CN107170981A - A kind of Mg Ni La alloys for hydrogen-bearing electrode of surface modification treatment and preparation method and application - Google Patents
A kind of Mg Ni La alloys for hydrogen-bearing electrode of surface modification treatment and preparation method and application Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- 238000012986 modification Methods 0.000 title claims abstract description 36
- 230000004048 modification Effects 0.000 title claims abstract description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 title claims abstract description 28
- 229910000858 La alloy Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000956 alloy Substances 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 50
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- 239000002096 quantum dot Substances 0.000 claims abstract description 25
- 239000010931 gold Substances 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000002114 nanocomposite Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 17
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005300 metallic glass Substances 0.000 claims abstract description 16
- 229910052737 gold Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
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- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
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- 244000131522 Citrus pyriformis Species 0.000 claims 1
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- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical group [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
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- 239000004575 stone Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
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- 235000011083 sodium citrates Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
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- 238000005339 levitation Methods 0.000 description 3
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- 229910020791 La—Mg—Ni Inorganic materials 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—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
-
- B22F1/0003—
-
- 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
- B22F1/14—Treatment of metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of Mg Ni La alloys for hydrogen-bearing electrode of surface modification treatment, it is using magnesium nickel group of the lanthanides non-crystaline amorphous metal as matrix, its area load has golden quantum dot/graphene nano composite membrane, nano Au particle is dispersed in graphene in the composite membrane, 5~10nm of particle diameter of nano Au particle, graphene thickness is 0.8~1nm；The component of the hydrogen-storing alloy as electrode is：Magnesium 34~36%, nickel 34~36%, lanthanum 24~26%, gold 1.5~2.5%, graphene 2~4%, it is to mix magnesium nickel group of the lanthanides non-crystaline amorphous metal, golden quantum dot/graphene composite film and tetrahydrofuran, to being obtained after the surface modification treatment of hydrogen-storing alloy as electrode, it has Corrosion Protection protrusion, the features such as electrochemistry capacitance height, good cycling stability.
Description
Technical field
The present invention relates to a kind of hydrogen-storing alloy as electrode and preparation method and application, more particularly to a kind of surface modification treatment
Mg-Ni-La alloys for hydrogen-bearing electrode and preparation method and application, belong to Metallic Functional Materials technical field.
Background technology
Magnesium-based electrode metal theoretical electrochemistry capacity reaches 1000mAhg-1, possess that hydrogen storage content is big, density is low, rich content and
Cheap the advantages of.The key problem of magnesium-based electrode metal is how to improve its cyclical stability.Over nearly 20 years, although magnesium-based
Hydrogen-storage alloy has obtained research and extremely rapidly development, but hydrogen condition is put in its harsh suction extensively and profoundly as electrode material
The shortcomings of (inhaling hydrogen discharging temperature height, dynamic performance poor) and electrode life short (decay resistance is low) hinders its reality should
With.Numerous researchs show：The circulation volume decline of Mg base hydrogen bearing alloy has with its corrosion in alkali lye closely to be contacted, especially
It is to cause capacity constantly to lose as the corrosion for inhaling protium Mg and as the corrosion for improving electro catalytic activity element Ni
Main cause.
Graphene is the two-dimensional material with individual layer laminated structure, according to《Science》(Xuesong Li,Weiwei
Cai,Jinho An,et al.Large-area synthesis of high-quality and uniform graphene
Films on copper foils [J] .Science, 2009,324,5932:1312-1314.) report：Graphene has high
Heat endurance, chemical stability and environment-friendly, and physics screen layer can be formed between metal surface and active medium, hinder
The corrosion factors such as water proof molecule, oxygen and ion reach metal surface；Nano-metal particle, particularly some noble metal nano amounts
Son point such as Au, Pd, Pt, Ag and ferromagnetic nano metal particle such as Ni, Co, Fe etc. are obtained because with important potential application
Extensive concern.Existing document (Si Y.C, Samulski E T, Synthesis of Water Soluble Graphene [J]
.Nano Lett.2008,8:1679-1683.) report by method physically or chemically by graphene and metallic nanoparticle subgroup
Synthetic composite material, as separating agent, these nano-particles not only can effectively prevent the reunion of graphene film interlayer, Er Qieke
To maintain its excellent physics, chemical property；As filler, these metal nanoparticles can more improve or even enhancing graphite
The performance of alkene-metal nano particle composite material, reaches nano metal particles and graphene cooperates with enhanced doulbe-sides' victory effect.
