrogen storage alloy, wherein the graphene-silica composite sol is prepared from the following raw materials in parts by weight: 1 part of ethyl orthosilicate, 0.05 part of graphene, 4 parts of ethanol and 4 parts of hydrochloric acid aqueous solution with the concentration of 0.05mol/L, and the preparation method comprises the following steps: adding ethyl orthosilicate into ethanol, uniformly mixing, adding graphene, performing ultrasonic dispersion, adding a hydrochloric acid aqueous solution, stirring for 0.5h to obtain graphene-silicon dioxide composite sol, wherein the mass ratio of the AB5 type hydrogen storage alloy powder coated once to the graphene-silicon dioxide composite sol is 1: 5.
example 2
A method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating comprises the following steps:
(1) push buttonChemical composition of LaNi3.6Co0.7Mn0.4Al0.3Weighing AB5 type hydrogen storage alloy raw material metal powder with the purity of more than 99 percent, preparing AB5 type hydrogen storage alloy by adopting a vacuum induction melting method under the protection of inert gas, and obtaining 300-mesh AB5 type hydrogen storage alloy powder by mechanical crushing, ball milling and screening;
(2) placing the AB5 type hydrogen storage alloy powder in the step (1) into a graphene-copper sulfate composite plating solution, plating for 2min under the ultrasonic treatment condition of 25 ℃ and 40kHz, filtering after plating, washing with deionized water and ethanol in sequence, and drying at 60 ℃ for 4h to obtain the AB5 type hydrogen storage alloy powder coated once, wherein the graphene-copper sulfate composite plating solution is prepared from the following raw materials in parts by weight: 5 parts of copper sulfate, 1 part of graphene, 0.5 part of EDTA and 1000 parts of deionized water, and the preparation method comprises the following steps: sequentially dissolving EDTA and copper sulfate in deionized water, adding graphene, and performing ultrasonic dispersion to obtain a graphene-copper sulfate composite plating solution, wherein the mass ratio of the AB5 type hydrogen storage alloy powder to the graphene-copper sulfate composite plating solution is 0.5: 10;
(3) mixing the primary coated AB5 type hydrogen storage alloy powder obtained in the step (2) with graphene-silicon dioxide composite sol, uniformly stirring, standing and aging for 48h, adding into a ball mill, placing the ball mill into a microwave generating device, performing ball milling for 3min under the condition of 600W microwave treatment, stopping the microwave treatment, continuing ball milling for 5min, repeating the steps for 5 times, taking out, adding into a mixer, and performing primary mixing under the conditions that the rotating speed is 400r/min and the temperature is 60 ℃, wherein the primary mixing time is 10 min; after the first mixing, performing secondary mixing at the rotation speed of 1200r/min and the temperature of 95 ℃ for 15min, and finally, preserving heat at 300 ℃ for 4h, and cooling to obtain the silica-graphene composite coated modified AB5 type hydrogen storage alloy, wherein the graphene-silica composite sol is prepared from the following raw materials in parts by weight: 2 parts of ethyl orthosilicate, 0.1 part of graphene, 8 parts of ethanol and 8 parts of hydrochloric acid aqueous solution with the concentration of 0.1mol/L, and the preparation method comprises the following steps: adding ethyl orthosilicate into ethanol, uniformly mixing, adding graphene, performing ultrasonic dispersion, adding a hydrochloric acid aqueous solution, stirring for 1 hour to obtain graphene-silicon dioxide composite sol, and coating AB5 type hydrogen storage alloy powder once, wherein the mass ratio of the graphene-silicon dioxide composite sol to the AB5 type hydrogen storage alloy powder is 1: 10.
example 3
A method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating comprises the following steps:
