CN106057499A - Preparation method of nickel alloy hollow sphere loaded core-shell structure particle electrode material - Google Patents
Preparation method of nickel alloy hollow sphere loaded core-shell structure particle electrode material Download PDFInfo
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- CN106057499A CN106057499A CN201610630204.2A CN201610630204A CN106057499A CN 106057499 A CN106057499 A CN 106057499A CN 201610630204 A CN201610630204 A CN 201610630204A CN 106057499 A CN106057499 A CN 106057499A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 53
- 239000002245 particle Substances 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 239000011258 core-shell material Substances 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 244
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 173
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 162
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 162
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 162
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 162
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 162
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 146
- 239000000843 powder Substances 0.000 claims abstract description 85
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000009792 diffusion process Methods 0.000 claims abstract description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 229910000792 Monel Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002105 nanoparticle Substances 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 238000004070 electrodeposition Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- -1 deionized water compound Chemical class 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002659 electrodeposit Substances 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 235000013877 carbamide Nutrition 0.000 claims description 10
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002790 naphthalenes Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000003990 capacitor Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a preparation method of a nickel alloy hollow sphere loaded core-shell structure particle electrode material, which comprises the following preparation processes: preparing macroporous nickel shell type micron powder; nano WO3Nucleus @ nickel and SiO2Preparing a shell type powder material; nickel-based metal copper and micron SiO2Carrying out composite codeposition on the core @ macroporous nickel shell type powder; copper element diffusion treatment and micron SiO2Removing the nucleus; nickel and nano WO3Core @ mesoporous nickel and SiO2Carrying out composite codeposition on the shell-type powder; nano WO3SiO of core surface shell2And removing the local area. The novel super capacitor electrode material prepared by the method has the excellent performances of high specific discharge capacity, rapid charge-discharge process and long cycle life.
Description
Technical field
The present invention relates to super capacitance electrode material field, particularly a kind of nickel alloy sky ball load core-shell structure particles electricity
The preparation method of pole material.
Background technology
Super capacitor not only has the characteristic of capacitor fast charging and discharging, and has energy-storage function, at movable electronic
Equipment, electronic and hybrid vehicle, Novel electric energy storage device field are with a wide range of applications.Research and development new electrode materials
It is the design preparation core with the ultracapacitor of high-energy-density, fast charging and discharging process, the premium properties such as have extended cycle life
Heart technical problem.Prepare super capacitance electrode material and there are two effective approach: one is to increase electrode material surface to amass, and two are
Improve the probability of electrode material reversible reaction.Porous structure material has high-specific surface area, and beneficially super capacitor obtains high energy
Metric density；Wherein, aperture size has vital impact to the surface area of porous material and the speed of electrolyte ion.Macropore
(> 50nm) electrolyte ion quickly moves when being conducive to charge and discharge process high current density, but its surface area is relatively low；Along with aperture
From mesopore size (2nm-50nm) to pore size (< 2nm) change, the surface area of porous material increases, but to electrolyte ion
The obstruction of movement increases.Transition metal oxide WO3There is high-specific capacitance super, but electric conductivity is poor.To sum up, prior art is deposited
In various weak points, a kind of novel super capacitance electrode material is prepared approach and is needed research and development appearance badly.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of nickel alloy sky ball load core-shell structure particles electrode
The preparation method of material, it prepares micro-meter scale macropore nickel alloy sky ball, this micro-meter scale macropore nickel alloy in nickel alloy surfaces
Empty outer surface of ball load WO3Core mesoporous nickel shell structural nano powder body, the electric conductivity of metal shelly well-formed, by with mistake
Cross metal-oxide and combine formation core@metal-back structure, it is achieved that the control of its composite performance.
The technical solution adopted for the present invention to solve the technical problems is: a kind of nickel alloy sky ball load core-shell structure particles
The preparation method of electrode material, comprises following preparation process:
Step [1] prepares macropore nickel shell mould micro-powder；
Step [2] prepares nanometer WO3Core@nickel and SiO2Shell mould powder body material；
Step [3] Ni substrate metallic copper and micron SiO2Core@macropore nickel shell mould powder body composite codeposition；
Step [4] copper DIFFUSION TREATMENT and micron SiO2The removal of core；
Step [5] nickel and nanometer WO3The mesoporous nickel of core@and SiO2Shell mould powder body composite codeposition；
Step [6] nanometer WO3The SiO of core surface shell2Local is removed.
Preferably, described step [1] concrete operations are:
A1. micron SiO2Core@macro-pore SiO2The preparation of shell model granule: by SiO2Micron particle adds in dehydrated alcohol,
Disperse 5-20 minute with ultrasound wave under room temperature, so that SiO2Micron particle is fully dispersed, forms micron SiO2Percentage by weight is
The ethanol disperse system of 40%-80%；Take this disperse system 300mL to join in 1000mL deionized water and be sufficiently mixed, add silicic acid
Four methyl ester make its concentration reach 320mL/L-580mL/L, add carbamide and make its concentration reach 110g/L-170g/L, add poly-second
Alkene pyrrolidone makes its concentration reach 5g/L-25g/L, adds bromine palm fibre trimethyl ammonium (CTAB) and makes its concentration reach 1.5g/L-4g/
L, makes this mixed system manage 2-4.5 hour；Obtain this system micron particle after filtration, at temperature is 70-110 DEG C, is incubated 1-
3 hours prepared micron SiO2Core@macro-pore SiO2Shell model micron particle.