(C.M.Praveen Kumar, T.V.Venkatesha, Rajashekhara Shabadi, the Preparation and such as Kumar
corrosion behavior of Ni and Ni–graphene composite coatings,Materials
Research Bulletin [J] .2013,48 (4)：1477-1483.) plated using the method for electro-deposition on the surface of mild steel
Ni/ graphene composite coatings, pass through the electro-chemical tests such as Tafel extrapolations, dynamic potential scanning, AC impedance and find, Ni/ stones
Black alkene composite coating shows corrosion resistance more more preferable than pure Ni.(Chen C.H, the Chung T.Y, Shen such as Chen
C.C,et al.Hydrogen storage performance in palladium-doped graphene/carbon
composites,Int.J.Hydrog.Energy[J].2013,38:3681-3688.) combine Pd nano particles and graphene material
Material, is made two-dimensional graphene nanometer sheet, a kind of brand-new hydrogen storage material is generated after being mixed with absorbent charcoal material, the hydrogen storage material
Hydrogen storage content can reach 0.82% (mass fraction) in the case where pressure is 10MPa states, be lifted compared to simple nanometer Pd material
Nearly 49%；(Lei Yun, Chen Feifei, the Li Rong such as the thunder rue of Wuhan University of Technology.Silver-graphene composite material it is in situ prepare and
Performance study, silicate circular [J] .2014,33 (1)：23-26) graphene is prepared by way of functional ionic is adsorbed in advance
With graphene/Ag composites, both specific capacitances are obtained for 12.57F/g and 47.41F/g by cyclic voltammetry, it is clear that stone
The specific capacitance of black alkene/Ag composites is more much higher than simple graphene.Xu of Institutes Of Technology Of Nanjing it is superfine (Xu C, Wang X,
Zhu J W.Fabrication of flexible metal-nanoparticle films using graphene oxide
sheets as substrates,J.Phys.Chem.C[J].2012,112(50):Graphite 19841-19848.) is utilized first
Olefinic oxide is prepared for graphene-metal (Au, Pt, Pd) nano-complex, and result of study shows：Graphene/Pt of preparation is multiple
Compound can as DMFC anode catalyst, the research, which is opened, prepares graphene-nano-particle complex
The new situation.But retrieval is found, about the side using graphene-supported golden quantum-dot modified Mg-Ni-La alloys for hydrogen-bearing electrode
Method and products thereof has not been reported with application.
The content of the invention
There is discharge capacity for magnesium-nickel-group of the lanthanides (Mg-Ni-La systems) amorphous electrode alloy in the prior art low, circulation is steady
A kind of qualitative not enough the problem of, the Mg-Ni-La series hydrogen-storing electrodes that the problem to be solved in the present invention is to provide surface modification treatment are closed
Gold and preparation method and application.
The Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment of the present invention is with magnesium-nickel-group of the lanthanides non-crystaline amorphous metal
For matrix, its area load has golden quantum dot/graphene nano composite membrane, it is characterised in that：Magnesium-the nickel-group of the lanthanides amorphous is closed
Gold is that chemical formula is Mg60-70Ni25-30La5-10Or (Mg60-70Ni25-30)90-100La2-10Non-crystaline amorphous metal；Golden quantum dot/the stone
Black alkene nano composite membrane is comprised the following steps：By graphene oxide in water ultrasonic disperse 30~60 minutes, recycle cell
Pulverizer is crushed 15 ± 5 minutes, is 1ml by chlorauric acid solution and graphene oxide:25~35mg ratio is to graphene oxide
The chlorauric acid solution of 0.05 mol/L is added in solution, is continued ultrasonically treated 10~30 minutes, then by sodium borohydride and oxidation stone
The mass ratio of black alkene is 1:0.2 ratio adds sodium borohydride into reaction solution, is warming up to 90 ± 2 DEG C, adds sodium citrate,
The mass ratio for making sodium citrate and graphene oxide is 1:0.2, production is collected by filtration in back flow reaction 7 ± 0.5 hours, natural cooling
Thing, is washed, and is dried, and grinding obtains golden quantum dot/graphene nano composite membrane, wherein nano Au particle is dispersed in stone
In black alkene, 5~10 nanometers of the particle diameter of nano Au particle, graphene thickness is 0.8~1 nanometer；The Mg- of the surface modification treatment
The component of Ni-La alloys for hydrogen-bearing electrode is by percentage to the quality：Magnesium 34~36%, nickel 34~36%, lanthanum 24~26%, gold
1.5~2.5%, graphene 2~4%.
In the Mg-Ni-La alloys for hydrogen-bearing electrode of above-mentioned surface modification treatment, it is further it is preferable that：The magnesium-
Nickel-group of the lanthanides non-crystaline amorphous metal is that chemical formula is Mg65Ni27La8Or (Mg65Ni27)95La5Non-crystaline amorphous metal；Golden quantum dot/the graphite
Alkene nano composite membrane is comprised the following steps：By graphene oxide in water ultrasonic disperse 45 minutes, recycle cell disruptor
Crush 15 minutes, be 1ml by chlorauric acid solution and graphene oxide:30mg ratio adds 0.05 into graphene oxide solution
The chlorauric acid solution of mol/L, continue ultrasonically treated 20 minutes, then by sodium borohydride and graphene oxide mass ratio be 1:
0.2 ratio adds sodium borohydride into reaction solution, is warming up to 90 DEG C, adds sodium citrate, makes sodium citrate and oxidation stone
The mass ratio of black alkene is 1:0.2, product is collected by filtration in back flow reaction 7 hours, natural cooling, washs, and dries, and grinding obtains
Golden quantum dot/graphene nano composite membrane, wherein nano Au particle is dispersed in graphene, the particle diameter 5 of nano Au particle
~10 nanometers, graphene thickness is 0.8~1 nanometer；The group of the Mg-Ni-La alloys for hydrogen-bearing electrode of the surface modification treatment
Divide and be by percentage to the quality：Magnesium 34~36%, nickel 34~36%, lanthanum 24~26%, gold 1.5~2.5%, graphene 2~
4%.
The preparation method of the Mg-Ni-La alloys for hydrogen-bearing electrode of the surface modification treatment of the present invention, step is：
By magnesium-nickel-group of the lanthanides non-crystaline amorphous metal, golden quantum dot/graphene nano composite membrane and tetrahydrofuran, by 0.7~1.3 gram:0.04~
0.06 gram:1.2~1.5ml ratio mixing, is positioned in high-energy ball milling instrument, the ball milling 30~60 under vacuum, room temperature condition altogether
Minute, with the surface modification treatment to magnesium-nickel-group of the lanthanides hydrogen-storing alloy as electrode, that is, obtain the Mg-Ni-La systems of surface modification treatment
Hydrogen-storing alloy as electrode.
In the preparation method of the Mg-Ni-La alloys for hydrogen-bearing electrode of above-mentioned surface modification treatment, further preferred embodiment
It is：By magnesium-nickel-group of the lanthanides non-crystaline amorphous metal, golden quantum dot/graphene nano composite membrane and tetrahydrofuran, by 1 gram:0.05 gram:1.3
~1.4ml ratio mixing, is positioned in high-energy ball milling instrument, ball milling 45 minutes, that is, obtain surface under vacuum, room temperature condition altogether
The Mg-Ni-La alloys for hydrogen-bearing electrode of modification.
