CN110052601A - A kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating - Google Patents
A kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating Download PDFInfo
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- CN110052601A CN110052601A CN201910357763.4A CN201910357763A CN110052601A CN 110052601 A CN110052601 A CN 110052601A CN 201910357763 A CN201910357763 A CN 201910357763A CN 110052601 A CN110052601 A CN 110052601A
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- B22F1/16—Metallic particles coated with a non-metal
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- 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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
- H01M4/385—Hydrogen absorbing alloys of the type LaNi5
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of methods of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating, AB5 type hydrogen storage alloy powder is first prepared using vacuum induction melting method, then the modified AB5 type hydrogen storage alloy of silica-graphene compound coating is obtained by the copper composite plating bath plating of graphene-sulfur acid and graphene-silica complex sol surface cladding processing method.Production method of the invention can play surface cladding protective effect to hydrogen bearing alloy; increase substantially its durability; to greatly promote the cyclical stability of hydrogen bearing alloy; the electrode performance of hydrogen bearing alloy can be taken into account again; excellent discharge capacity and high-rate discharge ability are made it have, to develop the product with Good All-around Property.
Description
Technical field
The present invention relates to hydrogen bearing alloy technical field more particularly to a kind of modified AB5 of silica-graphene compound coating
The method of type hydrogen storage alloy.
Background technique
With the development of economy, the consumption of the fossil energies such as coal, petroleum, natural gas constantly accelerates, while also exacerbating ring
Border pollution.Hydrogen Energy is a kind of from a wealth of sources, rich reserves green clean energy resourcies, have numerous excellent characteristics, and Hydrogen Energy is deposited
Storage is the key that can Hydrogen Energy move towards practical.Hydrogen bearing alloy is a kind of high performance hydrogen storage material, is referred in certain temperature and pressure
It under power, reversibly largely absorbs, the intermetallic compounds of storage and release hydrogen, the crucial material as Ni-MH secondary battery
Material, plays a key effect to the performance superiority and inferiority of battery.In order to make Ni-MH secondary battery that there is high-energy density, good electric discharge
Characteristic and cycle life, exploitation high-performance hydrogen bearing alloy are extremely important.
In the various hydrogen bearing alloys researched and developed at present, the discharge capacity of AB5 type hydrogen storage alloy is higher, conduct
The important production material of Ni-MH secondary battery cathode, obtains extensive commercial applications.But the antioxygen of AB5 type hydrogen storage alloy
Change, anti-powdering and corrosion resistant ability are poor, and performance degradation, stable circulation are easy to happen in charge and discharge process repeatedly
The performances such as property and cycle life still need to improve.Cladding processing in surface is carried out to hydrogen storing alloy powder, is formed on its surface protective layer, it can
It is a kind of effective solution for improving its cyclical stability to improve the durability of alloyed powder.For example, on hydrogen bearing alloy surface
Copper facing can play the role of anti-corrosion protective layer, improve the cyclical stability of hydrogen bearing alloy.But in air due to copper plate
It is not sufficiently stable, discharge performance is decreased obviously after storing in air；And copper-plating technique is more demanding, and coarse copper plate is not only
Excellent anti-corrosion, electric action cannot be played, can also discharge stability be made to decline.In addition, single surface coating modification hydrogen storage is closed
Fitting has biggish limitation, not only limited to the promotion of cyclical stability, but also is difficult to General Promotion hydrogen bearing alloy
The chemical properties such as discharge capacity, high-rate discharge ability.Therefore, how the comprehensive performance of General Promotion hydrogen bearing alloy, be
A current important topic.
Summary of the invention
The purpose of the present invention is making up the defect of prior art, it is modified to provide a kind of silica-graphene compound coating
The method of AB5 type hydrogen storage alloy, this method can play surface cladding protective effect to hydrogen bearing alloy, it is durable to increase substantially its
Property, to greatly promote the cyclical stability of hydrogen bearing alloy, and the electrode performance of hydrogen bearing alloy can be taken into account, made it have excellent
Discharge capacity and high-rate discharge ability, to develop the product with Good All-around Property.
