CN107658151A - A kind of foam ambrose alloy super capacitor electrode and its preparation technology - Google Patents
A kind of foam ambrose alloy super capacitor electrode and its preparation technology Download PDFInfo
- Publication number
- CN107658151A CN107658151A CN201710973119.0A CN201710973119A CN107658151A CN 107658151 A CN107658151 A CN 107658151A CN 201710973119 A CN201710973119 A CN 201710973119A CN 107658151 A CN107658151 A CN 107658151A
- Authority
- CN
- China
- Prior art keywords
- foam
- parts
- nickel
- super capacitor
- capacitor electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 122
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 46
- 239000000956 alloy Substances 0.000 title claims abstract description 46
- 239000003990 capacitor Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 106
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000010949 copper Substances 0.000 claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 claims abstract description 67
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 25
- 229910000792 Monel Inorganic materials 0.000 claims description 22
- 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 22
- 238000007747 plating Methods 0.000 claims description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 18
- 230000036571 hydration Effects 0.000 claims description 17
- 238000006703 hydration reaction Methods 0.000 claims description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 17
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005275 alloying Methods 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 229910052701 rubidium Inorganic materials 0.000 abstract description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000002079 cooperative effect Effects 0.000 abstract description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000570 Cupronickel Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Uniform alloy body is formed after uniformly preparing using foam copper nickel coating, heat treatment as matrix and thereon the present invention relates to one kind, the foam ambrose alloy super capacitor electrode and its preparation technology with high specific surface area and pseudo-capacitance characteristic, its advantage is：The present invention prepares electrode using base metal as matrix, with nickel and copper, even all relatively low compared to its preparation cost for pure nickel compared to being prepared with platinum, rubidium metal；The pseudo-capacitance property of nickel oxide is dramatically utilized, and it is formed a good cooperative effect with copper metal, forms an electrochemical capacitance, with high specific capacitance, chemical property well and with the very good circulation life-span；Preparation process is pollution-free, does not produce the material of pollution environment or harmful to human, more green.
Description
Technical field
The present invention relates to a kind of electrode field, more particularly to one kind uniformly to prepare nickel plating using foam copper as matrix and thereon
Uniform alloy body is formed after layer, heat treatment, the foam ambrose alloy super capacitor electrode with high specific surface area and pseudo-capacitance characteristic
And its preparation technology.
Background technology
Capacitor is formed by pressing from both sides one layer of insulation dielectric between two blocks of metal electrodes.It is electric when being added between two metal electrodes
During pressure, electric charge will be stored on electrode, so capacitor is energy-storage travelling wave tube, and electrode is exactly the pass for determining capacitor energy-storage property
Key section.
The accumulation of energy is based on caused by faraday's reaction " pseudo-capacitance " in electrochemical capacitor, and its size is with that can produce
The proportional relation of amount of raw " pseudo-capacitance " active material.In specific electrolyte, some metal oxide electrode surfaces can be entered
The quick faraday's reaction of row and show " pseudo-capacitance " characteristic.
Nickel metal is a kind of base metal, is always the ideal material for producing high quality electrode, its price is less than platinum, rubidium
Deng the noble metal with high electrical property, but its performance peak value such as reachable specific capacitance, electric conductivity is high in theory, be not weaker than
Above-mentioned two kinds of metal oxide containing precious metals of platinum and rubidium, and the price of nickel compared to platinum, it is such as cheaper, meet the need of large-scale production
Ask.
But nickel also possesses certain strategic value simultaneously, if matrix nickel material is replaced as into copper, but also with above-mentioned nickel
Outstanding chemical property, then it is a kind of splendid mode for preparing high-performance electrode.Copper has as a kind of more cheap metal
Outstanding electric conductivity, and nickel also have good synergy, thus prepare a kind of high performance ambrose alloy by suitable mode
Combination electrode is the key of the present invention.
