CN110512228A - A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material - Google Patents
A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material Download PDFInfo
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- CN110512228A CN110512228A CN201910871606.5A CN201910871606A CN110512228A CN 110512228 A CN110512228 A CN 110512228A CN 201910871606 A CN201910871606 A CN 201910871606A CN 110512228 A CN110512228 A CN 110512228A
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- Prior art keywords
- nickel
- foam
- plating
- solution
- beaker
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 512
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 254
- 239000006260 foam Substances 0.000 title claims abstract description 219
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000007747 plating Methods 0.000 claims abstract description 73
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 62
- 239000000126 substance Substances 0.000 claims abstract description 46
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229910018104 Ni-P Inorganic materials 0.000 claims abstract description 8
- 229910018536 Ni—P Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 35
- 238000011049 filling Methods 0.000 claims description 27
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000003760 magnetic stirring Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- 239000010431 corundum Substances 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 15
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 13
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 11
- 239000001119 stannous chloride Substances 0.000 claims description 11
- 235000011150 stannous chloride Nutrition 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000002203 pretreatment Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 5
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 210000000038 chest Anatomy 0.000 claims description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000527 sonication Methods 0.000 description 12
- 230000006872 improvement Effects 0.000 description 9
- 239000003755 preservative agent Substances 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 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 description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013064 chemical raw material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- -1 dosage is as follows Chemical compound 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- XATZQMXOIQGKKV-UHFFFAOYSA-N nickel;hydrochloride Chemical compound Cl.[Ni] XATZQMXOIQGKKV-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 231100000481 chemical toxicant Toxicity 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material preparation methods, it is related to hydrogen energy source applied technical field, pretreatment including foamed nickel current collector, prepare chemical nickel phosphorus plating plating solution, Electroless Ni-P Coating is loaded on foam nickel sheet surface, prepares nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and the preparation of nickel phosphide/nickel foam self-supporting electrode.Nickel phosphide obtained by the present invention/nickel foam self-supporting electrode electro Chemical catalytic hydrogen evolution is had excellent performance, property efficient stable, have a wide range of application, required material is from a wealth of sources, and preparation process is convenient, requires pH value condition wide in range, preparation process green non-pollution, technology implementation process is succinctly easy to operate, at low cost, is easy to industrialization promotion.
Description
Technical field
The present invention relates to hydrogen energy source applied technical field, especially a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material
The preparation method of material.
Background technique
The important measure that efficient renewable and clean energy resource is current response environment and energy problem is developed, efficiently can be again
In raw energy resource system, the crucial energy storage means full of potentiality are exactly to convert electrical energy into the chemistry stored with fuel forms
Can, most important and simplest step is exactly to decompose aquatic products hydrogen during this.With the industrial production hydrogen for relying on non-renewable energy
Method is compared, and water electrolysis hydrogen producing is concerned because it has the characteristics that device is simple, production hydrogen purity is high, energy transformation ratio is high；
Catalyst of the efficiency of aquatic products hydrogen dependent on cathode hydrogen evolution reaction and two half-reactions of anode oxygen uptake is decomposed, thus is used for electrochemistry
The performance superiority and inferiority of cathode hydrogen evolution catalysts is the key that restrict hydrogen production by water decomposition efficiency.Currently, it is main industrially to decompose water
Traditional platinum based catalyst is relied on, but in view of noble metals such as platinum bases because it is few, expensive without being able to satisfy in earth's crust reserves
It is engineered the defect of application demand, so to researching and developing, from a wealth of sources, easy to use, catalytic hydrogen evolution performance efficiency is stable, inexpensive easy
The non-precious metal catalyst obtained is very urgent.In addition, during producing hydrogen, different electrolysis units such as pem fuel electricity
Pond, microbiological fuel cell etc. require difference, therefore, base metal based electrochemical cathode hydrogen evolution catalysis material to the pH of electrolytic cell
Except have the characteristics that catalytic hydrogen evolution performance efficiency it is stable, it is cheap and easy to get in addition to, should also have the wide pH scope of application, this is that green produces hydrogen
The core of behave.
In base metal base cathode catalysis material, nickel-phosphorus alloy and using nickel phosphide as the transition metal phosphide of representative by
In cheap and easy to get and received significant attention as liberation of hydrogen material.Domestic and foreign scholars have carried out many researchs in this field, probe into phosphorus
Change the preparation approach of nickel and evaluates the research emphasis that its water electrolysis is the field from Hydrogen Evolution Performance.Currently, the solution such as hydrothermal synthesis
Phase reaction prepares nickel phosphide and mainly white phosphorus or tri-n-octyl phosphine is applied to make phosphorus source, but the range of reaction temperature is by a fixed limit
System, and the toxicity of reaction process intermediate product is big.For this purpose, scholars improve above-mentioned operation, patent
CN109650360A discloses a kind of method that phosphatization nano nickel particles are continuously prepared using micro passage reaction, and being will be organic
Nickel presoma and organic phosphorus sources mixing, after being diluted using the more carbon organic matters of higher boiling as diluent, gained suspension is passed through
Ultrasonic treatment is directly injected into reaction, products therefrom in micro passage reaction and obtains after precipitating, separation, washing and vacuum drying
Phosphatization nano nickel particles.Though made phosphatization nano nickel particles have the characteristics that size is minimum, uniform in size, good dispersion, need
With a variety of toxic chemical substances such as triphenylphosphine and 1- octadecylene, harm to the human body is big.Patent CN109267095A is referred to one
The preparation method of kind new phosphide nickel catalytic material, synthesizes nitrogenous, phosphorus atoms metal organic frameworks with microlayer model method first
Presoma, is then sintered heat treatment under 900~1100 DEG C of high temperature to it, is then prepared for nickel phosphide catalytic hydrogen evolution material, should
Although method is not necessarily to additional phosphorus source, a variety of toxic chemical substances are used when precursor preparation, harm to the human body is big, and