In order to achieve the above objectives, the technical solution used in the present invention are as follows:
A kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating, comprising the following steps:
(1) raw metal powder of the purity 99% or more is weighed by the chemical composition of AB5 type hydrogen storage alloy, in indifferent gas
Under body protection, AB5 type hydrogen storage alloy is prepared using vacuum induction melting method, is sieved by mechanical crushing, ball milling, obtains AB5 type
Hydrogen-bearing alloy powder；
(2) step (1) the AB5 type hydrogen storage alloy powder is placed in graphene-sulfur acid copper composite plating bath and carries out plating,
It filters after plating, is once wrapped then in turn through deionized water, ethanol washing in 30-60 DEG C of drying process 2-4h
Cover AB5 type hydrogen storage alloy powder；
(3) the primary cladding AB5 type hydrogen storage alloy powder for obtaining step (2) and graphene-silica complex sol
Stirred evenly after mixing, then ball mill is added in still aging 24-48h, ball mill is placed in microwave generating apparatus carry out it is micro-
Wave assists ball-milling treatment, is added in batch mixer after taking-up and carries out heating mixing treatment, cold finally in 200-300 DEG C of heat preservation 2-4h
But the modified AB5 type hydrogen storage alloy of silica-graphene compound coating is obtained afterwards.
Preferably, the chemical composition of the AB5 type hydrogen storage alloy is LaNi3.6Co0.7Mn0.4Al0.3。
Preferably, the AB5 type hydrogen storage alloy powder is 200-300 mesh.
Preferably, the graphene-sulfur acid copper composite plating bath is prepared by weight by following raw materials: copper sulphate 1-5
Part, 0.1-1 parts of graphene, 0.1-0.5 parts of EDTA, 800-1000 parts of deionized water；The preparation method is as follows: by EDTA, copper sulphate
It is successively dissolved in deionized water, then addition graphene ultrasonic disperse is uniform, obtains graphene-sulfur acid copper composite plating bath.
Preferably, the mass ratio of the AB5 type hydrogen storage alloy powder and the graphene-sulfur acid copper composite plating bath is
(0.5-1): (5-10).
Preferably, the plating carries out under the conditions of 20-25 DEG C, 30-40kHz ultrasonic treatment, plating time 1-2min.
Preferably, the graphene-silica complex sol is prepared by weight by following raw materials: positive silicic acid second
1-2 parts of ester, 0.05-0.1 parts of graphene, 4-8 parts of ethyl alcohol, concentration is 4-8 parts of aqueous hydrochloric acid solution of 0.05-0.1mol/L；Preparation
Method is as follows: first ethyl orthosilicate being added in ethyl alcohol and is uniformly mixed, graphene ultrasonic disperse is then added, adds hydrochloric acid water
Solution stirs 0.5-1h, obtains graphene-silica complex sol.
Preferably, the primary cladding AB5 type hydrogen storage alloy powder and the graphene-silica complex sol matter
Amount is than being (1-2): (5-10).
Preferably, specific step is as follows for the microwave-assisted ball-milling treatment: prior under 400-600W microwave treatment conditions
Then ball milling 1-3min stops microwave treatment, continue ball milling 3-5min, and above-mentioned steps are repeated 2-5 times.
Preferably, the detailed process of the heating mixing treatment is as follows: prior to revolving speed be 200-400r/min, temperature is
A mixing is carried out under conditions of 40-60 DEG C, the time of a mixing is 5-10min；It is in revolving speed after mixing
800-1200r/min, temperature carry out rerolling under conditions of being 85-95 DEG C, the time of rerolling is 10-15min.