Patent Office of the People's Republic of China disclosed a kind of patent of invention of the preparation method of super capacitor electrode on November 11st, 2015
Application, apply for notification number CN105047433A, the invention uses carbon-based material, as resorcinol, hydroquinones, formaldehyde, furfural,
The carbon materials such as graphene, it is subject to hydrated cobalt chloride, hydrated nickel chloride or zinc acetate as catalyst, is formed in carbon material surface micro-
Pore structure or defect, to increase electrode-electric solution liquid contact area, strengthen its scheme as capacitance electrode performance, but this its with
Carbon material is primary raw material, is not the optimal selection of super capacitor electrode, and its preparation technology very complicated, industrialized production
Cost is higher, and its specific capacitance also has to be hoisted, certain pollution problem in preparation process also be present.
The content of the invention
The electrode used to solve above-mentioned capacitor exist prepare cost height, material expensive, process for producing it is cumbersome and
The problems such as easily causing larger pollution and limited specific capacitance, base is used as the invention provides one kind using copper metal instead of nickel metal
Body, prepare cost it is relatively low, have high specific capacitance, chemical property well and with the foam ambrose alloy in very good circulation life-span
Super capacitor electrode.
It is a further object of the present invention to provide a kind of preparation technology of foam ambrose alloy super capacitor electrode.
To achieve the above object, the present invention uses following technical scheme：
A kind of foam ambrose alloy super capacitor electrode, the preparing raw material of the foam ambrose alloy super capacitor electrode include following parts by weight
Several materials：Six hydration nickel sulfate 50-65 parts, Nickel dichloride hexahydrate 20-28 parts, boric acid 6-8 parts, citric acid 2-3 parts, lauryl amine
8-12 parts, Nickelous nitrate hexahydrate 6-7.5 parts.
Preferably, the preparing raw material of the foam ambrose alloy super capacitor electrode includes the material of following parts by weight：Six
Hydration nickel sulfate 55-60 parts, Nickel dichloride hexahydrate 23-25 parts, boric acid 6.5-7.5 parts, citric acid 2-2.5 parts, lauryl amine 10-12
Part, Nickelous nitrate hexahydrate 7-7.5 parts.
Preferably, the six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid, citric acid, lauryl amine and six nitric hydrates
Nickel purity is all higher than 98%.
A kind of preparation technology of foam ambrose alloy super capacitor electrode, the preparation technology include following preparation process：
1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 2.5-3
In the deionized water of times parts by weight, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electricity
Pole, apply stable constant current to foam copper sheet and to electrode and carry out 15-20min plating, obtain nickel plated foam copper；
2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 600-650
Heat treatment is diffused under the conditions of DEG C, its programming rate is 5 DEG C of min-1, soaking time 120-150min, after furnace cooling
Taking-up obtains foam monel；
3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 15-20 times of parts by weight, by six nitric hydrates
Nickel is dissolved in the ethanol solution of 25-30 times of parts by weight, by the ethanol solution of lauryl amine and the ethanol solution of Nickelous nitrate hexahydrate
It is mixed evenly, is transferred in industrial autoclave, by step 2）Obtained foam monel, which is placed in mixed liquor, to be soaked
1-2h is steeped, then industrial autoclave is fully sealed, 10-12h, furnace cooling are incubated under the conditions of 180-200 DEG C
After obtain the foam ambrose alloy super capacitor electrode.
Preferably, the step 1）Described foam copper sheet is equipped with to electrode in its tow sides, using double anode
The mode of plating is carried out, and anode is preferably active carbon anode.Double anode plating stirs plating compared to usually used single anode,
With the advantages of uniformity is higher, coating is more uniform, and electroplating efficiency can greatly improve, and shorten electroplating time, accelerate
The process of industrialized production.
Preferably, the step 3）Middle be placed in foam monel when being soaked in mixed liquor can use sealing decompression leaching
Bubble, pumps the air pressure in industrial autoclave to 0.8atm under air-proof condition.
Preferably, the step 1）Voltage constant current is 0.04-0.06A/cm during middle plating-2。
Preferably, the step 1）Used foam copper thickness is 0.5-2mm.