Need that high-temperature operation, energy consumption is high.Existing technological deficiency is prepared based on current nickel phosphide, seeks that a kind of material is from a wealth of sources, preparation
Process is convenient, green non-pollution, the nickel phosphide system for being easy to industrialization promotion, Hydrogen Evolution Performance efficient stable and the width pH scope of application
Standby technology is the important measure for promoting the dissociation hydrogen manufacturing of cathode water power.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material systems
The electrochemical catalysis Hydrogen Evolution Performance of Preparation Method, obtained product is excellent, and property efficient stable has a wide range of application, required material
From a wealth of sources, preparation process is convenient, requires wide in range, preparation process green non-pollution to pH value condition, technology implementation process is succinct
It is easy to operate, it is at low cost, it is easy to industrialization promotion.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of preparation method of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material, comprising the following steps:
(1) pretreatment of foamed nickel current collector: nickel foam is cut into specified size, and carries out pre-treatment；Pre-treatment is obtained
Foam nickel sheet be immersed in stannous chloride solution, sufficiently react and be immersed in palladium chloride solution after cleaning up, it is sufficiently anti-
Should after clean and dry；
(2) prepare chemical nickel phosphorus plating plating solution: with certain proportion by nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride according to
Secondary to be added in the container for filling distilled water, heating stirring is allowed to be completely dissolved；Sodium hypophosphite is added into solution, heating is stirred
It mixes and makes it dissolve, ammonium hydroxide is added dropwise into solution after solution is cooled to room temperature solution ph is adjusted to 4.6~5.0,
It is stirred for uniformly, obtaining chemical nickel plating phosphor bath；
(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface: heating chemical nickel plating phosphor bath to certain temperature, by step
(1) processed foam nickel sheet is immersed in chemical nickel plating phosphor bath in, keeps bath temperature, is controlled plating time, is sufficiently applied
Foam nickel sheet cleaning, drying is taken out after plating；
(4) it prepares nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating: hexamethylenetetramine and six is weighed with certain proportion
Nitric hydrate nickel is placed in the beaker for filling deionized water, is stirred to dissolve, and solution is poured into polytetrafluoroethyllining lining, so
Polytetrafluoroethyllining lining is put into reaction kettle afterwards, hydro-thermal reaction is carried out after heating and obtains nickel hydroxide/containing nickel-phosphorus coating
Nickel foam presoma, and by its cleaning, drying；
(5) nickel phosphide/nickel foam self-supporting electrode preparation: by nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and
Sodium hypophosphite powder is respectively put into two corundum porcelain boats, and two corundum porcelain boats are put into the tube furnace furnace for having nitrogen atmosphere
In thorax, heating furnace simultaneously obtains nickel phosphide/nickel foam electrochemical function liberation of hydrogen material by phosphating reaction after keeping the temperature a period of time,
A kind of specifically nickel phosphide/nickel foam self-supporting electrode.
Technical solution of the present invention further improvement lies in that: the pre-treatment step in step (1) includes the bubble after cutting
Foam nickel sheet is placed in the beaker for filling acetone, is then placed the beaker in ultrasonic cleaner and is ultrasonically treated, then will place
Foam nickel sheet after reason is taken out from beaker, is cleaned 5 times with deionized water, is put into the beaker for fill hydrochloric acid and performs etching, so
After place the beaker in ultrasonic cleaner and be ultrasonically treated, foam nickel sheet is taken out from beaker later, uses deionized water
Cleaning 5 times, after foam nickel sheet be placed in the beaker for fill dehydrated alcohol be ultrasonically treated, then treated by dehydrated alcohol
Foam nickel sheet is taken out from beaker, cleans 5 juxtapositions with deionized water and dries in a vacuum drying oven.
Technical solution of the present invention further improvement lies in that: in step (1) by foam nickel sheet be immersed in density be 10g/L chlorine
Pass through ultrasonic cleaning machine at room temperature while change in stannous solution and be ultrasonically treated, later by foam nickel sheet from stannous chloride
It takes out in solution, is cleaned 5 times with deionized water；It again will be in the palladium chloride solution of foam nickel sheet submergence 0.2g/L and by super
Sound washer is ultrasonically treated at room temperature, later takes out foam nickel sheet from palladium chloride solution, with deionized water by its
Cleaning 5 times；The foam nickel sheet of washes clean is finally placed in a vacuum drying oven drying.
Technical solution of the present invention further improvement lies in that: nickel sulfate, sodium hypophosphite, citric acid, fourth in step (2)
Diacid, sodium acetate, ammonium acid fluoride mass ratio be 25~30:15~30:10~15:3~5:3~5:3~5.
Technical solution of the present invention further improvement lies in that: first by nickel sulfate, citric acid, succinic acid, second in step (2)
Sour sodium, ammonium acid fluoride are added in the beaker for filling distilled water, and are placed the beaker on magnetic stirring apparatus, Stirring control rotation
Button simultaneously opens computer heating control switch, and control solution temperature is 40~50 DEG C, and agitating solution is completely dissolved each reagent being added；Again
Sodium hypophosphite is added in solution, is stirred to dissolve, after sodium hypophosphite is completely dissolved, closes magnetic stirring apparatus
Computer heating control switch, makes solution temperature cooled to room temperature.
Technical solution of the present invention further improvement lies in that: step sets the beaker for filling chemical nickel plating phosphor bath in (3)
In the temperature constant magnetic stirring water bath for filling deionized water, heating chemical nickel-plated phosphor bath temperature is to 80~85 DEG C, by foam
Nickel sheet is immersed in chemical nickel plating phosphor bath, and keeping bath temperature is 80~85 DEG C, and control plating time is 40~60min；It is complete
Foam nickel sheet is chemically taken out after full response in nickel plating phosphor bath, clean 5 times with deionized water, after place it in vacuum and do
It is dried in dry case.
Technical solution of the present invention further improvement lies in that: hexamethylenetetramine and Nickelous nitrate hexahydrate in step (4)
Mole the ratio between be 1:1.
Technical solution of the present invention further improvement lies in that:: the amount of loading with of foam nickel sheet surface nickel phosphorus coating in step (3)
The ratio between mole with sodium hypophosphite is 1:5, and the amount of loading with i.e. foam nickel sheet is of poor quality before and after chemical plating.
Technical solution of the present invention further improvement lies in that: step puts the corundum porcelain boat for holding sodium hypophosphite in (5)
Close to tube furnace nitrogen inlet side, heating furnace is to 300 DEG C and keeps the temperature 2h.
Technical solution of the present invention further improvement lies in that: in step (5) by two corundum porcelain boats in tube furnace burner hearth
After centre places, nitrogen cylinder switching knob is opened, slowly enters nitrogen in tube furnace, the intake of nitrogen is 10~30 mL/
min；Diamond heating switch is opened simultaneously, and fire box temperature is made to be increased to 300 DEG C by room temperature with the heating rate of 1~5 DEG C/min,
Temperature is kept to make nickel hydroxide/2 h of nickel foam presoma phosphating reaction containing nickel-phosphorus coating.