A2. micron SiO2Core@nickel and SiO2The preparation of shell mould powder body: by SiO2Core@macro-pore SiO2Shell model micron particle adds
Enter in tetrahydronaphthalene, and add nickel acetylacetonate, form micron SiO2Core@macro-pore SiO2Shell model micron particle percentage by weight
For the tetrahydronaphthalene disperse system that 40%-50%, acetylacetone,2,4-pentanedione nickel concentration are 410g/L-670g/L, take this disperse system 500mL and add
In the acetone of 100mL and be sufficiently mixed, at room temperature with 10-40kHz, 60-110W/cm2Under conditions of ultrasonic 0.5-1.5 little
Time prepare micron SiO2Core@nickel and SiO2Shell mould powder body.
A3. the preparation of macropore nickel shell mould micro-powder: the Fluohydric acid. with deionized water compound concentration as 6-16mL/L, takes system
Standby 12-35g micron SiO2Core@nickel and SiO2Shell mould powder body adds in the hydrofluoric acid solution of 500mL preparation, etch 20-60 minute
To remove micron SiO2Core and the SiO on surface thereof2Shell, thus obtain macropore nickel shell mould micro-powder.
Preferably, described step [2] concrete operations are:
B1. nanometer WO3The mesoporous SiO of core@2The preparation of shell model granule: by WO3Nano-particle adds in dehydrated alcohol, in room
Disperse 30-60 minute with ultrasound wave under temperature, so that WO3Nano-particle is fully dispersed, forms nanometer WO3Percentage by weight is 20%-
The ethanol disperse system of 60%；Take this disperse system 400mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate
Make its concentration reach 110-230mL/L and 160-270mL/L respectively with positive silicic acid propyl ester, add carbamide and make its concentration reach 80-
210g/L, adds polyvinylpyrrolidone and makes its concentration reach 2-12g/L, add bromine palm fibre trimethyl ammonium (CTAB) and make its concentration reach
To 0.5-2g/L, this mixed system is made to manage 1-3 hour；Obtain this system nano-particle after filtration, be 90-130 DEG C in temperature
Nanometer WO is prepared after being incubated 0.5-1.5 hour3The mesoporous SiO of core@2Shell mould powder body model nano-particle.
B2. nanometer WO3Core@nickel and SiO2The preparation of shell mould powder body material: by WO3The mesoporous SiO of core@2Shell model nano-particle
Add in decahydronaphthalenes, and add nickel acetylacetonate, form nanometer WO3The mesoporous SiO of core@2Core-shell type nanometer weight percentage is
25%-60%, acetylacetone,2,4-pentanedione nickel concentration are the decahydronaphthalenes disperse system of 220g/L-360g/L, take this disperse system 400mL and join
The acetone of 150mL is sufficiently mixed, at room temperature with 20-50kHz, 80-120W/cm2Ultrasonic 1-2.5 hour of condition prepare and receive
Rice WO3Core@nickel and SiO2Shell mould powder body material.
Preferably, described step [3] concrete operations are:
It is analytically pure copper sulfate, dimethylformamide base sodium sulfonate, micron SiO by concentration2Core@macropore nickel shell mould powder
Body, dipotassium hydrogen phosphate, the phosphoric acid of 60% and ethylene thiourea add in deionized water, form electrodeposit liquid A, using metal nickel plate as
Negative electrode, metal copper plate is anode；With current density range as 50mA/cm2-180mA/cm2Carry out electro-deposition, and stir with ultrasound wave
Mix, at room temperature electro-deposition 0.5-1.2 hour, be prepared into nickel plate surface metal copper/micron SiO2Core@macropore nickel shell mould powder is combined
Layer.
Preferably, copper sulfate, dimethylformamide base sodium sulfonate, micron SiO in electrodeposit liquid A described in step [3]2
The concentration of core@macropore nickel shell mould powder body, dipotassium hydrogen phosphate, the phosphoric acid of 60% and ethylene thiourea be respectively 120g/L-170g/L,
30g/L-90g/L, 130g/L-180g/L, 12g/L-50g/L, 40mL/L-75mL/L and 0.5g/L-3g/L.
Preferably, described step [4] concrete operations are:
C1. copper DIFFUSION TREATMENT: will be through Ni substrate surface copper and micron SiO2Core@macropore nickel shell mould powder body is combined coprecipitated
Long-pending sample loads Muffle furnace and is heated up to 700-850 DEG C, is incubated and within 2-7 hour, realizes nickel plate surface metal copper/micron SiO2Core@is big
The copper of hole nickel shell mould powder composite bed is to nickel plate and the diffusion of macropore nickel shell, so that monel area load micron
SiO2Core@macropore nickel alloy shell granule.
C2. micron SiO2The removal of core: the Fluohydric acid. with deionized water compound concentration as 10-22mL/L, will be through copper
The sample that obtains after DIFFUSION TREATMENT immerses in hydrofluoric acid solution, and etch 40-60 minute is to remove micron SiO2Core, thus at ambrose alloy
Alloy surface obtains macropore nickel alloy micron spherical shell.
Preferably, described step [5] concrete operations are:
It is analytically pure nickel fluoborate, nanometer WO by concentration3The mesoporous nickel of core@and SiO2Shell mould powder body, disodium hydrogen phosphate, fourth
Acetylenic glycols and 60% phosphoric acid are sequentially added in deionized water, form electrodeposit liquid B；Macropore nickel alloy micron spherical shell is obtained with surface
Monel be negative electrode, rustless steel is anode；With current density range as 80-120mA/cm2Carry out electro-deposition, and with ultrasonic
Ripple stirs, at room temperature electro-deposition 20-50 minute, so that the macropore nickel alloy micron spherical shell load on monel surface
WO3The mesoporous nickel of core@and SiO2 core-shell type nanometer granule.