Nickel foam is a kind of material with three-dimensional porous structure, is received much concern in electro-catalysis field, is led in electrochemistry
Domain upstream is widely applied, such as the electrode material of ultracapacitor, the nickel foam nickel electric conductivity prepared are prepared with nickel foam
It is excellent, obtain very high power density and energy density.And nickel is used widely as alloying element, it fights as a kind of
Slightly noble metal, has the nickel resources of more than half all to stainless steel making, causes nickel resources constantly to reduce, so if using nickel
Copper alloy makees matrix, and cost will substantially reduce.
Foam copper is equally a kind of material with three-dimensional porous structure, has that specific surface area is big, porosity is high and right
The features such as excellent electrical properties, along with matrix copper processing is less expensive, one layer of nickel is prepared on foam copper surface using as preparing foam
The matrix of monel be it is most suitable only.Monel has good room-temperature mechanical property and elevated temperature strength, has high resistance to
Corrosion and wearability, easy processing is nonmagnetic, and purposes is quite extensive, such as manufactures travelling-wave tubes, aero-engine and other electron tubes,
Monel is all more outstanding structural material in these fields.
Monel is contrasted with single nickel simple substance or copper simple substance, and its conductivity is not weak and copper simple substance, and two
Person's combination can improve the hardness and wearability of elemental copper, greatly improve its physical property, and both interactions after combination
Its pseudo-capacitance characteristic is set also to be improved.A small amount of nickel is only adulterated on copper, just can possess the characteristics of foregoing, from price
Upper be far below directly uses nickel foam.
Cu-Ni bianry alloys are all mutually dissolved completely in the whole compositional ranges of solid-state and liquid, and
Solid-state is substitutional solid solution, has fcc class formations so that the mixing of both Cu-Ni alloys characteristic is more uniform, has nickel
With the outstanding property of both copper.
Step 3）It is a kind of hydrothermal synthesis reaction in the reaction of industrial autoclave, Hydrothermal Synthesiss are also known as hydro-thermal method, category
The category of liquid chemical method.Refer in the pressure vessel of sealing, using water as solvent, the change that is carried out under conditions of HTHP
Learn reaction.Hydrothermal Synthesiss refer to temperature in 100 ~ 1000oC, under conditions of pressure is 1MPa ~ 1GPa, are using hydrous matter
Synthesized in chemical reaction.Under subcritical and supercritical water heat condition, hydro-thermal reaction can replace some high temperature solid state reactions,
Because reaction is in molecular level, reactivity is improved.And heterogeneous nucleation and heterogeneous nucleation mechanism due to hydro-thermal reaction
And the diffusion mechanism of solid phase reaction, the noval chemical compound and new material that can not be prepared with other method can be produced.
Hydro-thermal reaction in the present invention causes the three-dimensional porous structure superficial growth nickel oxygen composition knot in foam monel
Structure, and growth of the lauryl amine to nickel oxygen possesses certain guiding and facilitation so that with two-dimensional nano piece shape during nickel oxide growth
Like growth, the foam monel for itself having three-dimensional porous structure has had great specific surface area, and three-dimensional porous
Body structure surface regrowth two-dimensional nano chip architecture so that the foam ambrose alloy super capacitor electrode specific surface area of present invention gained enters one
Step is greatly increased.
The beneficial effects of the invention are as follows：The present invention prepares electrode using base metal as matrix, with nickel and copper, compared to
Platinum, rubidium metal prepare even all relatively low compared to its preparation cost for pure nickel；Dramatically utilize the quasi- electricity of nickel oxide
Capacitive matter, and it is formed a good cooperative effect with copper metal, an electrochemical capacitance is formed, with high ratio electricity
Hold, chemical property is good and has the very good circulation life-span；Preparation process is pollution-free, does not produce pollution environment or endangers people
The material of body, it is more green.
Brief description of the drawings
Fig. 1 is foam base plate 10.0kx SEM figure of the present invention after double anode electronickelling；
Fig. 2 is that the SEM of foam ambrose alloy super capacitor electrode obtained by the present invention schemes, left figure 2000x SEM, right figure 5000x
SEM；
Fig. 3 is electrode in 6.0molL-1CV curves in KOH solution（Sweep fast 5mVs-1）, wherein a is prepared by the present invention
A kind of foam ambrose alloy super capacitor electrode, b be with conventional process prepare nickel electrode control sample；
Fig. 4 is electrode in 6.0molL-1The different CV curves swept under speed in KOH solution.