By adopting the above-described technical solution, the technological progress achieved by the present invention is:
Nickel phosphide obtained by the present invention/nickel foam self-supporting electrode electro Chemical catalytic hydrogen evolution is had excellent performance, property efficient stable,
Have a wide range of application, there is efficient catalytic to produce hydrogen efficiency in acid, alkaline medium, in electrochemical catalysis hydrogen manufacturing, hydrodesulfurization, choosing
Selecting property adds hydrogen and other hydrogen-involved reaction fields to have broad application prospects.The present invention relates to material source needed for technique is wide
General, raw material is cheap and easy to get, and preparation process is convenient, wide in range to pH value condition requirement, and preparation process green non-pollution, technology was implemented
Journey is succinctly easy to operate, is conducive to large-scale industrial production application.
The corundum porcelain boat for holding sodium hypophosphite is placed on close to tube furnace nitrogen inlet side, to ensure ortho phosphorous acid
The phosphine gas that sodium decomposes can make its phosphatization with the nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating comes into full contact with,
Improve reaction efficiency.
Without the adhesive effect of binder, nickel phosphide liberation of hydrogen catalyst loads with secured, change on nickel foam supporter
Stablize.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of untreated nickel foam；
Fig. 2 is the partial enlarged view of Fig. 1；
Fig. 3 is to load with the scanning electron microscope diagram of the foam nickel sheet of Electroless Ni-P Coating on surface；
Fig. 4 is the partial enlarged view of Fig. 3；
Fig. 5 is the X-ray diffraction spectrogram of nickel phosphide/nickel foam self-supporting electrode and nickel foam；
Fig. 6 is that the linear scan of the nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glass-carbon electrode in acid medium lies prostrate
Peace method curve；
Fig. 7 is that the linear scan of the nickel phosphide/nickel foam self-supporting electrode, nickel foam, commercial glass-carbon electrode in alkaline medium lies prostrate
Peace method curve.
Specific embodiment
Technical solution of the present invention and working principle are done further specifically below with reference to schematic diagram and specific embodiment
It is bright.Part relevant to the technical solution of the claims in the present invention is illustrated only in attached drawing of the invention, and not all, the present invention
Specific embodiment be also only through the optimal embodiment in part technical solution of the present invention be illustrated, not realize
Whole specific technical solutions of the object of the invention, embodiment part cannot function as the range of the claims in the present invention protection.Below
The present invention is described in further details in conjunction with the embodiments:
Embodiment 1
(1) pretreatment of foamed nickel current collector:
1. the cutting and pre-treatment of nickel foam:
Commercially available nickel foam is cut into the small pieces that length and width is all 2cm first, is then placed in the foam nickel sheet after cutting
In the beaker for filling 50mL acetone, vessel port is sealed with preservative film, then places the beaker in ultrasonic cleaner and is surpassed
Sonication, the power of ultrasonic cleaner are 90W, sonication treatment time 30min, and realization at room temperature removes foam nickel sheet
Oil；The foam nickel sheet after carrying out oil removal treatment with acetone under ultrasound is taken out from beaker later, it is cleaned 5 with deionized water
It is secondary, then by after acetone treatment and washes clean foam nickel sheet be placed in fill 50mL concentration be 2mol/L hydrochloric acid beaker in into
Row etching, vessel port is sealed with preservative film, then places the beaker in ultrasonic cleaner and is ultrasonically treated, ultrasonic wave is clear
The power for washing device is 90W, sonication treatment time 30min.Later by under ultrasound with the hydrochloric acid nickel foam that performs etching that treated
Piece takes out from beaker, it is cleaned 5 times with deionized water, finally by simultaneously the foam nickel sheet of washes clean is placed in after HCl treatment
It fills in the beaker of 50mL dehydrated alcohol and removes other impurities.The sealing of vessel port preservative film is placed the beaker into ultrasonic cleaning
It is ultrasonically treated in device, the power of ultrasonic cleaner is 90W, sonication treatment time 30min.It later will be at dehydrated alcohol
Foam nickel sheet after reason is taken out from beaker, it is cleaned 5 juxtapositions in a vacuum drying oven in 60 DEG C of temperature with deionized water
Lower drying, the vacuum degree of vacuum oven are -0.1MPa.
2. the activation processing of foam nickel sheet:
Pretreated foam nickel sheet is immersed in the stannous chloride solution of pre-prepared 10g/L, it is ultrasonic at room temperature
10~20min is handled, the power of ultrasonic cleaner used is 90W, foam nickel sheet taken out from stannous chloride solution later,
And it is cleaned 5 times with deionized water.
3. the sensitized treatment of foam nickel sheet:
Foam nickel sheet after activation processing is immersed in the palladium chloride solution of pre-prepared 0.2g/L, at room temperature at ultrasound
20~30min is managed, the power of ultrasonic cleaner used is 90W, later takes out foam nickel sheet from palladium chloride solution, is used in combination
Deionized water is cleaned 5 times；Finally the foam nickel sheet of washes clean is placed in a vacuum drying oven and is dried at a temperature of 60 DEG C,
The vacuum degree of vacuum oven is -0.1MPa.
(2) chemical nickel phosphorus plating plating solution is prepared:
1. chemical raw material used:
The mass ratio relationship of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate, ammonium acid fluoride, dosage is as follows,
Nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium acid fluoride=25:15:10:3:3:3；
2. the process for preparation of chemical nickel plating phosphor bath:
Nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride are added sequentially in the beaker for filling 1L distilled water first,
And place the beaker on magnetic stirring apparatus, Stirring control handle and computer heating control switch are opened, control solution temperature is 40
~50 DEG C, agitating solution is completely dissolved each reagent being added；
After being completely dissolved etc. above-mentioned each reagent, then sodium hypophosphite is added in solution, stirred to dissolve, to ortho phosphorous acid
After sodium is completely dissolved, the computer heating control switch of magnetic stirring apparatus is closed, makes solution temperature by 40~50 DEG C of cooled to room temperatures；
It is 4.6 that the ammonia spirit that mass percentage concentration is 25%, which is added dropwise in solution to adjust solution ph, with dropper, together
When pH meter probe is placed in solution to the variation for monitoring pH value, to pH value adjustment after solution delayed by magnetic stirring apparatus
10~20min of slow stirring, that is, prepared chemical nickel plating phosphor bath used.
