CN107151805A - Foam rare earth-nickel alloys and preparation method thereof, purposes - Google Patents
Foam rare earth-nickel alloys and preparation method thereof, purposes Download PDFInfo
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- CN107151805A CN107151805A CN201710229632.9A CN201710229632A CN107151805A CN 107151805 A CN107151805 A CN 107151805A CN 201710229632 A CN201710229632 A CN 201710229632A CN 107151805 A CN107151805 A CN 107151805A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
Abstract
This application discloses a kind of foam rare earth-nickel alloys and preparation method thereof, purposes.The foam rare earth-nickel alloys are foam La Ni, Ce Ni, Nd Ni, Sm Ni, Dy Ni or Ho Ni alloys, and the foam rare earth-nickel alloys maintain the aperture consistent with Commercial foam nickel and through-hole rate.The application discloses a kind of preparation method of foam rare earth-nickel alloys again, comprises the following steps：Using spectroscopically pure graphite electric conductor or inertia electric conductor as anode, nickel foam carries out cyclic voltammetry as negative electrode in electrochemical workstation, obtains the reduction potential that rare earth ion forms intermetallic compound on foam nickel electrode；Recycle electrochemical workstation or potentiostat to use to be electrolysed 12 hours under the conditions of the reduction potential of different set, obtain the foam rare earth-nickel alloys material of solid state stability opening.Foam rare earth-nickel alloys of the present invention can be as conventional commercial nickel foam as hydrogen storage and the carrier of liberation of hydrogen material, but itself has superior hydrogen storage and liberation of hydrogen ability.
Description
Technical field
Foamed alloy and rare earth alloy technical field are prepared the present invention relates to electrochemistry, and in particular in high-temperature molten salt system
Middle electrolytic preparation foam rare earth-nickel alloys and preparation method thereof, purposes.
Background technology
Rare earth-nickel alloys (such as LaNi5) and its derivative have quick charge/discharge capacity, reversible hydrogen storage capacity high
Performance, is a kind of ideal hydrogen storage material, is widely used in battery industry.And foam nickel-base alloy is used as a kind of green wood
Material, due to its high-melting-point, light weight, specific surface area is big, specific strength is high, it is corrosion-resistant the advantages of, in space shuttle and hypervelocity flight
The wide application in the fields such as Metallic Thermal Protection Systems, auto industry and the new energy of device.Foam rare earth-nickel alloys can be by both
Premium properties is combined together, and constitutes a kind of new type functional material for being expected to apply in fields such as battery, automobile and new energy.
Industrial at present, the preparation method of hydrogen bearing alloy is mainly alloy melting method, this method using high pure metal as precursor,
Therefore high with cost, preparation flow is complicated, the shortcomings of environmental pollution is heavy；And obtained simply block materials, it is impossible to will
Alloy foam.And the method for preparing foamed alloy has casting, solid powder embedding, spraying process, soaking paste sponge sintering at present
Method, electro-deposition diffusion method etc.；And it is industrial, mainly using electro-deposition method, it regard polyurethane sponge as premise, alkaline electroless plating
Nickel conducting, then another/various metals electrolytic deposition is thermally decomposed remove poly- ammonia in organic electrolyte in nickel plating, finally
Ester sponge obtains foamed alloy finished product.Due in organic electrolyte, can only by the relatively low transition elements of activity (such as Fe, Co,
Cu, Cr, Zn, Mn, Mo etc.) ion is electrolytic reduced to metal.Therefore, the preparation of foamed alloy at present truly can only office
Limit is in transition metal alloy aspect.It is higher for activity, if the more negative metallic element of reduction potential (such as rare earth element) ion not
It can be electrolysed in organic electrolyte and obtain metal.
The content of the invention
In view of drawbacks described above of the prior art or deficiency, expect that a kind of foam truly easily prepared of offer is dilute
Soil-nickel alloy liberation of hydrogen material.