Preferably, nickel fluoborate, nanometer WO in electrodeposit liquid B described in step [5]3The mesoporous nickel of core@and SiO2Shell mould powder
The concentration of body, disodium hydrogen phosphate, butynediols and 60% phosphoric acid be respectively 135-180g/L, 170-260g/L, 10-80g/L,
25-40g/L and 30-90mL/L.
Preferably, described step [6] concrete operations are:
Fluohydric acid. with deionized water compound concentration as 14-35mL/L, will load WO3The mesoporous nickel of core@and SiO2Shell mould is received
The monel of rice grain immerses in the hydrofluoric acid solution of above-mentioned preparation, and etch 0.5-1.5 hour is to remove nanometer WO3Core surface
The SiO of shell2, so that nickel alloy sky ball load nanometer WO on monel surface3Core/mesoporous nickel shell granule.
The positive effect of the present invention: the inventive method prepares micro-meter scale macropore nickel alloy sky ball in nickel alloy surfaces, its
It is high that macroporous structure feature and nickel alloy sky ball play electrolyte ion reservoir effect, beneficially charge and discharge process at charge and discharge process
During electric current density, electrolyte ion quickly moves；Nickel alloy sky outer surface of ball load WO3Core@mesoporous nickel core-shell nanoparticles effectively increases
Add the surface area of this electrode material；WO3It is the most special that core@mesoporous nickel shell structure not only combines metallic nickel shell electric conductivity
Point, and achieve WO3The performance characteristic of high-specific capacitance super.Novel super capacitance electrode material prepared by the present invention has height
Energy density, fast charging and discharging process, the premium properties that has extended cycle life.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of electrode material of the present invention；
Fig. 2 is the surface texture schematic diagram of electrode material of the present invention；
Fig. 3 is the charge and discharge cycles number of times graph of a relation with specific discharge capacity of embodiment 1 and embodiment 2；
Fig. 4 be embodiment 1 and embodiment 2 respectively under 2.5A/g and 40A/g electric current density charging capacity percentage ratio with fill
The graph of a relation of electricity time.
Detailed description of the invention
Below in conjunction with the accompanying drawings to a preferred embodiment of the present invention will be described in detail.
With reference to Fig. 1 and Fig. 2, the preferred embodiment of the present invention provides a kind of nickel alloy sky ball load core-shell structure particles electrode material
The preparation method of material, follows these steps to order and carries out:
(1) micron SiO2Core@macro-pore SiO2The preparation of shell model: by SiO2Micron particle adds in dehydrated alcohol, in room temperature
Under disperse 5-20 minute with ultrasound wave, so that SiO2Micron particle is fully dispersed, forms micron SiO2Percentage by weight is 40%-
The ethanol disperse system of 80%；Take this disperse system 300mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate
Make its concentration reach 320mL/L-580mL/L, add carbamide and make its concentration reach 110g/L-170g/L, add polyvinyl pyrrole
Alkanone makes its concentration reach 5g/L-25g/L, adds bromine palm fibre trimethyl ammonium (CTAB) and makes its concentration reach 1.5g/L-4g/L, makes this
Mixed system manages 2-4.5 hour；Filter this system micron particle, be 1-3 hour prepared micron of 70-110 DEG C of insulation in temperature
SiO2Core@macro-pore SiO2Shell model.
(2) micron SiO2Core@nickel and SiO2The preparation of shell mould powder body: by SiO2Core@macro-pore SiO2Shell model micron particle adds
Enter in tetrahydronaphthalene, and add nickel acetylacetonate, form micron SiO2Core@macro-pore SiO2Shell model micron particle percentage by weight
For the tetrahydronaphthalene disperse system that 40%-50%, acetylacetone,2,4-pentanedione nickel concentration are 410g/L-670g/L, take this disperse system 500mL and add
Acetone to 100mL is sufficiently mixed, at room temperature with 10-40kHz, and 60-110W/cm2Ultrasonic 0.5-1.5 hour prepared micron
SiO2Core@nickel and SiO2Shell mould powder body.
(3) preparation of macropore nickel shell mould micro-powder: the Fluohydric acid. with deionized water compound concentration as 6-16mL/L, will system
Standby 12-35g micron SiO2Core@nickel and SiO2Shell mould powder body adds in the hydrofluoric acid solution of 500mL preparation, etch 20-60 minute
To remove micron SiO2Core and the SiO on surface thereof2Shell, thus obtain macropore nickel shell mould micro-powder.
(4) nanometer WO3The mesoporous SiO of core@2The preparation of shell model: by WO3Nano-particle adds in dehydrated alcohol, at room temperature
Disperse 30-60 minute with ultrasound wave, so that WO3Nano-particle is fully dispersed, forms nanometer WO3Percentage by weight is 20%-60%
Ethanol disperse system；Take this disperse system 400mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate and just
Silicic acid propyl ester makes its concentration reach 110mL/L-230mL/L and 160mL/L-270mL/L respectively, adds carbamide and makes its concentration reach
80g/L-210g/L, adds polyvinylpyrrolidone and makes its concentration reach 2g/L-12g/L, add bromine palm fibre trimethyl ammonium (CTAB)
Make its concentration reach 0.5g/L-2g/L, make this mixed system manage 1-3 hour；This system nano-particle is obtained, in temperature after filtration
Degree is incubated 0.5-1.5 hour prepared nanometer WO at 90-130 DEG C3Core@mesoporous SiO2 shell mould powder body model.