(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface:
1. the beaker for filling chemical nickel plating phosphor bath is placed in the temperature constant magnetic stirring water bath for filling deionized water, heating makes
Bath temperature is 80 DEG C；
2. foam nickel sheet activated in step (1) and sensitized treatment is soaked after chemical nickel phosphorus plating bath temperature rises to 80 DEG C
Not in chemical nickel plating phosphor bath, nickel-phosphorus coating is deposited in foam nickel sheet surface chemical plating, bath temperature is kept during plating
It is 80 DEG C, plating time 40min；
3. after chemical plating plating, foam nickel sheet chemically being taken out in nickel plating phosphor bath, is first cleaned 5 with deionized water
It is secondary, it then places it in vacuum oven and is dried at a temperature of 60 DEG C, the vacuum degree of vacuum oven is -0.1MPa；
4. calculating the amount of loading with of foam nickel sheet surface nickel phosphorus coating, the as nickel phosphor plating of poor quality before and after foam nickel sheet chemistry plating
The amount of loading with of layer.
(4) nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating is prepared:
1. preparing material used:
Material used in the preparation of nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating have the pure grade hexamethylenetetramine of analysis,
Nickelous nitrate hexahydrate, the molar ratio relationship of above-mentioned raw materials dosage are hexamethylenetetramine: Nickelous nitrate hexahydrate=2:1；
2. nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating preparation process:
Precise 1.402g hexamethylenetetramine and 1.454g Nickelous nitrate hexahydrate are placed in the burning for filling 20mL deionized water
In cup, then places it on magnetic stirring apparatus and stir to dissolve uniformly, mixing time 6h, whipping temp is room
Temperature；Solution is poured into the polytetrafluoroethyllining lining that volume is 25mL after stirring, is then put into polytetrafluoroethyllining lining
In reaction kettle, is put it into after tightening and carry out hydro-thermal reaction 10h in the burner hearth that temperature is 100 DEG C, after stove is cooled to room temperature,
The presoma prepared is taken out and is respectively cleaned three times with deionized water and ethyl alcohol, is finally placed it in vacuum oven 60
It is dried at a temperature of DEG C, the vacuum degree of vacuum oven is -0.1MPa, has obtained nickel hydroxide/foam containing nickel-phosphorus coating
Nickel presoma.
(5) nickel phosphide/nickel foam self-supporting electrode is prepared:
1. preparing material used:
Nickel phosphide/material used in the preparation of nickel foam self-supporting electrode has the pure grade sodium hypophosphite of analysis and nickel hydroxide/contains
The nickel foam presoma of nickel-phosphorus coating, sodium hypophosphite and nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating quality
Than carrying out metered amount in the ratio between nickel foam on piece amount of loading with sodium hypophosphite and nickel-phosphorus coating；Foam nickel sheet surface nickel phosphorus coating
The amount of loading with and sodium hypophosphite the ratio between mole be 1:5；
2. nickel phosphide/nickel foam self-supporting electrode preparation process:
A, nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and sodium hypophosphite powder two have been respectively put into just first
In beautiful porcelain boat, two corundum porcelain boats are then put into tube furnace burner hearth center, wherein the corundum porcelain boat for holding sodium hypophosphite is answered
Be placed on close to tube furnace nitrogen inlet side, with ensure phosphine gas that sodium hypophosphite is decomposed can with nickel hydroxide/
Nickel foam presoma containing nickel-phosphorus coating, which comes into full contact with, makes its phosphatization；
B, after two corundum porcelain boats place in tube furnace burner hearth center, nitrogen cylinder switching knob is opened, nitrogen is slowly entered
In tube furnace, the intake of nitrogen is 10mL/min；Diamond heating switch is opened simultaneously, makes fire box temperature with 1 DEG C/min's
Heating rate is increased to 300 DEG C by room temperature, makes nickel hydroxide/nickel foam presoma phosphatization containing nickel-phosphorus coating anti-at 300 DEG C
Answer 2h；
C, after phosphating reaction, tube furnace power supply is closed, fire box temperature cooled to room temperature is made, it is cooling to tube furnace burner hearth
To room temperature, nickel hydroxide after phosphorating treatment/nickel foam presoma containing nickel-phosphorus coating is taken out, has been obtained for water power
Dissociate nickel phosphide/nickel foam self-supporting electrode used in liberation of hydrogen.
(6) nickel phosphide/nickel foam self-supporting electrode electrochemical cathode Hydrogen Evolution Performance is tested:
Using standard three electrode system, using nickel foam, business platinum carbon electrode and made nickel phosphide/nickel foam self-supporting electrode as
Working electrode, saturation Ag/AgCl electrode are reference electrode, and carbon-point is to utilize Shanghai Chen Hua CHI660E electrochemical operation to electrode
Stand, using linear sweep voltammetry, respectively 0.5mol/L sulfuric acid, 1.0mol/L potassium hydroxide solution in carry out Hydrogen Evolution Performance
Evaluation, relative to reversible hydrogen electrode current potential, test scope is 0~-0.7V, sweep speed 2mV/s.
Fig. 1, Fig. 2 are the scanning electron microscope diagrams of untreated nickel foam, and the surface of foam nickel sheet is not passed through completely
Processing.It can be seen that reticulating structure inside foam nickel sheet, it is interweaved, the smooth no protrusion in surface has metal lines.
Fig. 3, Fig. 4 are to load with the scanning electron microscope diagram of the foam nickel sheet of Electroless Ni-P Coating on surface, in foam
After nickel surface chemical nickel phosphorus plating then two steps in low temperature synthesis nickel phosphide scanning electron microscope (SEM) photograph, as can be seen from the figure radius be
For 4 μm or so of flower-shaped nickel phosphide homoepitaxial on foam nickel skeleton, flower-shaped phosphatization nickel surface is relatively rough, and there are many hole knots
Structure is capable of providing bigger specific surface area active.
Fig. 5 is the X-ray diffraction spectrogram of nickel phosphide/nickel foam self-supporting electrode and nickel foam, and horizontal x-axis indicates angle
(°), longitudinal y-axis indicate intensity (a.u.), wherein the three strong peaks of 2 θ=44.8 °, 52.2 °, 76.8 ° appearance nearby are respectively
(111) (200) (220) crystal face of nickel, remaining peak of flower-shaped nickel phosphide/nickel foam of generation other than these three strong peaks and phosphorus
The diffraction maximum standard card for changing nickel matches and crystallinity is good.