Embodiment
Embodiment 1
A kind of preparation technology of foam ambrose alloy super capacitor electrode, the preparation technology include following preparation process：
1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 2.5 times
In the deionized water of parts by weight, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electrode,
Apply stable constant current to foam copper sheet and to electrode and carry out 15min plating, voltage constant current is 0.06A/cm during plating-2, obtain
To nickel plated foam copper；
2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 650 DEG C of bars
Heat treatment is diffused under part, its programming rate is 5 DEG C of min-1, soaking time 150min, take out and obtain after furnace cooling
Foam monel；
3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 20 times of parts by weight, by Nickelous nitrate hexahydrate
It is dissolved in the ethanol solution of 25 times of parts by weight, the ethanol solution of the ethanol solution of lauryl amine and Nickelous nitrate hexahydrate is mixed and stirred
Mix uniformly, be transferred in industrial autoclave, by step 2）Obtained foam monel is placed in immersion 2h in mixed liquor, adopts
With sealing decompression immersion, the air pressure in industrial autoclave is pumped to 0.8atm, then to industrial high under air-proof condition
Pressure reactor is fully sealed, and 10h is incubated under the conditions of 200 DEG C, the foam ambrose alloy super capacitor is obtained after furnace cooling
Electrode.
The step 1）Used foam copper thickness is 0.5mm；The preparation of the foam ambrose alloy super capacitor electrode is former
Material includes the material of following parts by weight：50 parts of six hydration nickel sulfate, 20 parts of Nickel dichloride hexahydrate, 8 parts of boric acid, 2 parts of citric acid,
12 parts of lauryl amine, 6 parts of Nickelous nitrate hexahydrate.
Embodiment 2
A kind of preparation technology of foam ambrose alloy super capacitor electrode, the preparation technology include following preparation process：
1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 3 times of weights
In the deionized water for measuring number, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electrode, it is right
Foam copper sheet and apply stable constant current to electrode and carry out 20min plating, voltage constant current is 0.04A/cm during plating-2, obtain
Nickel plated foam copper；
2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 600 DEG C of bars
Heat treatment is diffused under part, its programming rate is 5 DEG C of min-1, soaking time 120min, take out and obtain after furnace cooling
Foam monel；
3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 20 times of parts by weight, by Nickelous nitrate hexahydrate
It is dissolved in the ethanol solution of 25 times of parts by weight, the ethanol solution of the ethanol solution of lauryl amine and Nickelous nitrate hexahydrate is mixed and stirred
Mix uniformly, be transferred in industrial autoclave, by step 2）Obtained foam monel is placed in immersion 1h in mixed liquor, adopts
With sealing decompression immersion, the air pressure in industrial autoclave is pumped to 0.8atm, then to industrial high under air-proof condition
Pressure reactor is fully sealed, and 12h is incubated under the conditions of 200 DEG C, the foam ambrose alloy super capacitor is obtained after furnace cooling
Electrode.
The step 1）Used foam copper thickness is 1mm；The preparing raw material of the foam ambrose alloy super capacitor electrode
Include the material of following parts by weight：65 parts of six hydration nickel sulfate, 28 parts of Nickel dichloride hexahydrate, 6 parts of boric acid, 3 parts of citric acid, ten
8 parts of diamines, 7.5 parts of Nickelous nitrate hexahydrate.
Embodiment 3
A kind of preparation technology of foam ambrose alloy super capacitor electrode, the preparation technology include following preparation process：
1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 3 times of weights
In the deionized water for measuring number, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electrode, it is right
Foam copper sheet and apply stable constant current to electrode and carry out 15min plating, voltage constant current is 0.06A/cm during plating-2, obtain
Nickel plated foam copper；
2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 650 DEG C of bars
Heat treatment is diffused under part, its programming rate is 5 DEG C of min-1, soaking time 120min, take out and obtain after furnace cooling
Foam monel；
3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 15 times of parts by weight, by Nickelous nitrate hexahydrate
It is dissolved in the ethanol solution of 30 times of parts by weight, the ethanol solution of the ethanol solution of lauryl amine and Nickelous nitrate hexahydrate is mixed and stirred
Mix uniformly, be transferred in industrial autoclave, by step 2）Obtained foam monel is placed in immersion 1.5h in mixed liquor,
Using sealing decompression immersion, the air pressure in industrial autoclave is pumped to 0.8atm, then to industry under air-proof condition
Autoclave is fully sealed, and 12h is incubated under the conditions of 180 DEG C, and the super electricity of foam ambrose alloy is obtained after furnace cooling
Hold electrode.