(1) according to the chemical composition of LaNi3.6Co0.7Mn0.4Al0.3Weighing AB5 type hydrogen storage alloy raw material metal powder with the purity of more than 99 percent, preparing AB5 type hydrogen storage alloy by adopting a vacuum induction melting method under the protection of inert gas, and obtaining 250-mesh AB5 type hydrogen storage alloy powder by mechanical crushing, ball milling and screening;
(2) placing the AB5 type hydrogen storage alloy powder in the step (1) into a graphene-copper sulfate composite plating solution, plating for 1.5min under the ultrasonic treatment conditions of 24 ℃ and 35kHz, filtering after plating, washing with deionized water and ethanol in sequence, and drying at 40 ℃ for 3h to obtain the one-time coated AB5 type hydrogen storage alloy powder, wherein the graphene-copper sulfate composite plating solution is prepared from the following raw materials in parts by weight: 2 parts of copper sulfate, 0.5 part of graphene, 0.3 part of EDTA and 900 parts of deionized water, wherein the preparation method comprises the following steps: sequentially dissolving EDTA and copper sulfate in deionized water, adding graphene, and performing ultrasonic dispersion to obtain a graphene-copper sulfate composite plating solution, wherein the mass ratio of the AB5 type hydrogen storage alloy powder to the graphene-copper sulfate composite plating solution is 0.8: 5;
(3) mixing the primary coated AB5 type hydrogen storage alloy powder obtained in the step (2) with graphene-silicon dioxide composite sol, uniformly stirring, standing and aging for 36h, adding into a ball mill, placing the ball mill into a microwave generating device, performing ball milling for 2min before 500W microwave treatment, stopping microwave treatment, continuing ball milling for 4min, repeating the steps for 3 times, taking out, adding into a mixer, and performing primary mixing for 6min before the rotation speed is 300r/min and the temperature is 50 ℃; after the first mixing, performing secondary mixing at the rotation speed of 1000r/min and the temperature of 90 ℃ for 12min, and finally, preserving heat at 250 ℃ for 3h, and cooling to obtain the silica-graphene composite coated modified AB5 type hydrogen storage alloy, wherein the graphene-silica composite sol is prepared from the following raw materials in parts by weight: 1.5 parts of ethyl orthosilicate, 0.08 part of graphene, 6 parts of ethanol and 8 parts of hydrochloric acid aqueous solution with the concentration of 0.06mol/L, and the preparation method comprises the following steps: adding ethyl orthosilicate into ethanol, uniformly mixing, adding graphene, performing ultrasonic dispersion, adding a hydrochloric acid aqueous solution, stirring for 0.6h to obtain graphene-silicon dioxide composite sol, wherein the mass ratio of the AB5 type hydrogen storage alloy powder coated once to the graphene-silicon dioxide composite sol is 1.5: 5.
comparative example 1
According to the chemical composition of LaNi3.6Co0.7Mn0.4Al0.3Weighing AB5 type hydrogen storage alloy raw material metal powder with the purity of more than 99 percent, preparing AB5 type hydrogen storage alloy by a vacuum induction melting method under the protection of inert gas, and obtaining AB5 type hydrogen storage alloy powder with 200 meshes through mechanical crushing, ball milling and screening.
A certain amount of samples prepared in the above examples 1-3 and comparative example 1 are respectively taken, uniformly mixed with the nickel carbonyl powder according to the proportion of 1:4, and then pressed into a hydrogen storage alloy electrode with the diameter of 20mm by a tablet press under the pressure of 20MPa, the positive electrode is a sintered NiOH2/NiOOH electrode, the electrolyte is 6mol/L KOH aqueous solution, the diaphragm is nylon non-woven fabric, the environmental temperature is kept at 25 +/-1 ℃, and the test results of discharge capacity, high rate and cycle life are shown in the following table:
Figure BDA0002045951530000061