The invention has the advantages that
The present invention forms graphene-copper on the type hydrogen storage alloy powder surface AB5 using the method for Ni-P and once wraps
Coating, the copper in clad have high catalytic activity and stronger absorption electronics, transport electrons ability, can quickly provide arrival
The electronics of electrode surface promotes the progress of storage hydrogen reaction, improves the discharge capacity of hydrogen bearing alloy；Graphene in clad has
Excellent electric conductivity, can be reduced the resistance of hydrogen-bearing alloy electrode, to improve high-rate discharge ability；By introducing in the plating solution
The chemically composited electroplating method of graphene not only plays the role of refining crystal grain in the forming process of coating, makes the group of copper plate
Knit finer and close, surface is more smooth, improves the quality of copper plate, further improve copper plate corrosion resistance and anti-air
Oxidisability to improve the cyclical stability of hydrogen bearing alloy, and can reinforce the combination of graphene Yu hydrogen bearing alloy surface,
It is uniformly distributed graphene in clad, more effectively improves the high-rate discharge ability of battery.
In addition, the secondary clad of silica-graphene is formed in cover surface using sol-gel method, one
Aspect, the fine and close clad of graphene-silica can effectively inhibit oxidation, the dusting of composite deposite, to assign hydrogen storage conjunction
The more excellent cyclical stability of gold, on the other hand, the discharge capacity etc. that surface coated silica will lead to hydrogen bearing alloy is put
Electrical property decline, and graphene can improve the discharge capacity of hydrogen bearing alloy, high-rate discharge ability, make to reduce cladding to putting
The adverse effect of electrical property reaches under the premise of further promoting hydrogen bearing alloy cyclical stability and takes into account wanting for discharge performance
It asks.
The present invention is after once cladding AB5 type hydrogen storage alloy powder is mixed with graphene-silica complex sol, first
Using microwave-assisted ball-milling treatment, stage heating mixing treatment is then carried out, comes into full contact with complex sol with alloy powder,
And homogeneous heating during forming secondary clad, thus improve the compactness of secondary clad, uniformity and its
With the binding force between a clad, guarantee cladding after hydrogen bearing alloy have good surface quality, discharge performance and
Cyclical stability.
In conclusion the present invention can not only increase substantially the cyclical stability of hydrogen bearing alloy, and hydrogen bearing alloy is put
Capacitance and high-rate discharge ability can be improved, to reach the discharge capacity of General Promotion hydrogen bearing alloy, high magnification
The purpose of discharge performance and cyclical stability.
Specific embodiment
Technical solution of the present invention is further described combined with specific embodiments below.
Embodiment 1
A kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating, comprising the following steps:
It (1) is LaNi by chemical composition3.6Co0.7Mn0.4Al0.3The AB5 type hydrogen storage alloy that purity is weighed 99% or more is former
Expect metal powder, under inert gas protection, AB5 type hydrogen storage alloy is prepared using vacuum induction melting method, by being mechanically pulverized,
Ball milling screening, obtains the AB5 type hydrogen storage alloy powder of 200 mesh；
(2) by step (1) the AB5 type hydrogen storage alloy powder be placed in graphene-sulfur acid copper composite plating bath in 20 DEG C,
Plating 1min under the conditions of 30kHz ultrasonic treatment, is filtered after plating, then in turn through deionized water, ethanol washing, in 30
DEG C be dried 2h, obtain once coating AB5 type hydrogen storage alloy powder, wherein graphene-sulfur acid copper composite plating bath is by following originals
Material is prepared by weight: 1 part of copper sulphate, 0.1 part of graphene, and 0.1 part of EDTA, 800 parts of deionized water, preparation method
It is as follows: EDTA, copper sulphate to be successively dissolved in deionized water, then addition graphene ultrasonic disperse is uniform, obtains graphene-
The mass ratio of copper sulphate composite plating bath, AB5 type hydrogen storage alloy powder and graphene-sulfur acid copper composite plating bath is 0.5:5；