The step 1）Used foam copper thickness is 2mm；The preparing raw material of the foam ambrose alloy super capacitor electrode
Include the material of following parts by weight：55 parts of six hydration nickel sulfate, 25 parts of Nickel dichloride hexahydrate, 7.5 parts of boric acid, citric acid 2.5
Part, 11.5 parts of lauryl amine, 7.5 parts of Nickelous nitrate hexahydrate.
Embodiment 4
A kind of preparation technology of foam ambrose alloy super capacitor electrode, the preparation technology include following preparation process：
1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 2.5 times
In the deionized water of parts by weight, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electrode,
Apply stable constant current to foam copper sheet and to electrode and carry out 15min plating, voltage constant current is 0.04A/cm during plating-2, obtain
To nickel plated foam copper；
2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 620 DEG C of bars
Heat treatment is diffused under part, its programming rate is 5 DEG C of min-1, soaking time 120min, take out and obtain after furnace cooling
Foam monel；
3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 20 times of parts by weight, by Nickelous nitrate hexahydrate
It is dissolved in the ethanol solution of 25 times of parts by weight, the ethanol solution of the ethanol solution of lauryl amine and Nickelous nitrate hexahydrate is mixed and stirred
Mix uniformly, be transferred in industrial autoclave, by step 2）Obtained foam monel is placed in immersion 2h in mixed liquor, adopts
With sealing decompression immersion, the air pressure in industrial autoclave is pumped to 0.8atm, then to industrial high under air-proof condition
Pressure reactor is fully sealed, and 12h is incubated under the conditions of 180 DEG C, the foam ambrose alloy super capacitor is obtained after furnace cooling
Electrode.
The step 1）Used foam copper thickness is 1mm；The preparing raw material of the foam ambrose alloy super capacitor electrode
Include the material of following parts by weight：55 parts of six hydration nickel sulfate, 25 parts of Nickel dichloride hexahydrate, 6.5 parts of boric acid, citric acid 2.5
Part, 12 parts of lauryl amine, 7.5 parts of Nickelous nitrate hexahydrate.
Embodiment 5
A kind of preparation technology of foam ambrose alloy super capacitor electrode, the preparation technology include following preparation process：
1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 3 times of weights
In the deionized water for measuring number, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electrode, it is right
Foam copper sheet and apply stable constant current to electrode and carry out 20min plating, voltage constant current is 0.06A/cm during plating-2, obtain
Nickel plated foam copper；
2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 600 DEG C of bars
Heat treatment is diffused under part, its programming rate is 5 DEG C of min-1, soaking time 120-150min, taken out after furnace cooling
Obtain foam monel；
3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 20 times of parts by weight, by Nickelous nitrate hexahydrate
It is dissolved in the ethanol solution of 30 times of parts by weight, the ethanol solution of the ethanol solution of lauryl amine and Nickelous nitrate hexahydrate is mixed and stirred
Mix uniformly, be transferred in industrial autoclave, by step 2）Obtained foam monel is placed in immersion 1h in mixed liquor, adopts
With sealing decompression immersion, the air pressure in industrial autoclave is pumped to 0.8atm, then to industrial high under air-proof condition
Pressure reactor is fully sealed, and 12h is incubated under the conditions of 180 DEG C, the foam ambrose alloy super capacitor is obtained after furnace cooling
Electrode.
The step 1）Used foam copper thickness is 0.5-2mm；The preparation of the foam ambrose alloy super capacitor electrode
Raw material includes the material of following parts by weight：60 parts of six hydration nickel sulfate, 23 parts of Nickel dichloride hexahydrate, 7.5 parts of boric acid, citric acid
2 parts, 10 parts of lauryl amine, 7 parts of Nickelous nitrate hexahydrate.