(5) nanometer WO3Core@nickel and SiO2The preparation of shell mould powder body material: by WO3The mesoporous SiO of core@2Shell model nano-particle
Add in decahydronaphthalenes, and add nickel acetylacetonate, form nanometer WO3The mesoporous SiO of core@2Shell mould powder body percentage by weight is
25%-60%, acetylacetone,2,4-pentanedione nickel concentration are the decahydronaphthalenes disperse system of 220g/L-360g/L, take this disperse system 400mL and join
The acetone of 150mL is sufficiently mixed, at room temperature with 20-50kHz, 80-120W/cm2Ultrasonic 1-2.5 hour prepared nanometer WO3
Core@nickel and SiO2Shell mould powder body material.
(6) it is analytically pure copper sulfate, dimethylformamide base sodium sulfonate, micron SiO by concentration2Core@macropore nickel shell mould
Powder body, dipotassium hydrogen phosphate, the phosphoric acid of 60% and ethylene thiourea add in deionized water, form above each component concentration and are respectively
120g/L-170g/L, 30g/L-90g/L, 130g/L-180g/L, 12g/L-50g/L, 40mL/L-75mL/L and 0.5g/L-3g/
The electrodeposit liquid of L.Using metal nickel plate as negative electrode, metal copper plate is anode；With current density range as 50mA/cm2-180mA/
cm2Carry out electro-deposition, and with ultrasonic stirring, at room temperature electro-deposition 0.5-1.2 hour, be prepared into nickel plate surface metal copper/
Micron SiO2Core@macropore nickel shell mould powder composite bed.
(7) copper DIFFUSION TREATMENT: will be through Ni substrate surface copper and micron SiO2Core@macropore nickel shell mould powder body is combined coprecipitated
Long-pending sample loads Muffle furnace and is heated up to 700-850 DEG C, is incubated and within 2-7 hour, realizes nickel plate surface metal copper/micron SiO2Core@is big
The copper of hole nickel shell mould powder composite bed is to nickel plate and the diffusion of macropore nickel shell, thus obtains monel area load micron
SiO2Core@macropore nickel alloy shell.
(8) micron SiO2The removal of core: the Fluohydric acid. with deionized water compound concentration as 10mL/L-22mL/L, will be through copper
The monel area load micron SiO that Elements Diffusion obtains after processing2Core@macropore nickel nickel alloy shell immerses hydrofluoric acid solution
In, etch removes micron SiO in 40-60 minute2Core, thus macropore nickel alloy micron spherical shell is obtained on monel surface.
(9) it is analytically pure nickel fluoborate, nanometer WO by concentration3The mesoporous nickel of core@and SiO2Shell mould powder body, disodium hydrogen phosphate,
Butynediols and 60% phosphoric acid are sequentially added in deionized water, and forming nickel fluoborate concentration is 135g/L-180g/L, nanometer WO3
The mesoporous nickel of core@and SiO2Shell mould powder concentration is 170g/L-260g/L, disodium hydrogen phosphate concentration is 10g/L-80g/L, butine two
Determining alcohol is 25g/L-40g/L and 60% phosphoric acid concentration is the electrodeposit liquid of 30mL/L-90mL/L.Obtain macropore nickel with surface to close
The monel of gold micron spherical shell is negative electrode, and rustless steel is anode；It is 80mA/cm at current density range2-120mA/cm2Bar
Electro-deposition is carried out, and with ultrasonic stirring, at room temperature electro-deposition 20-50 minute, thus big on monel surface under part
Hole nickel alloy micron spherical shell has loaded WO3The mesoporous nickel of core@and SiO2Core-shell type nanometer granule.
(10) Fluohydric acid. with deionized water compound concentration as 14-35mL/L, will load WO3The mesoporous nickel of core@and SiO2Shell
The monel of type nano-particle immerses in above-mentioned hydrofluoric acid solution, and etch 0.5-1.5 hour is to remove nanometer WO3Core surface shell
SiO2, thus nickel alloy sky ball load nanometer WO on monel surface3Core/mesoporous nickel shell.
Specific embodiment be given below:
Embodiment 1
(1) micron SiO2Core@macro-pore SiO2The preparation of shell model: by SiO2Micron particle adds in dehydrated alcohol, in room temperature
Under disperse 15 minutes with ultrasound wave, so that SiO2Micron particle is fully dispersed, forms micron SiO2Percentage by weight is the second of 48%
Alcohol disperse system；Take this disperse system 300mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate and make its concentration
Reach 360mL/L, add carbamide and make its concentration reach 150g/L, add polyvinylpyrrolidone and make its concentration reach 7g/L, add
Entering bromine palm fibre trimethyl ammonium (CTAB) makes its concentration reach 2g/L, makes this mixed system manage 3.5 hours；This system is obtained after filtration
Micron particle, is incubated 2 hours prepared micron SiO at temperature is 90 DEG C2Core@macro-pore SiO2Shell model.
(2) micron SiO2Core@nickel and SiO2The preparation of shell mould powder body: by SiO2Core@macro-pore SiO2Shell model micron particle adds
Enter in tetrahydronaphthalene, and add nickel acetylacetonate, form micron SiO2Core@macro-pore SiO2Shell model micron particle percentage by weight
Be 45%, acetylacetone,2,4-pentanedione nickel concentration be the tetrahydronaphthalene disperse system of 470g/L, take this disperse system 500mL and join the third of 100mL
Ketone is sufficiently mixed, at room temperature with 35kHz, and 80W/cm2Ultrasonic 1 hour prepared micron SiO2Core@nickel and SiO2Shell mould powder body.