(3) the primary cladding AB5 type hydrogen storage alloy powder for obtaining step (2) and graphene-silica complex sol
It is stirred evenly after mixing, it is still aging that ball mill is then added for 24 hours, ball mill is placed in microwave generating apparatus, prior to 400W
Then ball milling 1min under microwave treatment conditions stops microwave treatment, continue ball milling 3min, above-mentioned steps are repeated 2 times, after taking-up
It is added in batch mixer, carries out a mixing, the time of a mixing under conditions of prior to revolving speed be 200r/min, temperature is 40 DEG C
For 5min；Rerolling, rerolling are carried out under conditions of revolving speed is 800r/min, temperature is 85 DEG C after mixing
Time be 10min, finally in 200 DEG C of heat preservation 2h, the modified AB5 type storage of silica-graphene compound coating is obtained after cooling
Hydrogen alloy, wherein graphene-silica complex sol is prepared by weight by following raw materials: 1 part of ethyl orthosilicate, stone
0.05 part of black alkene, 4 parts of ethyl alcohol, concentration is 4 parts of aqueous hydrochloric acid solution of 0.05mol/L, the preparation method is as follows: first by ethyl orthosilicate
It is added in ethyl alcohol and is uniformly mixed, graphene ultrasonic disperse is then added, add aqueous hydrochloric acid solution stirring 0.5h, obtain graphite
Alkene-silica complex sol, it is primary to coat AB5 type hydrogen storage alloy powder and graphene-silica complex sol quality
Than for 1:5.
Embodiment 2
A kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating, comprising the following steps:
It (1) is LaNi by chemical composition3.6Co0.7Mn0.4Al0.3The AB5 type hydrogen storage alloy that purity is weighed 99% or more is former
Expect metal powder, under inert gas protection, AB5 type hydrogen storage alloy is prepared using vacuum induction melting method, by being mechanically pulverized,
Ball milling screening, obtains the AB5 type hydrogen storage alloy powder of 300 mesh；
(2) by step (1) the AB5 type hydrogen storage alloy powder be placed in graphene-sulfur acid copper composite plating bath in 25 DEG C,
Plating 2min under the conditions of 40kHz ultrasonic treatment, is filtered after plating, then in turn through deionized water, ethanol washing, in 60
DEG C be dried 4h, obtain once coating AB5 type hydrogen storage alloy powder, wherein graphene-sulfur acid copper composite plating bath is by following originals
Material is prepared by weight: 5 parts of copper sulphate, 1 part of graphene, 0.5 part of EDTA, 1000 parts of deionized water, preparation method is such as
Under: EDTA, copper sulphate are successively dissolved in deionized water, then addition graphene ultrasonic disperse is uniform, obtains graphene-sulfur
The mass ratio of sour copper composite plating bath, AB5 type hydrogen storage alloy powder and graphene-sulfur acid copper composite plating bath is 0.5:10；
(3) the primary cladding AB5 type hydrogen storage alloy powder for obtaining step (2) and graphene-silica complex sol
It is stirred evenly after mixing, then still aging 48h is added ball mill, ball mill is placed in microwave generating apparatus, prior to 600W
Then ball milling 3min under microwave treatment conditions stops microwave treatment, continue ball milling 5min, above-mentioned steps are repeated 5 times, after taking-up
It is added in batch mixer, carries out a mixing, the time of a mixing under conditions of prior to revolving speed be 400r/min, temperature is 60 DEG C
For 10min；Rerolling is carried out after mixing under conditions of revolving speed is 1200r/min, temperature is 95 DEG C, it is secondary mixed
The time of material is 15min, and finally in 300 DEG C of heat preservation 4h, the modified AB5 type of silica-graphene compound coating is obtained after cooling
Hydrogen bearing alloy, wherein graphene-silica complex sol is prepared by weight by following raw materials: 2 parts of ethyl orthosilicate,
0.1 part of graphene, 8 parts of ethyl alcohol, concentration is 8 parts of aqueous hydrochloric acid solution of 0.1mol/L, the preparation method is as follows: first by ethyl orthosilicate
It is added in ethyl alcohol and is uniformly mixed, graphene ultrasonic disperse is then added, add aqueous hydrochloric acid solution stirring 1h, obtain graphene-
Silica complex sol, primary cladding AB5 type hydrogen storage alloy powder are with graphene-silica complex sol mass ratio
1:10.