The preparation method of above-mentioned magnesium-nickel-group of the lanthanides non-crystaline amorphous metal is：According to the stoichiometric proportion dispensing of the alloy, that is, press
According to alloy Mg60-70Ni25-30La5-10Or (Mg60-70Ni25-30)90-100La2-10, preferably according to alloy Mg65Ni27La8Or
(Mg65Ni27)95La5Stoichiometric proportion dispensing, then melting is uniform in vacuum levitation melting stove；By the uniform alloy of melting
It is placed in multifunctional amorphous synthesis device, Mg-Ni-La amorphous electrode alloys is prepared using melt-quenching method, speed of quenching is 25-35m/
S, preferably 30m/s.
The Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment of the present invention is preparing high-capacity electrode material
In application.
High capacitance prepared by the Mg-Ni-La alloys for hydrogen-bearing electrode of the surface modification treatment prepared using the inventive method
Electrode material is measured, discharge capacity is verified by experiments and has and be greatly improved.Such as the Mg of surface modification treatment65Ni27La8Alloy maximum is put
Capacitance is 827.6mAh/g, and capability retention is 77.75% after being circulated through 50；And the Mg of non-modified processing65Ni27La8
Alloy maximum discharge capacity is 580.8mAh/g, and capability retention is 43.06% after being circulated through 50.Comparing to find, through this
Method is modified to alloy progress surface, and maximum discharge capacity improves 246.8mAh/g；Capability retention after being circulated through 50
Improve 34.69%.
The present invention provides a kind of Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment and preparation method and application.
Experiment is confirmed：The Mg-Ni-La amorphous electrode alloy discharge capacities prepared using the inventive method, which are had, to be greatly improved, and is followed simultaneously
Ring stability is obviously improved.The quantum-dot modified Mg-Ni-La systems storage hydrogen of novel graphite alkene gold-supported disclosed in this invention
Electrode metal and preparation method thereof, will provide reference frame for the combination property for improving other hydrogen-storing alloy as electrode.
Brief description of the drawings
The XRD spectra of golden quantum dot/graphene nano composite membrane in Fig. 1 present invention.
Wherein：A is the spectrogram of reduced graphene；B is that (technique be reality for the spectrogram of golden quantum dot/graphene nano composite membrane
Apply described in example).
The TEM spectrograms of golden quantum dot/graphene nano composite membrane in Fig. 2 present invention (technique is described in embodiment).
The processing of Fig. 3 the inventive method/(technique is embodiment institute to untreated Mg-Ni-La amorphous electrodes alloy SEM spectrograms
State), Mg-Ni-La amorphous electrode alloy SEM spectrograms.
Wherein：a：Before modified；b：It is modified.
Embodiment
Present invention protection content is further elaborated with reference to embodiment, in order to the present invention it should be appreciated that
Present invention protection content not limited to this.Content i.e. described in embodiment is only used for understanding and illustrates the present invention, without should
Also without limitation on the protection domain described in the claims in the present invention.
General explanation：Non-crystaline amorphous metal is solidified by super chilling, and atom has little time ordered arrangement crystallization during alloy graining, obtains
The solid alloy arrived, it is longrange disorder structure, and the crystal grain without crystal alloy, crystal boundary are present.
Surface, which is modified, to be referred on the premise of material or product originality energy is kept, assign its surface new performance, such as hydrophilic
Property, biocompatibility, antistatic property, dyeability etc..Process for modifying surface is changed using the method for chemistry, physics
The chemical composition or institutional framework of material or workpiece surface are to improve a class heat treatment technics of machine parts or material property.It
Including thermo-chemical treatment (nitriding, carburizing, metallic cementation etc.)；Face coat (low-voltage plasma spraying, low-tension arc spraying, laser
Remelting is compound to wait thin film coating, physical vapour deposition (PVD), chemical vapor deposition etc.) and nonmetallic coating technology etc..These are to strong
Change the technology of part or material surface, assign part high temperature resistant, anticorrosion, wear-resistant, antifatigue, radiation proof, conduction, magnetic conduction etc.
Various new characteristics.Make the part worked originally under high speed, high temperature, high pressure, heavy duty, corrosive medium environment, improve reliable
Property, service life is extended, had a great economic significance and promotional value.