(3) preparation of macropore nickel shell mould micro-powder: the Fluohydric acid. with deionized water compound concentration as 11mL/L, will preparation
15g micron SiO2Core@nickel and SiO2Shell mould powder body adds the hydrofluoric acid solution 500mL of above-mentioned preparation, and etch is removed micro-in 30 minutes
Rice SiO2Core and the SiO on surface thereof2Shell, thus obtain macropore nickel shell mould micro-powder.
(4) nanometer WO3The mesoporous SiO of core@2The preparation of shell model: by WO3Nano-particle adds in dehydrated alcohol, at room temperature
Disperse 40 minutes with ultrasound wave, so that WO3Nano-particle is fully dispersed, forms nanometer WO3Percentage by weight be 30% ethanol divide
Dissipate system；Take this disperse system 400mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate and positive silicic acid propyl ester
Make its concentration reach 130mL/L and 170mL/L respectively, add carbamide and make its concentration reach 110g/L, add polyvinylpyrrolidine
Ketone makes its concentration reach 10g/L, adds bromine palm fibre trimethyl ammonium (CTAB) and makes its concentration reach 1.5g/L, makes this mixed system manage
1.5 hour；Filter this system nano-particle, be 1 hour prepared nanometer WO3 core@mesoporous SiO2 shell mould powder of 93 DEG C of insulations in temperature
Body Model.
(5) nanometer WO3Core@nickel and SiO2The preparation of shell mould powder body material: by WO3The mesoporous SiO of core@2Shell model nano-particle
Add in decahydronaphthalenes, and add nickel acetylacetonate, form nano WO3The mesoporous SiO of core@2Shell mould powder body percentage by weight is
35%, acetylacetone,2,4-pentanedione nickel concentration is the decahydronaphthalenes disperse system of 240g/L, takes this disperse system 400mL and joins the acetone of 150mL
It is sufficiently mixed, at room temperature with 30kHz, 90W/cm2Ultrasonic 1.5 hours prepared nanometers WO3Core@nickel and SiO2Shell mould powder body material.
(6) it is analytically pure copper sulfate, dimethylformamide base sodium sulfonate, micron SiO by concentration2Core@macropore nickel shell mould
Powder body, dipotassium hydrogen phosphate, the phosphoric acid of 60% and ethylene thiourea add in deionized water, form above each component concentration and are respectively
The electrodeposit liquid of 150g/L, 50g/L, 140g/L, 22g/L, 60mL/L and 2.5g/L.Using metal nickel plate as negative electrode, metallic copper
Plate is anode；With current density range as 150mA/cm2Carry out electro-deposition, and with ultrasonic stirring, at room temperature electro-deposition 1 is little
Time, it is prepared into nickel plate surface metal copper/micron SiO2Core@macropore nickel shell mould powder composite bed.
(7) copper DIFFUSION TREATMENT: will be through Ni substrate surface copper and micron SiO2Core@macropore nickel shell mould powder body is combined coprecipitated
Long-pending sample loads Muffle furnace and is heated up to 750 DEG C, is incubated and within 4 hours, realizes nickel plate surface metal copper/micron SiO2Core@macropore nickel shell
The copper of type powder composite bed is to nickel plate and the diffusion of macropore nickel shell, thus obtains monel area load micron SiO2Core@
Macropore nickel alloy shell.
(8) micron SiO2The removal of core: the Fluohydric acid. with deionized water compound concentration as 12mL/L, will spread through copper
The monel area load micron SiO obtained after process2The Fluohydric acid. that core@macropore nickel nickel alloy shell immerses above-mentioned preparation is molten
Liquid, etch removes micron SiO in 45 minutes2Core, thus macropore nickel alloy micron spherical shell is obtained on monel surface.
(9) it is analytically pure nickel fluoborate, nanometer WO by concentration3The mesoporous nickel of core@and SiO2Shell mould powder body, disodium hydrogen phosphate,
Butynediols and 60% phosphoric acid are sequentially added in deionized water, formed above-mentioned each concentration of component be respectively 145g/L, 180g/L,
The electrodeposit liquid of 70g/L, 35g/L and 50mL/L.The monel obtaining macropore nickel alloy micron spherical shell on surface is negative electrode, no
Rust steel is anode；With current density range as 100mA/cm2Carry out electro-deposition, and with ultrasonic stirring, at room temperature electro-deposition
Time is 35 minutes, thus the macropore nickel alloy micron spherical shell on monel surface has loaded WO3The mesoporous nickel of core@and SiO2Shell
Type nano-particle.
(10) Fluohydric acid. with deionized water compound concentration as 15mL/L, will load WO3The mesoporous nickel of core@and SiO2Shell mould
The monel of nano-particle immerses the hydrofluoric acid solution of above-mentioned preparation, and etch 1 hour is to remove nanometer WO3Core surface shell
SiO2, thus nickel alloy sky ball load nanometer WO on monel surface3Core/mesoporous nickel shell.
Embodiment 2
(1) micron SiO2Core@macro-pore SiO2The preparation of shell model: by SiO2Micron particle adds in dehydrated alcohol, in room temperature
Under disperse 20 minutes with ultrasound wave, so that SiO2Micron particle is fully dispersed, forms micron SiO2Percentage by weight is the second of 60%
Alcohol disperse system；Take this disperse system 300mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate and make its concentration
Reach 500mL/L, add carbamide and make its concentration reach 170g/L, add polyvinylpyrrolidone and make its concentration reach 20g/L, add
Entering bromine palm fibre trimethyl ammonium (CTAB) makes its concentration reach 1.5g/L, makes this mixed system manage 2 hours；This system is obtained after filtration
Micron particle, is 1.5 hours prepared micron SiO of 100 DEG C of insulations in temperature2Core@macro-pore SiO2Shell model.