Embodiment 3
A kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating, comprising the following steps:
It (1) is LaNi by chemical composition3.6Co0.7Mn0.4Al0.3The AB5 type hydrogen storage alloy that purity is weighed 99% or more is former
Expect metal powder, under inert gas protection, AB5 type hydrogen storage alloy is prepared using vacuum induction melting method, by being mechanically pulverized,
Ball milling screening, obtains the AB5 type hydrogen storage alloy powder of 250 mesh；
(2) by step (1) the AB5 type hydrogen storage alloy powder be placed in graphene-sulfur acid copper composite plating bath in 24 DEG C,
Plating 1.5min under the conditions of 35kHz ultrasonic treatment, is filtered after plating, then in turn through deionized water, ethanol washing, in
40 DEG C of drying process 3h, obtain once coating AB5 type hydrogen storage alloy powder, wherein graphene-sulfur acid copper composite plating bath is by following
Raw material is prepared by weight: 2 parts of copper sulphate, 0.5 part of graphene, and 0.3 part of EDTA, 900 parts of deionized water, preparation method
It is as follows: EDTA, copper sulphate to be successively dissolved in deionized water, then addition graphene ultrasonic disperse is uniform, obtains graphene-
The mass ratio of copper sulphate composite plating bath, AB5 type hydrogen storage alloy powder and graphene-sulfur acid copper composite plating bath is 0.8:5；
(3) the primary cladding AB5 type hydrogen storage alloy powder for obtaining step (2) and graphene-silica complex sol
It is stirred evenly after mixing, then still aging 36h is added ball mill, ball mill is placed in microwave generating apparatus, prior to 500W
Then ball milling 2min under microwave treatment conditions stops microwave treatment, continue ball milling 4min, above-mentioned steps are repeated 3 times, after taking-up
It is added in batch mixer, carries out a mixing, the time of a mixing under conditions of prior to revolving speed be 300r/min, temperature is 50 DEG C
For 6min；After mixing in revolving speed be 1000r/min, it is at a temperature of 90 °C under the conditions of carry out rerolling, it is secondary mixed
The time of material is 12min, and finally in 250 DEG C of heat preservation 3h, the modified AB5 type of silica-graphene compound coating is obtained after cooling
Hydrogen bearing alloy, wherein graphene-silica complex sol is prepared by weight by following raw materials: ethyl orthosilicate 1.5
Part, 0.08 part of graphene, 6 parts of ethyl alcohol, concentration is 8 parts of aqueous hydrochloric acid solution of 0.06mol/L, the preparation method is as follows: first by positive silicon
Acetoacetic ester is added in ethyl alcohol and is uniformly mixed, and graphene ultrasonic disperse is then added, and adds aqueous hydrochloric acid solution stirring 0.6h, obtains
Graphene-silica complex sol, it is primary to coat AB5 type hydrogen storage alloy powder and graphene-silica complex sol
Mass ratio is 1.5:5.
Comparative example 1
It is LaNi by chemical composition3.6Co0.7Mn0.4Al0.3Weigh AB5 type hydrogen storage alloy raw material gold of the purity 99% or more
Belong to powder, under inert gas protection, AB5 type hydrogen storage alloy is prepared using vacuum induction melting method, by mechanical crushing, ball milling
Screening, obtains the AB5 type hydrogen storage alloy powder of 200 mesh.