Fig. 6 is that nickel phosphide/nickel foam self-supporting electrode in acid medium, nickel foam, commercial glass-carbon electrode are linearly swept
Voltammetry curve is retouched, is the polarization curve in the sulfuric acid solution of pH=0 0.5mol/L, horizontal x-axis indicates potential, and unit is
mV；Longitudinal y-axis indicates current density, and unit is mA/cm2.Sweep speed is 2mV/s, and using commercial platinum carbon electrode, electric current is close
Degree is -10mA/cm2Corresponding voltage is -78mV, better than the most of phosphide catalysis materials having disclosed at present.
Fig. 7 is that nickel phosphide/nickel foam self-supporting electrode in alkaline medium, nickel foam, commercial glass-carbon electrode are linearly swept
Voltammetry curve to be retouched, is the polarization curve in the potassium hydroxide solution of pH=14 1.0mol/L, horizontal x-axis indicates potential,
Unit is mV；Longitudinal y-axis indicates current density, and unit is mA/cm2.Sweep speed is 2mV/s, using commercial platinum carbon electrode,
Current density is -10mA/cm2Corresponding voltage is -91mV, compared to the most of phosphide catalysis materials having disclosed at present
With obvious gain effect.
Embodiment 2
(1) pretreatment of foamed nickel current collector:
1. the cutting and pre-treatment of nickel foam:
Commercially available nickel foam is cut into the small pieces that length and width is all 2cm first, is then placed in the foam nickel sheet after cutting
In the beaker for filling 50mL acetone, vessel port is sealed with preservative film, then places the beaker in ultrasonic cleaner and is surpassed
Sonication, the power of ultrasonic cleaner are 90W, sonication treatment time 30min, and realization at room temperature removes foam nickel sheet
Oil；The foam nickel sheet after carrying out oil removal treatment with acetone under ultrasound is taken out from beaker later, it is cleaned 5 with deionized water
It is secondary, then by after acetone treatment and washes clean foam nickel sheet be placed in fill 50mL concentration be 2mol/L hydrochloric acid beaker in into
Row etching, vessel port is sealed with preservative film, then places the beaker in ultrasonic cleaner and is ultrasonically treated, ultrasonic wave is clear
The power for washing device is 90W, sonication treatment time 30min.Later by under ultrasound with the hydrochloric acid nickel foam that performs etching that treated
Piece takes out from beaker, it is cleaned 5 times with deionized water, finally by simultaneously the foam nickel sheet of washes clean is placed in after HCl treatment
It fills in the beaker of 50mL dehydrated alcohol and removes other impurities.The sealing of vessel port preservative film is placed the beaker into ultrasonic cleaning
It is ultrasonically treated in device, the power of ultrasonic cleaner is 90W, sonication treatment time 30min.It later will be at dehydrated alcohol
Foam nickel sheet after reason is taken out from beaker, it is cleaned 5 juxtapositions in a vacuum drying oven in 60 DEG C of temperature with deionized water
Lower drying, the vacuum degree of vacuum oven are -0.1MPa.
2. the activation processing of foam nickel sheet:
Pretreated foam nickel sheet is immersed in the stannous chloride solution of pre-prepared 10g/L, it is ultrasonic at room temperature
10~20min is handled, the power of ultrasonic cleaner used is 90W, foam nickel sheet taken out from stannous chloride solution later,
And it is cleaned 5 times with deionized water.
3. the sensitized treatment of foam nickel sheet:
Foam nickel sheet after activation processing is immersed in the palladium chloride solution of pre-prepared 0.2g/L, at room temperature at ultrasound
20~30min is managed, the power of ultrasonic cleaner used is 90W, later takes out foam nickel sheet from palladium chloride solution, is used in combination
Deionized water is cleaned 5 times；Finally the foam nickel sheet of washes clean is placed in a vacuum drying oven and is dried at a temperature of 60 DEG C,
The vacuum degree of vacuum oven is -0.1MPa.
(2) chemical nickel phosphorus plating plating solution is prepared:
1. chemical raw material used:
The mass ratio relationship of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate, ammonium acid fluoride, dosage is as follows,
Nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium acid fluoride=28:23:13:4:4:4；
2. the process for preparation of chemical nickel plating phosphor bath:
Nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride are added sequentially in the beaker for filling 1L distilled water first,
And place the beaker on magnetic stirring apparatus, Stirring control handle and computer heating control switch are opened, control solution temperature is 40
~50 DEG C, agitating solution is completely dissolved each reagent being added；
After being completely dissolved etc. above-mentioned each reagent, then sodium hypophosphite is added in solution, stirred to dissolve, to ortho phosphorous acid
After sodium is completely dissolved, the computer heating control switch of magnetic stirring apparatus is closed, makes solution temperature by 40~50 DEG C of cooled to room temperatures；
It is 4.8 that the ammonia spirit that mass percentage concentration is 25%, which is added dropwise in solution to adjust solution ph, with dropper, together
When pH meter probe is placed in solution to the variation for monitoring pH value, to pH value adjustment after solution delayed by magnetic stirring apparatus
10~20min of slow stirring, that is, prepared chemical nickel plating phosphor bath used.
(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface:
1. the beaker for filling chemical nickel plating phosphor bath is placed in the temperature constant magnetic stirring water bath for filling deionized water, heating makes
Bath temperature is 83 DEG C；
2. foam nickel sheet activated in step (1) and sensitized treatment is soaked after chemical nickel phosphorus plating bath temperature rises to 83 DEG C
Not in chemical nickel plating phosphor bath, nickel-phosphorus coating is deposited in foam nickel sheet surface chemical plating, bath temperature is kept during plating
It is 83 DEG C, plating time 50min；
3. after chemical plating plating, foam nickel sheet chemically being taken out in nickel plating phosphor bath, is first cleaned 5 with deionized water
It is secondary, it then places it in vacuum oven and is dried at a temperature of 60 DEG C, the vacuum degree of vacuum oven is -0.1MPa；
4. calculating the amount of loading with of foam nickel sheet surface nickel phosphorus coating, the as nickel phosphor plating of poor quality before and after foam nickel sheet chemistry plating
The amount of loading with of layer.