(2) micron SiO2Core@nickel and SiO2The preparation of shell mould powder body: by SiO2Core@macro-pore SiO2Shell model micron particle adds
Enter in tetrahydronaphthalene, and add nickel acetylacetonate, form micron SiO2Core@macro-pore SiO2Shell model micron particle percentage by weight
Be 50%, acetylacetone,2,4-pentanedione nickel concentration be the tetrahydronaphthalene disperse system of 520g/L, take this disperse system 500mL and join the third of 100mL
Ketone is sufficiently mixed, at room temperature with 40kHz, and 90W/cm2Ultrasonic 1.5 hours prepared micron SiO2Core@nickel and SiO2Shell mould powder body.
(3) preparation of macropore nickel shell mould micro-powder: the Fluohydric acid. with deionized water compound concentration as 14mL/L, will preparation
20g micron SiO2Core@nickel and SiO2Shell mould powder body adds in the hydrofluoric acid solution of the above-mentioned preparation of 500mL, and etch is removed for 45 minutes
Micron SiO2Core and the SiO on surface thereof2Shell, thus obtain macropore nickel shell mould micro-powder.
(4) nanometer WO3The mesoporous SiO of core@2The preparation of shell model: by WO3Nano-particle adds in dehydrated alcohol, at room temperature
Disperse 50 minutes with ultrasound wave, so that WO3Nano-particle is fully dispersed, forms nanometer WO3Percentage by weight be 40% ethanol divide
Dissipate system；Take this disperse system 400mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate and positive silicic acid propyl ester
Make its concentration reach 120mL/L and 210mL/L respectively, add carbamide and make its concentration reach 130g/L, add polyvinylpyrrolidine
Ketone makes its concentration reach 8g/L, adds bromine palm fibre trimethyl ammonium (CTAB) and makes its concentration reach 2g/L, makes this mixed system manage 2 little
Time；Filter this system nano-particle, at temperature is 100 DEG C, is incubated 1.5 hours prepared nanometer WO3 core@mesoporous SiO2 shell mould powder
Body Model.
(5) nanometer WO3Core@nickel and SiO2The preparation of shell mould powder body material: by WO3The mesoporous SiO of core@2Shell model nano-particle
Add in decahydronaphthalenes, and add nickel acetylacetonate, form nano WO3The mesoporous SiO of core@2Shell mould powder body percentage by weight is
40%, acetylacetone,2,4-pentanedione nickel concentration is the decahydronaphthalenes disperse system of 310g/L, takes this disperse system 400mL and joins the acetone of 150mL
It is sufficiently mixed, at room temperature with 50kHz, 110W/cm2Ultrasonic 2 hours prepared nanometers WO3Core@nickel and SiO2Shell mould powder body material.
(6) it is analytically pure copper sulfate, dimethylformamide base sodium sulfonate, micron SiO by concentration2Core@macropore nickel shell mould
Powder body, dipotassium hydrogen phosphate, the phosphoric acid of 60% and ethylene thiourea add in deionized water, form above each component concentration and are respectively
The electrodeposit liquid of 135g/L, 60g/L, 170g/L, 40g/L, 50mL/L and 3g/L.Using metal nickel plate as negative electrode, metal copper plate
For anode；With current density range as 170mA/cm2Carry out electro-deposition, and with ultrasonic stirring, at room temperature electro-deposition 1.2 is little
Time, it is prepared into nickel plate surface metal copper/micron SiO2Core@macropore nickel shell mould powder composite bed.
(7) copper DIFFUSION TREATMENT: will be through Ni substrate surface copper and micron SiO2Core@macropore nickel shell mould powder body is combined coprecipitated
Long-pending sample loads Muffle furnace and is heated up to 800 DEG C, is incubated and within 5 hours, realizes nickel plate surface metal copper/micron SiO2Core@macropore nickel shell
The copper of type powder composite bed is to nickel plate and the diffusion of macropore nickel shell, thus obtains monel area load micron SiO2Core@
Macropore nickel alloy shell.
(8) micron SiO2The removal of core: the Fluohydric acid. with deionized water compound concentration as 18mL/L, will spread through copper
The monel area load micron SiO obtained after process2The Fluohydric acid. that core@macropore nickel nickel alloy shell immerses above-mentioned preparation is molten
Liquid, etch removes micron SiO in 50 minutes2Core, thus macropore nickel alloy micron spherical shell is obtained on monel surface.
(9) it is analytically pure nickel fluoborate, nanometer WO by concentration3The mesoporous nickel of core@and SiO2Shell mould powder body, disodium hydrogen phosphate,
Butynediols and 60% phosphoric acid are sequentially added in deionized water, formed above-mentioned each concentration of component be respectively 160g/L, 210g/L,
The electrodeposit liquid of 60g/L, 40g/L and 60mL/L.The monel obtaining macropore nickel alloy micron spherical shell on surface is negative electrode, no
Rust steel is anode；With current density range as 90mA/cm2Carry out electro-deposition, and with ultrasonic stirring, at room temperature during electro-deposition
Between be 40 minutes, thus the macropore nickel alloy micron spherical shell on monel surface has loaded WO3The mesoporous nickel of core@and SiO2 shell mould
Nano-particle.
(10) Fluohydric acid. with deionized water compound concentration as 20mL/L, will load WO3The mesoporous nickel of core@and SiO2Shell mould
The monel of nano-particle immerses the hydrofluoric acid solution of above-mentioned preparation, and etch removes nanometer WO in 1.5 hours3Core surface shell
SiO2, thus nickel alloy sky ball load nanometer WO on monel surface3Core/mesoporous nickel shell.