Mg-Ni-La hydrogen-storage alloys belong to middle warm type hydrogen-storage alloy, inhale hydrogen desorption kineticses poor performance, but because it stores hydrogen greatly,
It is lightweight, aboundresources, reasonable price, it is considered to be most have the storage alloy material for hydrogen of development potentiality.Current research direction is main
It is to use element substitution, surface treatment, the electrolyte for being suitable for La-Mg-Ni series hydrogen storage alloys of new preparation process and searching newly
Formula inhales hydrogen discharging rate to solve to inhale hydrogen discharging temperature, raising, and solves La-Mg-Ni series hydrogen storage alloy electrodes in alkali lye
The problems such as corrosion-resistant, cycle life is short, discharge capacity decay is fast.
The invention provides Mg-Ni-La alloys for hydrogen-bearing electrode of a kind of surface modification treatment and preparation method thereof with
Prepare the application in high-capacity electrode material.
Embodiment 1
(1) preparation of amorphous electrode alloy：
According to Mg65Ni27La8Chemical dosage ratio weighs Mg, Ni, La metal derby (purity that purity is more than 99.5%：
99.5%, purchased from Xibei Inst. of Non-Ferrous Metals) totally 100 grams in vacuum levitation melting stove (CXZGX-0.1 types, Shanghai morning prosperous electricity
Stove Co., Ltd) in melt back, take melted metal to be placed in multifunctional amorphous synthesis device (LZK-12A types, copper roller surface
Linear velocity 0-78.5m/s, Shenyang multifunctional vacuum crystallite equipment manufacturing) in, use melt-quenching method (speed of quenching is 30m/s) system
Standby Mg65Ni27La8Amorphous electrode alloy.
(2) preparation of golden quantum dot/graphene nano composite membrane：
200mg graphene oxides are added in 200ml distilled water, (KQ116 types, city of Kunshan's ultrasonic instrument is limited for ultrasound
Company) it is scattered 45 minutes, crushed 15 minutes using cell disruptor, then add the chlorine gold of the mol/Ls of 6.67ml 0.05 thereto
Acid solution (analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group), continues ultrasound 20 minutes, 1g sodium borohydrides is added, in 90 DEG C
1g sodium citrates are added under water bath condition, back flow reaction 7 hours, natural cooling is washed after being neutral to filtrate, filtering,
Product after air drying 24h, takes out grinding in vacuum drying chamber (DZF6050 types, the upper grand experimental facilities Co., Ltd of Nereid),
Golden quantum dot/graphene nano composite membrane is obtained, wherein nano Au particle is dispersed in graphene, the grain of nano Au particle
5~10 nanometers of footpath, graphene thickness is 0.8~1 nanometer.
(3) preparation and test of modified electrode：
Mg-Ni-La non-crystaline amorphous metals, golden quantum dot/graphene nano composite membrane and tetrahydrofuran (THF) are pressed into a certain amount of ratio
(alloy：1 gram, golden quantum dot/graphene nano composite membrane：0.05 gram, THF：1.2~1.5 milliliters) mixing be placed on high energy ball
Grind in instrument (Emax types, German Lay is speeded), in vacuum condition, at room temperature ball milling 45 minutes, alloy can obtain new Mg- after taking out
Ni-La alloys for hydrogen-bearing electrode.
The component of the Mg-Ni-La alloys for hydrogen-bearing electrode of above-mentioned surface modification treatment is by percentage to the quality：Magnesium 34~
36%th, nickel 34~36%, lanthanum 24~26%, gold 1.5~2.5%, graphene 2~4%.
The novel electrode alloyed powder and nickel powder are mixed into powder by 1: 4 mass ratio, binding agent by 2.5wt.% the CMC aqueous solution
It is modulated into ptfe emulsion (60%) by 1: 2 volume ratio, the mass ratio of alloyed powder and binding agent is 3：2, take foam
On a diameter of 20.5mm of nickel sheet disc, the two sides that the slurry of mixed powder and binding agent is uniformly applied to nickel foam disc, and
Slurry is penetrated into the space of nickel foam as far as possible, drying box (DZF6050 types, the limited public affairs of the upper grand experimental facilities of Nereid are put into after coating
Department), dry after 8h and take out at 60 DEG C, be put into powder compressing machine compacting, kept for 10 seconds under 10MPa pressure.Again with hook weldering
Method copper wire is welded in nickel sheet, negative plate prepare complete；The preparation technology of positive plate and negative plate it is identical, difference
It is in and is replaced in hydrogen-storage alloy powder with nickel hydroxide, and nickel powder presses 9:1 mass ratio mixing, the disc diameter of its foam nickel sheet takes
For 25mm.