(4) nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating is prepared:
1. preparing material used:
Material used in the preparation of nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating have the pure grade hexamethylenetetramine of analysis,
Nickelous nitrate hexahydrate, the molar ratio relationship of above-mentioned raw materials dosage are hexamethylenetetramine: Nickelous nitrate hexahydrate=2:1；
2. nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating preparation process:
Precise 1.402g hexamethylenetetramine and 1.454g Nickelous nitrate hexahydrate are placed in the burning for filling 20mL deionized water
In cup, then places it on magnetic stirring apparatus and stir to dissolve uniformly, mixing time 6h, whipping temp is room
Temperature；Solution is poured into the polytetrafluoroethyllining lining that volume is 25mL after stirring, is then put into polytetrafluoroethyllining lining
In reaction kettle, is put it into after tightening and carry out hydro-thermal reaction 10h in the burner hearth that temperature is 100 DEG C, after stove is cooled to room temperature,
The presoma prepared is taken out and is respectively cleaned three times with deionized water and ethyl alcohol, is finally placed it in vacuum oven 60
It is dried at a temperature of DEG C, the vacuum degree of vacuum oven is -0.1MPa, has obtained nickel hydroxide/foam containing nickel-phosphorus coating
Nickel presoma.
(5) nickel phosphide/nickel foam self-supporting electrode is prepared:
1. preparing material used:
Nickel phosphide/material used in the preparation of nickel foam self-supporting electrode has the pure grade sodium hypophosphite of analysis and nickel hydroxide/contains
The nickel foam presoma of nickel-phosphorus coating, sodium hypophosphite and nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating quality
Than carrying out metered amount in the ratio between nickel foam on piece amount of loading with sodium hypophosphite and nickel-phosphorus coating；Foam nickel sheet surface nickel phosphorus coating
The amount of loading with and sodium hypophosphite the ratio between mole be 1:5；
2. nickel phosphide/nickel foam self-supporting electrode preparation process:
A, nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and sodium hypophosphite powder two have been respectively put into just first
In beautiful porcelain boat, two corundum porcelain boats are then put into tube furnace burner hearth center, wherein the corundum porcelain boat for holding sodium hypophosphite is answered
Be placed on close to tube furnace nitrogen inlet side, with ensure phosphine gas that sodium hypophosphite is decomposed can with nickel hydroxide/
Nickel foam presoma containing nickel-phosphorus coating, which comes into full contact with, makes its phosphatization；
B, after two corundum porcelain boats place in tube furnace burner hearth center, nitrogen cylinder switching knob is opened, nitrogen is slowly entered
In tube furnace, the intake of nitrogen is 20mL/min；Diamond heating switch is opened simultaneously, makes fire box temperature with 3 DEG C/min's
Heating rate is increased to 300 DEG C by room temperature, makes nickel hydroxide/nickel foam presoma phosphatization containing nickel-phosphorus coating anti-at 300 DEG C
Answer 2h；
C, after phosphating reaction, tube furnace power supply is closed, fire box temperature cooled to room temperature is made, it is cooling to tube furnace burner hearth
To room temperature, nickel hydroxide after phosphorating treatment/nickel foam presoma containing nickel-phosphorus coating is taken out, has been obtained for water power
Dissociate nickel phosphide/nickel foam self-supporting electrode used in liberation of hydrogen.
(6) nickel phosphide/nickel foam self-supporting electrode electrochemical cathode Hydrogen Evolution Performance is tested:
Using standard three electrode system, using nickel foam, business platinum carbon electrode and made nickel phosphide/nickel foam self-supporting electrode as
Working electrode, saturation Ag/AgCl electrode are reference electrode, and carbon-point is to utilize Shanghai Chen Hua CHI660E electrochemical operation to electrode
Stand, using linear sweep voltammetry, respectively 0.5mol/L sulfuric acid, 1.0mol/L potassium hydroxide solution in carry out Hydrogen Evolution Performance
Evaluation, relative to reversible hydrogen electrode current potential, test scope is 0~-0.7V, sweep speed 2mV/s.
Its Hydrogen Evolution Performance and the made sample of embodiment 1 are without marked difference, so be no longer described in detail.
Embodiment 3
(1) pretreatment of foamed nickel current collector:
1. the cutting and pre-treatment of nickel foam:
Commercially available nickel foam is cut into the small pieces that length and width is all 2cm first, is then placed in the foam nickel sheet after cutting
In the beaker for filling 50mL acetone, vessel port is sealed with preservative film, then places the beaker in ultrasonic cleaner and is surpassed
Sonication, the power of ultrasonic cleaner are 90W, sonication treatment time 30min, and realization at room temperature removes foam nickel sheet
Oil；The foam nickel sheet after carrying out oil removal treatment with acetone under ultrasound is taken out from beaker later, it is cleaned 5 with deionized water
It is secondary, then by after acetone treatment and washes clean foam nickel sheet be placed in fill 50mL concentration be 2mol/L hydrochloric acid beaker in into
Row etching, vessel port is sealed with preservative film, then places the beaker in ultrasonic cleaner and is ultrasonically treated, ultrasonic wave is clear
The power for washing device is 90W, sonication treatment time 30min.Later by under ultrasound with the hydrochloric acid nickel foam that performs etching that treated
Piece takes out from beaker, it is cleaned 5 times with deionized water, finally by simultaneously the foam nickel sheet of washes clean is placed in after HCl treatment
It fills in the beaker of 50mL dehydrated alcohol and removes other impurities.The sealing of vessel port preservative film is placed the beaker into ultrasonic cleaning
It is ultrasonically treated in device, the power of ultrasonic cleaner is 90W, sonication treatment time 30min.It later will be at dehydrated alcohol
Foam nickel sheet after reason is taken out from beaker, it is cleaned 5 juxtapositions in a vacuum drying oven in 60 DEG C of temperature with deionized water
Lower drying, the vacuum degree of vacuum oven are -0.1MPa.
2. the activation processing of foam nickel sheet:
Pretreated foam nickel sheet is immersed in the stannous chloride solution of pre-prepared 10g/L, it is ultrasonic at room temperature
10~20min is handled, the power of ultrasonic cleaner used is 90W, foam nickel sheet taken out from stannous chloride solution later,
And it is cleaned 5 times with deionized water.
3. the sensitized treatment of foam nickel sheet:
Foam nickel sheet after activation processing is immersed in the palladium chloride solution of pre-prepared 0.2g/L, at room temperature at ultrasound
20~30min is managed, the power of ultrasonic cleaner used is 90W, later takes out foam nickel sheet from palladium chloride solution, is used in combination
Deionized water is cleaned 5 times；Finally the foam nickel sheet of washes clean is placed in a vacuum drying oven and is dried at a temperature of 60 DEG C,
The vacuum degree of vacuum oven is -0.1MPa.