The Na of preparation 0.5mol/L2SO4Solution, loads with the nickel alloy base nickel alloy sky ball of 20mm × 20mm × 10mm
Nanometer WO3 core@mesoporous nickel shell electrode material is working electrode, and saturated glycosides mercury electrode is reference electrode, and platinum guaze is to electrode, test
Above-described embodiment charge and discharge cycles number of times and the relation of specific discharge capacity, its result is as shown in Figure 3；Test display, through the present invention
Electrode material prepared by the method for embodiment 1 and embodiment 2 shows identical charge-discharge performance, and its initial discharge specific capacity is about
For 990F/g, after circulating 1200 times, specific discharge capacity is about 870F/g, and after circulating 1200 times, specific discharge capacity remains in that 88%.
Testing embodiment charging capacity percentage ratio and relation in charging interval under 2.5A/g and 40A/g electric current density, its result is such as
Shown in Fig. 4；Test result shows, under 2.5A/g and 40A/g electric current density, embodiment (embodiment 1 and embodiment 2) charging reaches
About 55 seconds and 4 seconds it are respectively necessary for during to 95% capacity.Test result indicate that, the nickel alloy sky ball load prepared according to the present invention is received
Rice WO3 core@mesoporous nickel shell electrode material has the advantages such as high specific discharge capacity, fast charging and discharging speed is fast, have extended cycle life.
Above-described only the preferred embodiments of the present invention, the explanation of it should be understood that above example is simply used
In helping to understand method and the core concept thereof of the present invention, the protection domain being not intended to limit the present invention, all the present invention's
Any amendment of being made within thought and principle, equivalent etc., should be included within the scope of the present invention.
Claims (9)
1. the preparation method of a nickel alloy sky ball load core-shell structure particles electrode material, it is characterised in that comprise following system
Standby step:
Step [1] prepares macropore nickel shell mould micro-powder；
Step [2] prepares nanometer WO3Core@nickel and SiO2Shell mould powder body material；
Step [3] Ni substrate metallic copper and micron SiO2Core@macropore nickel shell mould powder body composite codeposition；
Step [4] copper DIFFUSION TREATMENT and micron SiO2The removal of core；
Step [5] nickel and nanometer WO3The mesoporous nickel of core@and SiO2Shell mould powder body composite codeposition；
Step [6] nanometer WO3The SiO of core surface shell2Local is removed.
The preparation method of a kind of nickel alloy sky ball the most according to claim 1 load core-shell structure particles electrode material, its
It is characterised by:
Described step [1] concrete operations are:
A1. micron SiO2Core@macro-pore SiO2The preparation of shell model granule: by SiO2Micron particle adds in dehydrated alcohol, in room temperature
Under disperse 5-20 minute with ultrasound wave, so that SiO2Micron particle is fully dispersed, forms micron SiO2Percentage by weight is 40%-
The ethanol disperse system of 80%；Take this disperse system 300mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate
Make its concentration reach 320mL/L-580mL/L, add carbamide and make its concentration reach 110g/L-170g/L, add polyvinyl pyrrole
Alkanone makes its concentration reach 5g/L-25g/L, adds bromine palm fibre trimethyl ammonium (CTAB) and makes its concentration reach 1.5g/L-4g/L, makes this
Mixed system manages 2-4.5 hour；Obtain this system micron particle after filtration, at temperature is 70-110 DEG C, is incubated 1-3 hour
Prepare micron SiO2Core@macro-pore SiO2Shell model micron particle；
A2. micron SiO2Core@nickel and SiO2The preparation of shell mould powder body: by SiO2Core@macro-pore SiO2Shell model micron particle adds four
In hydrogenated naphthalene, and add nickel acetylacetonate, form micron SiO2Core@macro-pore SiO2Shell model micron particle percentage by weight is
40%-50%, acetylacetone,2,4-pentanedione nickel concentration are the tetrahydronaphthalene disperse system of 410g/L-670g/L, take this disperse system 500mL and join
In the acetone of 100mL and be sufficiently mixed, at room temperature with 10-40kHz, 60-110W/cm2Under conditions of ultrasonic 0.5-1.5 hour
Prepare micron SiO2Core@nickel and SiO2Shell mould powder body；
A3. the preparation of macropore nickel shell mould micro-powder: the Fluohydric acid. with deionized water compound concentration as 6-16mL/L, takes preparation
12-35g micron SiO2Core@nickel and SiO2Shell mould powder body adds in the hydrofluoric acid solution of 500mL preparation, and etch 20-60 minute is to go
Except micron SiO2Core and the SiO on surface thereof2Shell, thus obtain macropore nickel shell mould micro-powder.