To achieve these goals, the embodiment of the present invention provides a kind of foam rare earth-nickel alloys, the foam rare earth-nickel
Alloy be foam La-Ni, Ce-Ni, Nd-Ni, Sm-Ni, Dy-Ni or Ho-Ni alloy, the foam rare earth-nickel alloys have with
The consistent aperture of Commercial foam nickel and through-hole rate.
The present invention also provides a kind of foam rare earth-nickel alloys as hydrogen storage and the purposes of the carrier of liberation of hydrogen material, and itself
With significant hydrogen storage and liberation of hydrogen ability.
The present invention provides a kind of preparation method of foam rare earth-nickel alloys again, comprises the following steps：
Using spectroscopically pure graphite electric conductor or inertia electric conductor as anode, nickel foam is as negative electrode in electrochemical operation
Stand and carry out cyclic voltammetry, obtain the reduction potential that rare earth ion forms intermetallic compound on foam nickel electrode；It is sharp again
Used and be electrolysed 1-2 hours under the conditions of the reduction potential of different set with electrochemical workstation or potentiostat, obtain solid-state
The foam rare earth-nickel alloys material of stable opening.
Specifically, a kind of preparation method of foam rare earth-nickel alloys, comprises the following steps：
(1) halide fused salt is put into cell reaction container, drying and dehydrating under vacuum condition, then halide fused salt is moved
Enter inert gas environment；
(2) the halide fused salt for treating step (1) is heated to 400-1000 DEG C, is then added in halide fused salt
Rare earth halide；
(3) negative electrode and anode inserting step (2) are added in the fused salt of rare earth halide, wherein negative electrode is nickel foam electricity
Pole, anode is spectroscopic pure electric conductor graphite or inertia electric conductor；
(4) cyclic voltammetry is carried out between step (3) negative electrode and anode using electrochemical workstation, determined dilute
Reduction potential of the native ion on foam nickel electrode；
(5) using electrochemical workstation or potentiostat under the conditions of the rare earth reduction potential that step (4) is determined, in the moon
Apply voltage between pole and anode；
(6) potentiostatic deposition is used, under the conditions of the reduction potential of different rare earths, the rare earth ion in fused salt is quickly gone back
Original deposits on foam nickel electrode and forms the foam rare earth-Ni alloy materials of different component.
Preferably, the mass ratio of the rare earth halide and halide fused salt is 1-5%.
Preferably, the molal weight ratio of the foamed alloy middle rare earth and nickel is 1/5,1/3,1/2 or 3/1.
Preferably, the temperature of the drying and dehydrating is 200-300 DEG C, and the time is 24-30 hours.
Preferably, described halide fused salt is single alkaline earth metal chloride or bifurcated alkali mixed halide
Molten salt system；The alkaline earth metal chloride is LiCl or CaCl2；The bifurcated alkali mixed halide be LiCl-KCl,
NaCl-KCl、NaCl-CaCl2, KF-KCl or LiF-CaF2。
Preferably, when from different molten salt systems, the temperature of the halide fused salt heating is respectively LiCl：650-
800℃；CaCl2：800-1000℃；LiCl-KCl：400-600℃；NaCl-KCl：700-900℃；KF-KCl：650-850
℃；LiF-CaF2：750-950℃.
Preferably, the rare earth halide is lanthanum trichloride (LaCl3), cerous chloride (CeCl3), neodymium trichloride
(NdCl3), samarium trichloride (SmCl3), dysprosium trichloride (DyCl3), tri-chlorination holmium (HoCl3) or lanthanum trifluoride (LaF3), it is borontrifluoride
Cerium (CeF3), borontrifluoride neodymium (NdF3), borontrifluoride samarium (SmF3), borontrifluoride dysprosium (DyF3) or holmium trifluoride (HoF3)。
The foam rare earth-nickel alloys of the present invention have significant hydrogen storage and liberation of hydrogen ability, can be as conventional commercial nickel foam
Like that as hydrogen storage and the carrier of liberation of hydrogen material, and itself there is significant hydrogen storage and liberation of hydrogen ability.It is expected in battery, automobile
With the new type functional candidate material of the field such as new energy application.Prepared the preparation method is that being modified in high-temperature molten salt
Foam rare earth-nickel alloys, prior art can not prepare foam rare earth-nickel alloys.The high temperature inorganic fused salt that the present invention is used is (such as
Alkali metal/alkaline-earth halide), good conductivity wider with decomposition electric potential, diffusion coefficient is big, the features such as solvability is strong,
, can be by the halide uniform dissolution of rare earth isoreactivity element as electrolyte carrier.In addition, nickel foam is in alkali metal/alkaline earth
Metal halide has very high stability.Therefore, lanthanum halide is dissolved in high-temperature molten salt, the moon is used as using nickel foam
Pole, electrolysis obtains foam lanthanum-nickel alloy material.The nickel foam of conventional commercial can be carried out electrolysis modifying by this method, be changed
Conventional method can only prepare the limitation of transition elements foam nickel-base alloy.