(2) chemical nickel phosphorus plating plating solution is prepared:
1. chemical raw material used:
The mass ratio relationship of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate, ammonium acid fluoride, dosage is as follows,
Nickel sulfate: sodium hypophosphite: citric acid: succinic acid: sodium acetate: ammonium acid fluoride=30:30:15:5:5:5；
2. the process for preparation of chemical nickel plating phosphor bath:
Nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride are added sequentially in the beaker for filling 1L distilled water first,
And place the beaker on magnetic stirring apparatus, Stirring control handle and computer heating control switch are opened, control solution temperature is 40
~50 DEG C, agitating solution is completely dissolved each reagent being added；
After being completely dissolved etc. above-mentioned each reagent, then sodium hypophosphite is added in solution, stirred to dissolve, to ortho phosphorous acid
After sodium is completely dissolved, the computer heating control switch of magnetic stirring apparatus is closed, makes solution temperature by 40~50 DEG C of cooled to room temperatures；
It is 5.0 that the ammonia spirit that mass percentage concentration is 25%, which is added dropwise in solution to adjust solution ph, with dropper, together
When pH meter probe is placed in solution to the variation for monitoring pH value, to pH value adjustment after solution delayed by magnetic stirring apparatus
10~20min of slow stirring, that is, prepared chemical nickel plating phosphor bath used.
(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface:
1. the beaker for filling chemical nickel plating phosphor bath is placed in the temperature constant magnetic stirring water bath for filling deionized water, heating makes
Bath temperature is 85 DEG C；
2. foam nickel sheet activated in step (1) and sensitized treatment is soaked after chemical nickel phosphorus plating bath temperature rises to 85 DEG C
Not in chemical nickel plating phosphor bath, nickel-phosphorus coating is deposited in foam nickel sheet surface chemical plating, bath temperature is kept during plating
It is 85 DEG C, plating time 60min；
3. after chemical plating plating, foam nickel sheet chemically being taken out in nickel plating phosphor bath, is first cleaned 5 with deionized water
It is secondary, it then places it in vacuum oven and is dried at a temperature of 60 DEG C, the vacuum degree of vacuum oven is -0.1MPa；
4. calculating the amount of loading with of foam nickel sheet surface nickel phosphorus coating, the as nickel phosphor plating of poor quality before and after foam nickel sheet chemistry plating
The amount of loading with of layer.
(4) nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating is prepared:
1. preparing material used:
Material used in the preparation of nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating have the pure grade hexamethylenetetramine of analysis,
Nickelous nitrate hexahydrate, the molar ratio relationship of above-mentioned raw materials dosage are hexamethylenetetramine: Nickelous nitrate hexahydrate=2:1；
2. nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating preparation process:
Precise 1.402g hexamethylenetetramine and 1.454g Nickelous nitrate hexahydrate are placed in the burning for filling 20mL deionized water
In cup, then places it on magnetic stirring apparatus and stir to dissolve uniformly, mixing time 6h, whipping temp is room
Temperature；Solution is poured into the polytetrafluoroethyllining lining that volume is 25mL after stirring, is then put into polytetrafluoroethyllining lining
In reaction kettle, is put it into after tightening and carry out hydro-thermal reaction 10h in the burner hearth that temperature is 100 DEG C, after stove is cooled to room temperature,
The presoma prepared is taken out and is respectively cleaned three times with deionized water and ethyl alcohol, is finally placed it in vacuum oven 60
It is dried at a temperature of DEG C, the vacuum degree of vacuum oven is -0.1MPa, has obtained nickel hydroxide/foam containing nickel-phosphorus coating
Nickel presoma.
(5) nickel phosphide/nickel foam self-supporting electrode is prepared:
1. preparing material used:
Nickel phosphide/material used in the preparation of nickel foam self-supporting electrode has the pure grade sodium hypophosphite of analysis and nickel hydroxide/contains
The nickel foam presoma of nickel-phosphorus coating, sodium hypophosphite and nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating quality
Than carrying out metered amount in the ratio between nickel foam on piece amount of loading with sodium hypophosphite and nickel-phosphorus coating；Foam nickel sheet surface nickel phosphorus coating
The amount of loading with and sodium hypophosphite the ratio between mole be 1:5；
2. nickel phosphide/nickel foam self-supporting electrode preparation process:
A, nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and sodium hypophosphite powder two have been respectively put into just first
In beautiful porcelain boat, two corundum porcelain boats are then put into tube furnace burner hearth center, wherein the corundum porcelain boat for holding sodium hypophosphite is answered
Be placed on close to tube furnace nitrogen inlet side, with ensure phosphine gas that sodium hypophosphite is decomposed can with nickel hydroxide/
Nickel foam presoma containing nickel-phosphorus coating, which comes into full contact with, makes its phosphatization；
B, after two corundum porcelain boats place in tube furnace burner hearth center, nitrogen cylinder switching knob is opened, nitrogen is slowly entered
In tube furnace, the intake of nitrogen is 30mL/min；Diamond heating switch is opened simultaneously, makes fire box temperature with 5 DEG C/min's
Heating rate is increased to 300 DEG C by room temperature, makes nickel hydroxide/nickel foam presoma phosphatization containing nickel-phosphorus coating anti-at 300 DEG C
Answer 2h；
C, after phosphating reaction, tube furnace power supply is closed, fire box temperature cooled to room temperature is made, it is cooling to tube furnace burner hearth
To room temperature, nickel hydroxide after phosphorating treatment/nickel foam presoma containing nickel-phosphorus coating is taken out, has been obtained for water power
Dissociate nickel phosphide/nickel foam self-supporting electrode used in liberation of hydrogen.
(6) nickel phosphide/nickel foam self-supporting electrode electrochemical cathode Hydrogen Evolution Performance is tested::
Using standard three electrode system, using nickel foam, business platinum carbon electrode and made nickel phosphide/nickel foam self-supporting electrode as
Working electrode, saturation Ag/AgCl electrode are reference electrode, and carbon-point is to utilize Shanghai Chen Hua CHI660E electrochemical operation to electrode
Stand, using linear sweep voltammetry, respectively 0.5mol/L sulfuric acid, 1.0mol/L potassium hydroxide solution in carry out Hydrogen Evolution Performance
Evaluation, relative to reversible hydrogen electrode current potential, test scope is 0~-0.7V, sweep speed 2mV/s.