The preparation method of a kind of nickel alloy sky ball the most according to claim 1 load core-shell structure particles electrode material, its
It is characterised by:
Described step [2] concrete operations are:
B1. nanometer WO3The mesoporous SiO of core@2The preparation of shell model granule: by WO3Nano-particle adds in dehydrated alcohol, at room temperature
Disperse 30-60 minute with ultrasound wave, so that WO3Nano-particle is fully dispersed, forms nanometer WO3Percentage by weight is 20%-60%
Ethanol disperse system；Take this disperse system 400mL to join in 1000mL deionized water and be sufficiently mixed, add quanmethyl silicate and just
Silicic acid propyl ester makes its concentration reach 110-230mL/L and 160-270mL/L respectively, adds carbamide and makes its concentration reach 80-210g/
L, adds polyvinylpyrrolidone and makes its concentration reach 2-12g/L, add bromine palm fibre trimethyl ammonium (CTAB) and make its concentration reach
0.5-2g/L, makes this mixed system manage 1-3 hour；Obtain this system nano-particle after filtration, be 90-130 DEG C of guarantor in temperature
Temperature prepares nanometer WO after 0.5-1.5 hour3The mesoporous SiO of core@2Shell mould powder body model nano-particle；
B2. nanometer WO3Core@nickel and SiO2The preparation of shell mould powder body material: by WO3The mesoporous SiO of core@2Shell model nano-particle adds
In decahydronaphthalenes, and add nickel acetylacetonate, form nanometer WO3The mesoporous SiO of core@2Core-shell type nanometer weight percentage is
25%-60%, acetylacetone,2,4-pentanedione nickel concentration are the decahydronaphthalenes disperse system of 220g/L-360g/L, take this disperse system 400mL and join
The acetone of 150mL is sufficiently mixed, at room temperature with 20-50kHz, 80-120W/cm2Ultrasonic 1-2.5 hour of condition prepare and receive
Rice WO3Core@nickel and SiO2Shell mould powder body material.
The preparation method of a kind of nickel alloy sky ball the most according to claim 1 load core-shell structure particles electrode material, its
It is characterised by:
Described step [3] concrete operations are:
It is analytically pure copper sulfate, dimethylformamide base sodium sulfonate, micron SiO by concentration2Core@macropore nickel shell mould powder body, phosphoric acid
Hydrogen dipotassium, the phosphoric acid of 60% and ethylene thiourea add in deionized water, form electrodeposit liquid A, using metal nickel plate as negative electrode, gold
Genus copper coin is anode；With current density range as 50mA/cm2-180mA/cm2Carry out electro-deposition, and with ultrasonic stirring, in room
Temperature lower electro-deposition 0.5-1.2 hour, is prepared into nickel plate surface metal copper/micron SiO2Core@macropore nickel shell mould powder composite bed.
The preparation method of a kind of nickel alloy sky ball the most according to claim 4 load core-shell structure particles electrode material, its
It is characterised by: copper sulfate, dimethylformamide base sodium sulfonate, micron SiO in electrodeposit liquid A described in step [3]2Core@macropore
The concentration of nickel shell mould powder body, dipotassium hydrogen phosphate, the phosphoric acid of 60% and ethylene thiourea is respectively 120g/L-170g/L, 30g/L-
90g/L, 130g/L-180g/L, 12g/L-50g/L, 40mL/L-75mL/L and 0.5g/L-3g/L.
The preparation method of a kind of nickel alloy sky ball the most according to claim 1 load core-shell structure particles electrode material, its
It is characterised by:
Described step [4] concrete operations are:
C1. copper DIFFUSION TREATMENT: will be through Ni substrate surface copper and micron SiO2Core@macropore nickel shell mould powder body composite codeposition
Sample loads Muffle furnace and is heated up to 700-850 DEG C, is incubated and within 2-7 hour, realizes nickel plate surface metal copper/micron SiO2Core@macropore nickel
The copper of shell mould powder composite bed is to nickel plate and the diffusion of macropore nickel shell, so that monel area load micron SiO2
Core@macropore nickel alloy shell granule；
C2. micron SiO2The removal of core: the Fluohydric acid. with deionized water compound concentration as 10-22mL/L, will be at copper diffusion
The sample that obtains after reason immerses in hydrofluoric acid solution, and etch 40-60 minute is to remove micron SiO2Core, thus at monel table
Face obtains macropore nickel alloy micron spherical shell.
The preparation method of a kind of nickel alloy sky ball the most according to claim 1 load core-shell structure particles electrode material, its
It is characterised by:
Described step [5] concrete operations are:
It is analytically pure nickel fluoborate, nanometer WO by concentration3The mesoporous nickel of core@and SiO2Shell mould powder body, disodium hydrogen phosphate, butine two
Alcohol and 60% phosphoric acid are sequentially added in deionized water, form electrodeposit liquid B；The nickel of macropore nickel alloy micron spherical shell is obtained with surface
Copper alloy is negative electrode, and rustless steel is anode；With current density range as 80-120mA/cm2Carry out electro-deposition, and stir with ultrasound wave
Mix, at room temperature electro-deposition 20-50 minute, so that the macropore nickel alloy micron spherical shell load WO on monel surface3Core@
Mesoporous nickel and SiO2 core-shell type nanometer granule.
The preparation method of a kind of nickel alloy sky ball the most according to claim 7 load core-shell structure particles electrode material, its
It is characterised by: nickel fluoborate, nanometer WO in electrodeposit liquid B described in step [5]3The mesoporous nickel of core@and SiO2Shell mould powder body, phosphoric acid
The concentration of disodium hydrogen, butynediols and 60% phosphoric acid is respectively 135-180g/L, 170-260g/L, 10-80g/L, 25-40g/L
And 30-90mL/L.
The preparation method of a kind of nickel alloy sky ball the most according to claim 1 load core-shell structure particles electrode material, its
It is characterised by:
Described step [6] concrete operations are:
Fluohydric acid. with deionized water compound concentration as 14-35mL/L, will load WO3The mesoporous nickel of core@and SiO2Core-shell type nanometer
The monel of grain immerses in the hydrofluoric acid solution of above-mentioned preparation, and etch 0.5-1.5 hour is to remove nanometer WO3Core surface shell
SiO2, so that nickel alloy sky ball load nanometer WO on monel surface3Core/mesoporous nickel shell granule.
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| CN116926542A (en) * | 2023-07-12 | 2023-10-24 | 北方工业大学 | Copper-nickel-diamond composite material with low friction coefficient and preparation method thereof |
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