Brief description of the drawings
By reading the detailed description made to non-limiting example made with reference to the following drawings, the application's is other
Feature, objects and advantages will become more apparent upon：
Fig. 1 is the implementation schematic diagram of molten-salt electrolysis provided in an embodiment of the present invention；
Fig. 2 is provided in an embodiment of the present invention in LiCl-KCl-LaCl3In (1.5wt.%) molten salt system, equal mass
Thread and foam nickel electrode on cyclic voltammetry curve figure；
Fig. 3 is electrolysed 1 on the thread and foam nickel electrode of equal mass respectively when being -2.0V provided in an embodiment of the present invention
The current versus time curve figure of hour；
Fig. 4 is the -1.8V provided in an embodiment of the present invention on foam nickel electrode, LiCl-KCl-LaCl3(1.5wt.%) melts
Foam LaNi after being electrolysed 2 hours in salt system5SEM (sem image, the scanning electron microscope image) surface topographies of alloy and (insert
Figure) XRD (X-ray diffraction, X-ray diffraction) component-part diagram；
Fig. 5 is the -1.8V provided in an embodiment of the present invention on foam nickel electrode, LiCl-KCl-LaCl3(1.5wt.%) melts
Foam LaNi under the conditions of high power (10 microns) after being electrolysed 2 hours in salt system5The SEM surface topography maps of alloy；
Fig. 6 is the -1.8V provided in an embodiment of the present invention on foam nickel electrode, LiCl-KCl-LaCl3(1.5wt.%) melts
Foam LaNi under the conditions of high power (10 microns) after being electrolysed 2 hours in salt system5The surface EDS elements of alloy are characterized；
Fig. 7 is the -2.0V provided in an embodiment of the present invention on foam nickel electrode, LiCl-KCl-LaCl3(1.5wt.%) melts
(a) SEM surface topography maps in foam lanthanum-nickel alloy section after being electrolysed 1 hour in salt system；
Fig. 8 is the -2.0V provided in an embodiment of the present invention on foam nickel electrode, LiCl-KCl-LaCl3(1.5wt.%) melts
The EDS elements in foam lanthanum-nickel alloy section after being electrolysed 1 hour in salt system are characterized；
Fig. 9 is nickel foam provided in an embodiment of the present invention and foam LaNi5Circulation volt of the electrode in 6mol%KOH solution
Pacify curve map；
Figure 10 is the foam nickel electrode provided in an embodiment of the present invention for collecting gas；
Figure 11 is the foam LaNi provided in an embodiment of the present invention for collecting gas5Electrode.
In figure：(1)-Ag/AgCl reference electrodes, (2)-indicator electrode, (3)-working electrode, (4)-and to electrode, (5)-electricity
Chem workstation, (6)-electric furnace heater, (7)-LiCl-KCl-LaCl3Fused salt, (8)-corundum crucible, (9)-glove box.
Degree degree of a representations in Fig. 4.
Embodiment
The application is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is used only for explaining related invention, rather than the restriction to the invention.It also should be noted that, in order to
It is easy to illustrate only the part related to invention in description, accompanying drawing.
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.Describe the application in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
The embodiment of the present invention provides a kind of foam rare earth-nickel alloys, the foam rare earth-nickel alloys be foam La-Ni,
Ce-Ni, Nd-Ni, Sm-Ni, Dy-Ni or Ho-Ni alloy, for stable rare earth-nickel intermetallic compound, the foam rare earth-
Nickel alloy has the aperture consistent with nickel foam and through-hole rate.