Electrolyte uses the mixed liquor of the 6mol/L KOH aqueous solution and the 17.5g/L LiOH aqueous solution.Experiment is used
The method of constant current charge-discharge is carried out on BTW2000 (Arbin) tester.Charging current is 100mAh/g, and discharge current is
50mAh/g, the charging interval is set to 12 hours.Charging stands 10 minutes after terminating, and then starts electric discharge, until voltage is reduced to zero
Volt；10 minutes are stood again, are started to charge up again afterwards into next circulation.Experiment is carried out at room temperature, each pair electrode built-in testing
50 circulations, to determine its activation and cycle performance.Whole process records charge/discharge capacity automatically by computer program control
Etc. each item data.
As shown in table 1, the Mg of surface-modified processing65Ni27La8Alloy maximum discharge capacity is 827.6mAh/g, through 50
Capability retention is 77.75% after individual circulation；And the Mg of non-modified processing65Ni27La8Alloy maximum discharge capacity is
580.8mAh/g, capability retention is 43.06% after being circulated through 50.Comparing to be found, surface is carried out to alloy through this method
Modified, maximum discharge capacity improves 246.8mAh/g；Capability retention improves 34.69% after being circulated through 50.
Table 1：Mg65Ni27La8Maximum discharge capacity (C before and after sample modificationmax), the discharge capacity (C after 50 circulations50)
With capability retention (CR) contrast
The comparative example of embodiment 2：Processing and Comparison of experiment results are individually modified to alloy surface using graphene
(1) preparation of amorphous electrode alloy：
According to Mg65Ni27La8Chemical dosage ratio weighs Mg, Ni, La metal derby (purity that purity is more than 99.5%：
99.5%, purchased from Xibei Inst. of Non-Ferrous Metals) totally 100 grams in vacuum levitation melting stove (CXZGX-0.1 types, Shanghai morning prosperous electricity
Stove Co., Ltd) in melt back, take melted metal to be placed in multifunctional amorphous synthesis device (LZK-12A types, copper roller surface
Linear velocity 0-78.5m/s, Shenyang multifunctional vacuum crystallite equipment manufacturing) in, use melt-quenching method (speed of quenching is 30m/s) system
Standby Mg65Ni27La8Amorphous electrode alloy.
(2) preparation of graphene nano film：
200mg graphite oxides are added in 200ml distilled water, ultrasonic (KQ116 types, the limited public affairs of city of Kunshan's ultrasonic instrument
Department) scattered 1 hour, in adding ethylene glycol 20ml back flow reactions under 85 DEG C of water bath conditions 1.5 hours, by reactant suction filtration while hot,
After washing is neutral to filtrate, product normal temperature in vacuum drying chamber (DZF6050 types, the upper grand experimental facilities Co., Ltd of Nereid)
Dry after 24h, take out grinding, obtain graphene nano film.
(3) preparation and test of modified electrode：
By Mg-Ni-La non-crystaline amorphous metals, graphene nano film by a certain amount of than (alloy：1 gram, graphene nano film：0.02
Gram) mixing be placed in high-energy ball milling instrument (Emax types, German Lay is speeded), in vacuum condition, at room temperature ball milling 60 minutes, alloy
The graphenic surface modification to Mg-Ni-La alloys for hydrogen-bearing electrode can be achieved after taking-up.