Its Hydrogen Evolution Performance and the made sample of embodiment 1 are without marked difference, so be no longer described in detail.
Claims (10)
1. a kind of nickel phosphide/nickel foam electrochemical function liberation of hydrogen material preparation method, it is characterised in that: the following steps are included:
(1) pretreatment of foamed nickel current collector: nickel foam is cut into specified size, and carries out pre-treatment；Pre-treatment is obtained
Foam nickel sheet be immersed in stannous chloride solution, sufficiently react and be immersed in palladium chloride solution after cleaning up, it is sufficiently anti-
Should after clean and dry；
(2) prepare chemical nickel phosphorus plating plating solution: with certain proportion by nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride according to
Secondary to be added in the container for filling distilled water, heating stirring is allowed to be completely dissolved；Sodium hypophosphite is added into solution, heating is stirred
It mixes and makes it dissolve, ammonium hydroxide is added dropwise into solution after solution is cooled to room temperature by solution ph and is adjusted to 4.6~5.0, then
It stirs evenly, obtains chemical nickel plating phosphor bath；
(3) Electroless Ni-P Coating is loaded on foam nickel sheet surface: heating chemical nickel plating phosphor bath to certain temperature, by step
(1) processed foam nickel sheet is immersed in chemical nickel plating phosphor bath in, keeps bath temperature, is controlled plating time, is sufficiently applied
Foam nickel sheet cleaning, drying is taken out after plating；
(4) it prepares nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating: hexamethylenetetramine and six is weighed with certain proportion
Nitric hydrate nickel is placed in the beaker for filling deionized water, is stirred to dissolve, and solution is poured into polytetrafluoroethyllining lining, so
Polytetrafluoroethyllining lining is put into reaction kettle afterwards, hydro-thermal reaction is carried out after heating and obtains nickel hydroxide/containing nickel-phosphorus coating
Nickel foam presoma, and by its cleaning, drying；
(5) nickel phosphide/nickel foam self-supporting electrode preparation: by nickel hydroxide/nickel foam presoma containing nickel-phosphorus coating and
Sodium hypophosphite powder is respectively put into two corundum porcelain boats, and two corundum porcelain boats are put into the tube furnace furnace for having nitrogen atmosphere
In thorax, heating furnace simultaneously obtains nickel phosphide/nickel foam electrochemical function liberation of hydrogen material by phosphating reaction after keeping the temperature a period of time,
A kind of specifically nickel phosphide/nickel foam self-supporting electrode.
2. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
Be: the pre-treatment step in step (1) includes that the foam nickel sheet after cutting is placed in the beaker for filling acetone, then will be burnt
Cup, which is placed in ultrasonic cleaner, to be ultrasonically treated, and then by treated, foam nickel sheet is taken out from beaker, uses deionization
Water cleans 5 times, is put into the beaker for fill hydrochloric acid and performs etching, and then places the beaker in ultrasonic cleaner and carries out at ultrasound
Reason, foam nickel sheet is taken out, cleaned 5 times from beaker with deionized water later, after foam nickel sheet be placed in fill dehydrated alcohol
Beaker in be ultrasonically treated, then by dehydrated alcohol, treated that foam nickel sheet is taken out from beaker, cleans 5 with deionized water
Secondary juxtaposition is dried in a vacuum drying oven.
3. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
It is: foam nickel sheet is immersed in while density is in 10g/L stannous chloride solution in step (1) and passes through ultrasound at room temperature
Washer is ultrasonically treated, and later takes out foam nickel sheet from stannous chloride solution, is cleaned 5 times with deionized water；
It will be ultrasonically treated at room temperature in the palladium chloride solution of foam nickel sheet submergence 0.2g/L and by ultrasonic cleaning machine again, later
Foam nickel sheet is taken out from palladium chloride solution, is cleaned 5 times with deionized water；Finally the foam nickel sheet of washes clean is set
It dries in a vacuum drying oven.
4. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
Be: the mass ratio of nickel sulfate, sodium hypophosphite, citric acid, succinic acid, sodium acetate, ammonium acid fluoride in step (2) is 25
~30:15~30:10~15:3~5:3~5:3~5.
5. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
Be: nickel sulfate, citric acid, succinic acid, sodium acetate, ammonium acid fluoride are added to the burning for filling distilled water in (2) by step first
It in cup, and places the beaker on magnetic stirring apparatus, opens Stirring control handle and computer heating control switch, control solution temperature
It is 40~50 DEG C, agitating solution is completely dissolved each reagent being added；Sodium hypophosphite is added in solution again, stirring makes it
Dissolution closes the computer heating control switch of magnetic stirring apparatus, naturally cools to solution temperature after sodium hypophosphite is completely dissolved
Room temperature.
6. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
It is: the beaker for filling chemical nickel plating phosphor bath is placed in the temperature constant magnetic stirring water bath for filling deionized water in step (3)
In, foam nickel sheet is immersed in chemical nickel plating phosphor bath by heating chemical nickel-plated phosphor bath temperature to 80~85 DEG C, keeps plating solution
Temperature is 80~85 DEG C, and control plating time is 40~60min；Nickel foam chemically is taken out in nickel plating phosphor bath after reaction completely
Piece is cleaned 5 times with deionized water, after place it in vacuum oven and dry.
7. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
Be: the ratio between mole of hexamethylenetetramine and Nickelous nitrate hexahydrate is 1:1 in step (4).
8. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
Be: the ratio between mole of the amount of loading with and sodium hypophosphite of foam nickel sheet surface nickel phosphorus coating is 1:5, the load in step (3)
Negative quantity, that is, foam nickel sheet is of poor quality before and after chemical plating.
9. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, feature
It is: the corundum porcelain boat for holding sodium hypophosphite is placed on close to tube furnace nitrogen inlet side, heating furnace in step (5)
To 300 DEG C and keep the temperature 2h.
10. a kind of nickel phosphide according to claim 1/nickel foam electrochemical function liberation of hydrogen material preparation method, special
Sign is: after placing two corundum porcelain boats in tube furnace burner hearth center in step (5), opening nitrogen cylinder switching knob, makes
Nitrogen slowly enters in tube furnace, and the intake of nitrogen is 10~30 mL/min；Diamond heating switch is opened simultaneously, makes furnace
Bore temperature is increased to 300 DEG C by room temperature with the heating rate of 1~5 DEG C/min, and temperature is kept to make nickel hydroxide/contain nickel-phosphorus coating
2 h of nickel foam presoma phosphating reaction.
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