Alternatively, the foam rare earth-nickel alloys are LaNi5, the foamed alloy maintains the aperture of Commercial foam nickel, such as
Shown in Fig. 4, Fig. 5 and Fig. 6, SEM shows that the original opening of nickel foam and skeleton structure do not have any change.XRD and EDS are further
It is intermetallic compound LaNi to confirm foam lanthanum-nickel alloy5.Change system elements, it is possible to provide other foam rare earth-nickel alloys,
Such as CeNi5,SmNi5Etc., not limited to this of the embodiment of the present invention.
Alternatively, the foam rare earth-nickel alloys are La3Ni, referring to Fig. 7 and Fig. 8, its SEM and section EDS appearance structures
And elementary analysis.Change electrolytic potential, ion concentration and time conditions, elements La can spread deep whole nickel bodies, obtain
Homogeneous foam lanthanum-nickel alloy of other phases.
The present invention also provides a kind of foam rare earth-nickel alloys as the purposes of liberation of hydrogen material support.
Foam rare earth-nickel alloys of the present invention can be as liberation of hydrogen material support, and itself has significant liberation of hydrogen ability.Such as
Shown in Fig. 9, Figure 10 and Figure 11, due to there is LaNi5Alloy, the liberation of hydrogen ability of nickel foam in itself is significantly improved, liberation of hydrogen
Current potential shuffles more than 300mV.The foam rare earth-nickel alloys of the present invention are expected to what is applied in fields such as battery, automobile and new energy
New type functional candidate material.
The present invention provides a kind of preparation method of foam rare earth-nickel alloys again, comprises the following steps：
Using spectroscopically pure graphite electric conductor or inertia electric conductor as anode, nickel foam is as negative electrode in electrochemical operation
Stand and carry out cyclic voltammetry, obtain the reduction potential that rare earth ion forms intermetallic compound on foam nickel electrode；It is sharp again
Used and be electrolysed 1-2 hours under the conditions of the reduction potential of different set with electrochemical workstation or potentiostat, obtain solid-state
The foam rare earth-nickel alloys material of stable opening.
Specifically, a kind of preparation method of foam rare earth-nickel alloys, comprises the following steps：
(1) halide fused salt is put into cell reaction container, drying and dehydrating under vacuum condition, then halide fused salt is moved
Enter inert gas environment；
(2) the halide fused salt for treating step (1) is heated to 400-1000 DEG C, is then added in halide fused salt
Rare earth halide；
(3) negative electrode and anode inserting step (2) are added in the fused salt of rare earth halide, wherein negative electrode is nickel foam electricity
Pole, anode is spectroscopically pure graphite electric conductor or inertia electric conductor；
(4) cyclic voltammetry is carried out between step (3) negative electrode and anode using electrochemical workstation, determined dilute
Reduction potential of the native ion on foam nickel electrode；
(5) using electrochemical workstation or potentiostat under the conditions of the rare earth reduction potential that step (4) is determined, in the moon
Apply voltage between pole and anode；
(6) potentiostatic deposition is used, under the conditions of the reduction potential of different rare earths, the rare earth ion in fused salt is quickly gone back
Original deposits on foam nickel electrode and forms the foam rare earth-Ni alloy materials of different component.
The preparation method that the present invention is used is the Direct Electrolysis modifying foam nickel in high-temperature molten salt, so that it is dilute to obtain foam
Soil-nickel alloy.
Preferably, the mass ratio of the rare earth halide and halide fused salt is 1-5%.
Preferably, the molal weight ratio of the foamed alloy middle rare earth and nickel is 1/5,1/3,1/2 or 3/1.