Sample made from a certain amount of above-described embodiment 1-3 and comparative example 1 is taken respectively, with carbonyl nickel powder in the ratio of 1:4
Diameter is pressed into as the hydrogen-bearing alloy electrode of 20mm with the pressure of 20MPa with tablet press machine after mixing, is just extremely sintered
NiOH2/NiOOH electrode, electrolyte are 6mol/L KOH aqueous solution, and diaphragm is nylon nonwoven fabrics, keep environment temperature 25 ± 1
DEG C, the test of discharge capacity, high magnification and cycle life is carried out, test result is as follows shown in table:
Claims (10)
1. a kind of method of the modified AB5 type hydrogen storage alloy of silica-graphene compound coating, which is characterized in that including following
Step:
(1) raw metal powder of the purity 99% or more is weighed by the chemical composition of AB5 type hydrogen storage alloy, is protected in inert gas
Under shield, AB5 type hydrogen storage alloy is prepared using vacuum induction melting method, is sieved by mechanical crushing, ball milling, obtains AB5 type hydrogen storage
Alloy powder；
(2) step (1) the AB5 type hydrogen storage alloy powder is placed in graphene-sulfur acid copper composite plating bath and carries out plating, plating
After filter, once coated then in turn through deionized water, ethanol washing in 30-60 DEG C of drying process 2-4h
AB5 type hydrogen storage alloy powder；
(3) the primary cladding AB5 type hydrogen storage alloy powder for obtaining step (2) is mixed with graphene-silica complex sol
After stir evenly, then ball mill is added in still aging 24-48h, by ball mill be placed in microwave generating apparatus carry out microwave it is auxiliary
Ball-milling treatment is helped, is added in batch mixer after taking-up and carries out heating mixing treatment, finally in 200-300 DEG C of heat preservation 2-4h, after cooling
Obtain the modified AB5 type hydrogen storage alloy of silica-graphene compound coating.
2. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the chemical composition of the AB5 type hydrogen storage alloy is LaNi3.6Co0.7Mn0.4Al0.3.
3. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the AB5 type hydrogen storage alloy powder is 200-300 mesh.
4. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the graphene-sulfur acid copper composite plating bath is prepared by weight by following raw materials: 1-5 parts of copper sulphate, stone
Black alkene 0.1-1 parts, EDTA0.1-0.5 parts, 800-1000 parts of deionized water；The preparation method is as follows: EDTA, copper sulphate is successively molten
Solution is in deionized water, and then addition graphene ultrasonic disperse is uniform, obtains graphene-sulfur acid copper composite plating bath.
5. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the mass ratio of the AB5 type hydrogen storage alloy powder and the graphene-sulfur acid copper composite plating bath is (0.5-1):
(5-10)。
6. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the plating carries out under the conditions of 20-25 DEG C, 30-40kHz ultrasonic treatment, plating time 1-2min.
7. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the graphene-silica complex sol is prepared by weight by following raw materials: ethyl orthosilicate 1-
2 parts, 0.05-0.1 parts of graphene, 4-8 parts of ethyl alcohol, concentration is 4-8 parts of aqueous hydrochloric acid solution of 0.05-0.1mol/L；Preparation method
It is as follows: first ethyl orthosilicate being added in ethyl alcohol and is uniformly mixed, graphene ultrasonic disperse is then added, adds aqueous hydrochloric acid solution
0.5-1h is stirred, graphene-silica complex sol is obtained.
8. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the primary cladding AB5 type hydrogen storage alloy powder and the graphene-silica complex sol mass ratio
For (1-2): (5-10).
9. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, specific step is as follows for the microwave-assisted ball-milling treatment: prior to ball milling under 400-600W microwave treatment conditions
Then 1-3min stops microwave treatment, continue ball milling 3-5min, and above-mentioned steps are repeated 2-5 times.
10. a kind of method of the modified AB5 type hydrogen storage alloy of silica according to claim 1-graphene compound coating,
It is characterized in that, the detailed process of the heating mixing treatment is as follows: prior to revolving speed being 200-400r/min, temperature 40-60
A mixing is carried out under conditions of DEG C, the time of a mixing is 5-10min；After mixing in revolving speed be 800-
1200r/min, temperature carry out rerolling under conditions of being 85-95 DEG C, the time of rerolling is 10-15min.
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| CN110788329A (en) * | 2019-11-07 | 2020-02-14 | 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 |
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