Claims (9)

1. a method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating is characterized by comprising the following steps:
(1) weighing raw material metal powder with the purity of more than 99 percent according to the chemical composition of the AB5 type hydrogen storage alloy, preparing the AB5 type hydrogen storage alloy by adopting a vacuum induction melting method under the protection of inert gas, and obtaining AB5 type hydrogen storage alloy powder by mechanical crushing, ball milling and screening;
(2) placing the AB5 type hydrogen storage alloy powder in the step (1) into graphene-copper sulfate composite plating solution for plating, filtering after plating, washing with deionized water and ethanol in sequence, and drying at 30-60 ℃ for 2-4h to obtain primary coated AB5 type hydrogen storage alloy powder;
(3) mixing the primary coated AB5 type hydrogen storage alloy powder obtained in the step (2) with graphene-silicon dioxide composite sol, uniformly stirring, standing and aging for 24-48h, adding into a ball mill, placing the ball mill into a microwave generating device for microwave-assisted ball milling treatment, taking out, adding into a mixer for heating and mixing treatment, finally preserving heat at 200 ℃ for 2-4h, and cooling to obtain silicon dioxide-graphene composite coated modified AB5 type hydrogen storage alloy; the specific flow of the heating and mixing treatment is as follows: firstly, mixing materials for one time under the conditions that the rotating speed is 200-400r/min and the temperature is 40-60 ℃, wherein the time for mixing materials for one time is 5-10 min; after the first mixing, the second mixing is carried out at the rotation speed of 800-.
2. The method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating according to claim 1, wherein the chemical composition of the AB5 type hydrogen storage alloy is LaNi3.6Co0.7Mn0.4Al0.3。
3. The method for modifying AB5 type hydrogen storage alloy by composite coating of silica-graphene as claimed in claim 1, wherein the AB5 type hydrogen storage alloy powder is 200-300 mesh.
4. The method for preparing the modified AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating according to claim 1, wherein the graphene-copper sulfate composite plating solution is prepared from the following raw materials in parts by weight: 1-5 parts of copper sulfate, 0.1-1 part of graphene, 0.1-0.5 part of EDTA, and 1000 parts of deionized water 800-; the preparation method comprises the following steps: and sequentially dissolving EDTA and copper sulfate in deionized water, and then adding graphene to perform ultrasonic dispersion uniformly to obtain the graphene-copper sulfate composite plating solution.
5. The method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating according to claim 1, wherein the mass ratio of AB5 type hydrogen storage alloy powder to the graphene-copper sulfate composite plating solution is (0.5-1): (5-10).
6. The method for preparing the modified AB5 type hydrogen storage alloy through composite coating of silicon dioxide and graphene according to claim 1, wherein the plating is performed at 20-25 ℃ and 30-40kHz under ultrasonic treatment for 1-2 min.
7. The method for preparing the modified AB5 type hydrogen storage alloy through composite coating of silicon dioxide and graphene according to claim 1, wherein the graphene-silicon dioxide composite sol is prepared from the following raw materials in parts by weight: 1-2 parts of ethyl orthosilicate, 0.05-0.1 part of graphene, 4-8 parts of ethanol and 4-8 parts of hydrochloric acid aqueous solution with the concentration of 0.05-0.1 mol/L; the preparation method comprises the following steps: adding ethyl orthosilicate into ethanol, uniformly mixing, adding graphene, performing ultrasonic dispersion, adding a hydrochloric acid aqueous solution, and stirring for 0.5-1h to obtain the graphene-silicon dioxide composite sol.
8. The method for modifying the AB5 type hydrogen storage alloy through composite coating of silicon dioxide and graphene as claimed in claim 1, wherein the mass ratio of the AB5 type hydrogen storage alloy powder coated at one time to the graphene-silicon dioxide composite sol is (1-2): (5-10).
9. The method for preparing the modified AB5 type hydrogen storage alloy through composite coating of silica and graphene according to claim 1, wherein the microwave-assisted ball milling treatment comprises the following specific steps: ball milling is carried out for 1-3min under the condition of 400-600W microwave treatment, then the microwave treatment is stopped, the ball milling is continued for 3-5min, and the steps are repeated for 2-5 times.
CN201910357763.4A 2019-04-30 2019-04-30 Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating Active CN110052601B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910357763.4A CN110052601B (en) 2019-04-30 2019-04-30 Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910357763.4A CN110052601B (en) 2019-04-30 2019-04-30 Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating

Publications (2)

Publication Number Publication Date
CN110052601A CN110052601A (en) 2019-07-26
CN110052601B true CN110052601B (en) 2021-06-11

Family

ID=67321608

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910357763.4A Active CN110052601B (en) 2019-04-30 2019-04-30 Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating

Country Status (1)

Country Link
CN (1) CN110052601B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110788329B (en) * 2019-11-07 2022-11-04 江苏集萃安泰创明先进能源材料研究院有限公司 Carbon-containing composite hydrogen storage alloy and preparation method thereof, composite solid hydrogen storage tank and hydrogen storage performance testing method
CN110842192B (en) * 2019-11-13 2020-08-25 四川大学 Nitrogen-doped porous carbon-coated hydrogen storage alloy powder and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101659700B1 (en) * 2015-12-24 2016-09-23 영남대학교 산학협력단 A novel method for the production of aluminum nitride and aluminum nitride-based composite substances
CN107500248B (en) * 2017-09-20 2020-02-18 扬州大学 Spherical core-shell type LaNiAl-SiO2Composite hydrogen storage material and preparation method thereof
CN108923034A (en) * 2018-07-16 2018-11-30 燕山大学 Surface coats the preparation method of reduced form graphene oxide-metal composite hydrogen bearing alloy and the negative electrode material of nickel-metal hydride battery

Also Published As

Publication number Publication date
CN110052601A (en) 2019-07-26

Similar Documents

Publication Publication Date Title
CN108767260B (en) Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof
CN112018349B (en) CoTe2/MXene composite material and preparation method thereof
CN110052601B (en) Method for modifying AB5 type hydrogen storage alloy through silicon dioxide-graphene composite coating
CN107180964A (en) A kind of microwave method prepares method and the application of blended metal oxide/graphene composite nano material
Shao et al. Effect of nanostructure and partial substitution on gas absorption and electrochemical properties in Mg2Ni-based alloys
CN109755515B (en) Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof
CN114162881B (en) Preparation method of anion in-situ doped high-nickel ternary cathode material
CN111410232A (en) Preparation method of manganese dioxide positive electrode material
CN106784705B (en) A kind of hydrogen storing alloy powder and its surface treatment method
CN108232187B (en) High-dispersion hexagonal nanosheet structure nickel-cobalt-manganese ternary cathode material and preparation method thereof
WO2011116539A1 (en) Method for preparing positive electrode material lifepo4/c of lithium ion battery
CN113451570A (en) MOF-derived core-shell-structured lithium ion battery negative electrode material and preparation method thereof
CN113421775A (en) NiO @ CoMoO4Preparation method of/NF capacitance electrode
CN114267841B (en) Preparation method and application of surface-fully-coated high-nickel single crystal ternary material
Cui et al. Preparation of spherical carbonated foam/Zn–Al layered double oxides composite anode and its superior cycling stability in Zinc–Nickel secondary batteries
Zhang et al. Enhanced electrochemical hydrogen storage performance of Ti49Zr26Ni25 alloy by doping with Pd nanoparticles deposited MWCNTs
CN102891298B (en) Surface modification method for Mg-Ni-Nd system hydrogen storage electrode alloy
CN110165199B (en) Modified anode material and preparation method thereof
CN107910540B (en) Preparation method of carbon-silicon negative electrode material and lithium ion battery
WO2023010970A1 (en) Lithium nickel manganese cobalt oxide positive electrode material of high-performance power battery and preparation method therefor
CN102368546B (en) Magnesium-based hydrogen-storage electrode alloy, and preparation method and application thereof
CN115411247A (en) Lithium battery positive electrode material and preparation method thereof
CN109755499B (en) Iron-nickel secondary battery negative electrode additive, preparation method, iron-based negative plate using additive and application
CN109686978B (en) Alkaline secondary battery iron electrode additive, preparation method, iron-based negative plate using additive and application
Sheng et al. Revealing the orbital interactions between dissimilar metal sites during oxygen reduction process

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