Preferably, described halide fused salt is single alkaline earth metal chloride or bifurcated alkali mixed halide
Molten salt system；The alkaline earth metal chloride is LiCl or CaCl2；The bifurcated alkali mixed halide be LiCl-KCl,
NaCl-KCl、NaCl-CaCl2, KF-KCl or LiF-CaF2。
Preferably, when from different molten salt systems, the temperature of the halide fused salt heating is respectively LiCl：650-
800℃；CaCl2：800-1000℃；LiCl-KCl：400-600℃；NaCl-KCl：700-900℃；KF-KCl：650-850
℃；LiF-CaF2：750-950℃.
Preferably, the rare earth halide is lanthanum trichloride (LaCl3), cerous chloride (CeCl3), neodymium trichloride
(NdCl3), samarium trichloride (SmCl3), dysprosium trichloride (DyCl3), tri-chlorination holmium (HoCl3) or lanthanum trifluoride (LaF3), it is borontrifluoride
Cerium (CeF3), borontrifluoride neodymium (NdF3), borontrifluoride samarium (SmF3), borontrifluoride dysprosium (DyF3) or holmium trifluoride (HoF3)。
It is the schematic diagram of experimental provision of the present invention referring to Fig. 1.By 100g LiCl-KCl-LaCl3Fused salt 7 is put into corundum earthenware
CrucibleIn, 200-300 DEG C is dehydrated more than 24 hours in vacuum drying chamber, then moves into inert gas
Glove box 9 in environment, is heated, thermocouple monitoring temperature is to 500 DEG C using intelligent program temperature control electric furnace heater 6.By bar
Shape nickel foam (10 × 2 × 50mm) is connected to aluminium wireOn, put alundum tubeWork electricity is made
Pole 3, working electrode 3 is foam nickel cathode.By spectroscopically pure graphite electric conductorMolybdenum filament in connection, puts just
Jade pipePaired electrode 4 processed.LiCl-KCl-1wt.%AgCl salt-mixtures are put into alundum tubeThe Ag/AgCl reference electrodes 1 that insertion filamentary silver is made.Nickel wire (1mm) is put into alundum tubeThe indicator electrode 2 of thread nickel is made, lanthanum-nickel alloy formation current potential is indicated.Tungsten filament (1mm) is put into corundum
PipeLanthanide ion concentration in the indicator electrode 2 of thread tungsten, monitoring fused salt is made.The insertion of above-mentioned electrode is molten
Salt constitutes electrolytic cell.
Before electrolysis, cyclic voltammetry scan is carried out in nickel foam and nickel wire using computer and electrochemical workstation 5, such as
Shown in Fig. 2, fast 20mV/s is swept, the current potential of reduction potential and formation alloy of the trivalent lanthanum ion in nickel foam is confirmed.Due to bubble
The specific surface area of foam nickel is very big, is electrolysed as Fig. 3 can be seen that under the same terms, and the electricity passed through in nickel foam is thread nickel electricity
More than 12 times of pole, it is a kind of electrolytic method of speed quickly to illustrate this.
During electrolysis, to working electrode 3 and current potential is applied respectively to electrode 4 using on electrochemical workstation or potentiostat 5
It is electrolysed.
After electrolysis is completed, ultrasound washes the salinity being bonded in foam nickel cathode 3 in ethylene glycol solution, then uses
Ethanol solution is rinsed well, is air-dried.Electrolysate carries out phase component, appearance structure and elementary analysis using XRD and SEM-EDS.
Embodiment 1
The minimum system eutectic salts lithium chloride of fusing point-potassium chloride salt (0.59LiCl-0.42KCl) 100g in halide is taken to put
Enter in cell reaction container corundum crucible 8,200 DEG C of vacuum dehydrations 24 hours, then move into the fused salt of drying and dehydrating lazy
Property gaseous environment in, be heated to 500 DEG C, lanthanum trichloride (LaCl then added in lithium chloride-potassium chloride salt3) 2g, obtain
Fused salt mixt.By in foam nickel cathode and spectroscopically pure graphite electric conductor anode insertion fused salt mixt；Existed using electrochemical workstation
Cyclic voltammetry is carried out between negative electrode and anode, reduction potential of the lanthanum ion on negative electrode is determined, is -1.8V in reduction potential
Under the conditions of, apply voltage between a cathode and an anode, potentiostatic deposition 2 hours, the lanthanum ion in fused salt mixt is quickly reduced
Deposit on foam nickel electrode, obtain foam LaNi5Alloy.