The modified electrode metal powder completed and nickel powder are mixed into powder by 1: 4 mass ratio, binding agent by 2.5wt.% CMC water
Solution and ptfe emulsion (60%) are modulated into by 1: 2 volume ratio, and the mass ratio of alloyed powder and binding agent is 3：2, take
The a diameter of 20.5mm of foam nickel sheet disc, the slurry of mixed powder and binding agent is uniformly applied to the two sides of nickel foam disc
On, and slurry is penetrated into the space of nickel foam as far as possible, drying box is put into after coating, and (DZF6050 types, the upper grand experimental facilities of Nereid has
Limit company), dry after 8h and take out at 60 DEG C, be put into powder compressing machine compacting, kept for 10 seconds under 10MPa pressure.Use again
Copper wire is welded in nickel sheet by the method for hooking weldering, and prepared by negative plate completes；The preparation technology of positive plate and negative plate it is identical, no
It is that hydrogen-storage alloy powder is replaced with nickel hydroxide with part, and nickel powder presses 9:1 mass ratio mixing, the disc of its foam nickel sheet is straight
Footpath is taken as 25mm.
Electrolyte uses the mixed liquor of the 6mol/L KOH aqueous solution and the 17.5g/L LiOH aqueous solution.Experiment is used
The method of constant current charge-discharge is carried out on BTW2000 (Arbin) tester.Charging current is 100mAh/g, and discharge current is
50mAh/g, the charging interval is set to 12 hours.Charging stands 10 minutes after terminating, and then starts electric discharge, until voltage is reduced to zero
Volt；10 minutes are stood again, are started to charge up again afterwards into next circulation.Experiment is carried out at room temperature, each pair electrode built-in testing
50 circulations, to determine its activation and cycle performance.Whole process records charge/discharge capacity automatically by computer program control
Etc. each item data.
As shown in table 2, the Mg through graphenic surface modification65Ni27La8Alloy maximum discharge capacity is 753.2mAh/
G, capability retention is 60.75% after being circulated through 50；And the Mg of non-modified processing65Ni27La8Alloy maximum discharge capacity is
580.8mAh/g, capability retention is 43.06% after being circulated through 50.Comparing to be found, surface is carried out to alloy through this method
Modified, maximum discharge capacity improves 172.4mAh/g；Capability retention improves 17.69% after being circulated through 50.
Table 2：Mg65Ni27La8Sample graphene before modified after maximum discharge capacity (Cmax), the discharge capacity after 50 circulations
(C50) and capability retention (CR) contrast
The result of above-described embodiment and comparative example is shown：Magnesium-nickel-group of the lanthanides hydrogen-storing alloy as electrode that the method for the present invention is obtained
It is considerably better than the alloy of single graphenic surface modification, and graphene-supported gold nano quantum dot surface modification
Alloy in maximum discharge capacity (Cmax), the discharge capacity (C after 50 circulations50) and capability retention (CR) on have synergy.
Claims (5)
1. a kind of Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment, the hydrogen-storing alloy as electrode is non-with magnesium-nickel-group of the lanthanides
Peritectic alloy is matrix, and its area load has golden quantum dot/graphene nano composite membrane, it is characterised in that：Magnesium-nickel-the group of the lanthanides
Non-crystaline amorphous metal is that chemical formula is Mg60-70Ni25-30La5-10Or (Mg60-70Ni25-30)90-100La2-10Non-crystaline amorphous metal；The gold amount
Sub- point/graphene nano composite membrane is comprised the following steps：By graphene oxide in water ultrasonic disperse 30~60 minutes, then profit
Crushed 15 ± 5 minutes with cell disruptor, be 1ml by chlorauric acid solution and graphene oxide:25~35mg ratio is to oxidation
Add the chlorauric acid solution of 0.05 mol/L in graphene solution, continue ultrasonically treated 10~30 minutes, then by sodium borohydride with
The mass ratio of graphene oxide is 1:0.2 ratio adds sodium borohydride into reaction solution, is warming up to 90 ± 2 DEG C, adds lemon
Lemon acid sodium, the mass ratio for making sodium citrate and graphene oxide is 1:0.2, back flow reaction 7 ± 0.5 hours, natural cooling, filtering
Product is collected, is washed, is dried, grinding obtains golden quantum dot/graphene nano composite membrane, wherein nano Au particle uniformly divides
Dissipate in graphene, 5~10 nanometers of the particle diameter of nano Au particle, graphene thickness is 0.8~1 nanometer；At the surface modification
The component of the Mg-Ni-La alloys for hydrogen-bearing electrode of reason is by percentage to the quality：Magnesium 34~36%, nickel 34~36%, lanthanum 24~
26%th, gold 1.5~2.5%, graphene 2~4%.