As shown in figure 3, under the conditions of -2.0V potentiostatic deposition, respectively on the thread and foam nickel electrode of equal mass
The current versus time curve of electrolysis 1 hour.As shown in Figure 4, Figure 5 and Figure 6, SEM shows the original opening of nickel foam and skeleton structure
There is no any change.XRD and EDS, which are further confirmed that in foam lanthanum-nickel alloy, intermetallic compound LaNi5。
Embodiment 2
It is substantially the same manner as Example 1, take the minimum system eutectic salts lithium chloride-potassium chloride salt of fusing point in halide
(0.59LiCl-0.42KCl) 100g, 250 DEG C of vacuum dehydrations are heated to 400 DEG C after 24 hours, add lanthanum trichloride
(LaCl3)2g.Electrolytic potential -1.8V, is electrolysed 1.5 hours.Obtain foam LaNi3Alloy.
Embodiment 3
It is substantially the same manner as Example 1, take the minimum system eutectic salts lithium chloride-potassium chloride salt of fusing point in halide
(0.59LiCl-0.42KCl) 100g, 250 DEG C of vacuum dehydrations are heated to 600 DEG C for 28 hours, add lanthanum trichloride (LaCl3)
5g.Electrolytic potential -2.0V, is electrolysed 1 hour.Obtain foam La3Ni alloys.
Embodiment 4
It is substantially the same manner as Example 1, take the minimum system eutectic salts lithium chloride-potassium chloride salt of fusing point in halide
(0.59LiCl-0.42KCl) 100g, 200 DEG C of vacuum dehydrations are heated to 500 DEG C after 24 hours, add cerous chloride
(CeCl3)2g.Electrolytic potential -1.8V, is electrolysed 1 hour.Obtain foam CeNi5Alloy.
Embodiment 5
It is substantially the same manner as Example 1, take the minimum system eutectic salts lithium chloride-potassium chloride salt of fusing point in halide
(0.59LiCl-0.42KCl) 100g, 200 DEG C of vacuum dehydrations are heated to 500 DEG C after 24 hours, add samarium trichloride
(SmCl3)3g.Electrolytic potential -2.0V, is electrolysed 1 hour.Obtain foam SmNi5Alloy.
Embodiment 6
It is substantially the same manner as Example 1, take the minimum system eutectic salts lithium chloride-potassium chloride salt of fusing point in halide
(0.59LiCl-0.42KCl) 100g, is heated to 500 DEG C after vacuum dehydration, add samarium trichloride (NdCl3)2g.Electrolytic potential-
1.8V, is electrolysed 1.5 hours.Obtain foam NdNi5Alloy.
Embodiment 7
It is substantially the same manner as Example 1, minimum system eutectic salts lithium chloride (LiCl) salt 100g of fusing point in halide is taken,
300 DEG C of vacuum dehydration is heated to 700 DEG C after 24 hours, add lanthanum trichloride (LaCl3)2g.Electrolytic potential -1.65V, electrolysis 1 is small
When.Obtain foam LaNi5Alloy.
Embodiment 8
It is substantially the same manner as Example 1, take the minimum system eutectic salts potassium fluoride-potassium chloride salt of fusing point in halide
(0.5KF-0.5KCl) 100g, is heated to 750 DEG C for 30 hours after 300 DEG C of vacuum dehydrations, adds lanthanum trifluoride (LaF3)2g.Electrolysis
Current potential -1.95V, is electrolysed 1 hour.Obtain foam LaNi5Alloy.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.People in the art
Member should be appreciated that invention scope involved in the application, however it is not limited to the technology of the particular combination of above-mentioned technical characteristic
Scheme, while should also cover in the case where not departing from the inventive concept, is carried out by above-mentioned technical characteristic or its equivalent feature
Other technical schemes formed by any combination.Such as features described above has similar work(with (but not limited to) disclosed herein
The technical characteristic of energy carries out technical scheme formed by replacement mutually.
Claims (10)
1. a kind of foam rare earth-nickel alloys, it is characterised in that the foam rare earth-nickel alloys are foam La-Ni, Ce-Ni, Nd-
Ni, Sm-Ni, Dy-Ni or Ho-Ni alloy, the foam rare earth-nickel alloys have the aperture consistent with Commercial foam nickel and through hole
Rate.
2. the foam rare earth-nickel alloys described in a kind of claim 1 are used as hydrogen storage and the purposes of liberation of hydrogen material support.
3. a kind of preparation method of foam rare earth-nickel alloys, it is characterised in that comprise the following steps：
Using spectroscopically pure graphite electric conductor or inertia electric conductor as anode, nickel foam is entered as negative electrode in electrochemical workstation
Row cyclic voltammetry, obtains the reduction potential that rare earth ion forms intermetallic compound on foam nickel electrode；Recycle electricity
Chem workstation or potentiostat are used to be electrolysed 1-2 hours under the conditions of the reduction potential of different set, obtains solid state stability
The foam rare earth-nickel alloys material of opening.
4. the preparation method of foam rare earth-nickel alloys according to claim 3, it is characterised in that comprise the following steps：
(1) halide fused salt is put into cell reaction container, drying and dehydrating under vacuum condition, then the immigration of halide fused salt is lazy
Property gaseous environment；
(2) the halide fused salt for treating step (1) is heated to 400-1000 DEG C, then adds rare earth in halide fused salt
Halide；
(3) negative electrode and anode inserting step (2) are added in the fused salt of rare earth halide；
(4) carry out cyclic voltammetry between step (3) negative electrode and anode using electrochemical workstation, determine rare earth from
Reduction potential of the son on foam nickel electrode；
(5) using electrochemical workstation or potentiostat under the conditions of the rare earth reduction potential that step (4) is determined, negative electrode with
Apply voltage between anode；
(6) potentiostatic deposition is used, under the conditions of the reduction potential of different rare earths, the rare earth ion in fused salt is heavy by quick reduction
Accumulate onto foam nickel electrode and formed the foam rare earth-Ni alloy materials of different component.
5. the preparation method of foam rare earth-nickel alloys according to claim 4, it is characterised in that the rare earth halide
Mass ratio with halide fused salt is 1-5%.
6. the preparation method of foam rare earth-nickel alloys according to claim 5, it is characterised in that in the foamed alloy
The molal weight ratio of rare earth and nickel is 1/5,1/3,1/2 or 3/1.
7. the preparation method of foam rare earth-nickel alloys according to claim 4, it is characterised in that the drying and dehydrating
Temperature is 200-300 DEG C, and the time is 24-30 hours.
8. the preparation method of the foam rare earth-nickel alloys according to claim any one of 4-7, it is characterised in that described
Halide fused salt is the molten salt system of single alkaline earth metal chloride or bifurcated alkali mixed halide；The alkaline-earth metal
Chloride is LiCl or CaCl2；The bifurcated alkali mixed halide is LiCl-KCl, NaCl-KCl, NaCl-CaCl2、KF-
KCl or LiF-CaF2。
9. the preparation method of foam rare earth-nickel alloys according to claim 8, it is characterised in that melted when from different
During salt system, the temperature of the halide fused salt heating is respectively LiCl：650-800℃；CaCl2：800-1000℃；LiCl-
KCl：400-600℃；NaCl-KCl：700-900℃；KF-KCl：650-850℃；LiF-CaF2：750-950℃.
10. preparation method according to claim 9, it is characterised in that the rare earth halide is lanthanum trichloride (LaCl3)、
Cerous chloride (CeCl3), neodymium trichloride (NdCl3), samarium trichloride (SmCl3), dysprosium trichloride (DyCl3), tri-chlorination holmium (HoCl3)
Or lanthanum trifluoride (LaF3), cerous fluoride (CeF3), borontrifluoride neodymium (NdF3), borontrifluoride samarium (SmF3), borontrifluoride dysprosium (DyF3) or
Holmium trifluoride (HoF3)。
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