2. the Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment according to claim 1, it is characterised in that：It is described
Magnesium-nickel-group of the lanthanides non-crystaline amorphous metal is that chemical formula is Mg65Ni27La8Or (Mg65Ni27)95La5Non-crystaline amorphous metal；The golden quantum dot/
Graphene nano composite membrane is comprised the following steps：By graphene oxide in water ultrasonic disperse 45 minutes, recycle cell powder
Broken machine is crushed 15 minutes, is 1ml by chlorauric acid solution and graphene oxide:30mg ratio is added into graphene oxide solution
The chlorauric acid solution of 0.05 mol/L, continues ultrasonically treated 20 minutes, then be by the mass ratio of sodium borohydride and graphene oxide
1:0.2 ratio adds sodium borohydride into reaction solution, is warming up to 90 DEG C, adds sodium citrate, makes sodium citrate and oxidation
The mass ratio of graphene is 1:0.2, product is collected by filtration in back flow reaction 7 hours, natural cooling, washs, and dries, and grinding is produced
To golden quantum dot/graphene nano composite membrane, wherein nano Au particle is dispersed in graphene, the particle diameter of nano Au particle
5~10 nanometers, graphene thickness is 0.8~1 nanometer；The group of the Mg-Ni-La alloys for hydrogen-bearing electrode of the surface modification treatment
Divide and be by percentage to the quality：Magnesium 34~36%, nickel 34~36%, lanthanum 24~26%, gold 1.5~2.5%, graphene 2~
4%.
3. the preparation method of the Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment described in claim 1 or 2, step is：
By magnesium-nickel-group of the lanthanides non-crystaline amorphous metal, golden quantum dot/graphene nano composite membrane and tetrahydrofuran, by 0.7~1.3 gram:0.04~
0.06 gram:1.2~1.5ml ratio mixing, is positioned in high-energy ball milling instrument, the ball milling 30~60 under vacuum, room temperature condition altogether
Minute, with the surface modification treatment to magnesium-nickel-group of the lanthanides hydrogen-storing alloy as electrode, that is, obtain the Mg-Ni-La systems of surface modification treatment
Hydrogen-storing alloy as electrode.
4. the preparation method of the Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment, its feature according to claim 3
It is：By magnesium-nickel-group of the lanthanides non-crystaline amorphous metal, golden quantum dot/graphene nano composite membrane and tetrahydrofuran, by 1 gram:0.05 gram:
1.3~1.4ml ratio mixing, is positioned in high-energy ball milling instrument, ball milling 45 minutes, that is, obtain under vacuum, room temperature condition altogether
The Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment.
5. the Mg-Ni-La alloys for hydrogen-bearing electrode of surface modification treatment described in claim 1 is preparing high-capacity electrode material
In application.
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Cited By (2)
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| CN108220728A (en) * | 2017-12-26 | 2018-06-29 | 钢铁研究总院 | A kind of high power capacity light graphite alkene catalytic rare earth magnesium-aluminum-based hydrogen storage material and preparation method |
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| CN102891298A (en) * | 2012-08-14 | 2013-01-23 | 青岛大学 | Surface modification method for Mg-Ni-Nd system hydrogen storage electrode alloy |
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| CN107824220A (en) * | 2017-11-09 | 2018-03-23 | 东南大学 | The preparation method of golden nanometer particle graphene melamine sponge composite |
| CN108220728A (en) * | 2017-12-26 | 2018-06-29 | 钢铁研究总院 | A kind of high power capacity light graphite alkene catalytic rare earth magnesium-aluminum-based hydrogen storage material and preparation method |
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Application publication date: 20170915 |