Above example 1-5 is detected：
1）Electronic Speculum test, multiplication factor are scanned to the foam base plate in the preparation process of embodiment 1 after double anode electronickelling
For 10.0kx, foam base plate plating nickel on surface layer is thicker after electroplating as shown in Figure 1, and nickel amount is sufficient；
2）The electrode that gained is prepared to embodiment 2 is scanned Electronic Speculum test, and wherein a is sweeping for 2.0kx multiples as shown in Figure 2
Face electron microscope, b are the scanning electron microscope (SEM) photograph of 5.0kx multiples, it can be clearly seen that covered with pole on the obtained electrode of embodiment 2
Its uniform and fine and close nickel oxide nano-sheet, substantially increase specific surface area；
3）The nickel base electrode prepared to embodiment 3 and with conventional process carries out electrochemical property test, and electrode is in 6.0molL- 1CV curves in KOH solution（Sweep fast 5mVs-1）, wherein a is a kind of foam ambrose alloy super capacitor electrode prepared by the present invention
Sample, b are the control sample of the nickel base electrode prepared with conventional process, can be clearly visible embodiment 3 as shown in Figure 3 with higher
Specific capacitance and more excellent chemical property；
4）The electrochemical property tests for sweeping speed different to embodiment 1-5 progress are as shown in Figure 4 electrode in 6.0molL- 1The different CV curves swept under speed in KOH solution.
Claims (8)
- A kind of 1. foam ambrose alloy super capacitor electrode, it is characterised in that the preparing raw material of the foam ambrose alloy super capacitor electrode Include the material of following parts by weight：Six hydration nickel sulfate 50-65 parts, Nickel dichloride hexahydrate 20-28 parts, boric acid 6-8 parts, lemon Sour 2-3 parts, lauryl amine 8-12 parts, Nickelous nitrate hexahydrate 6-7.5 parts.
- 2. a kind of foam ambrose alloy super capacitor electrode according to claim 1, it is characterised in that the foam ambrose alloy is super The preparing raw material of capacitance electrode includes the material of following parts by weight：Six hydration nickel sulfate 55-60 parts, Nickel dichloride hexahydrate 23- 25 parts, boric acid 6.5-7.5 parts, citric acid 2-2.5 parts, lauryl amine 10-12 parts, Nickelous nitrate hexahydrate 7-7.5 parts.
- A kind of 3. foam ambrose alloy super capacitor electrode according to claim 2, it is characterised in that six hydrated sulfuric acid Nickel, Nickel dichloride hexahydrate, boric acid, citric acid, lauryl amine and Nickelous nitrate hexahydrate purity are all higher than 98%.
- 4. a kind of preparation technology of foam ambrose alloy super capacitor electrode as described in Claim 1-3 any one, its feature exist In the preparation technology includes following preparation process：1）The uniform nickel plating in foam copper surface：Six hydration nickel sulfate, Nickel dichloride hexahydrate, boric acid and citric acid are dissolved in its 2.5-3 In the deionized water of times parts by weight, electroplate liquid is made, installs foam copper sheet, is set up in foam copper sheet face side to electricity Pole, apply stable constant current to foam copper sheet and to electrode and carry out 15-20min plating, obtain nickel plated foam copper；2）Alloying Treatment：By step 1）Obtained nickel plated foam copper is placed under nitrogen protection atmosphere, is placed in stove in 600-650 Heat treatment is diffused under the conditions of DEG C, its programming rate is 5 DEG C of min-1, soaking time 120-150min, after furnace cooling Taking-up obtains foam monel；3）Nickel oxide nano-sheet structure growth：Lauryl amine is dissolved in the ethanol solution of its 15-20 times of parts by weight, by six nitric hydrates Nickel is dissolved in the ethanol solution of 25-30 times of parts by weight, by the ethanol solution of lauryl amine and the ethanol solution of Nickelous nitrate hexahydrate It is mixed evenly, is transferred in industrial autoclave, by step 2）Obtained foam monel, which is placed in mixed liquor, to be soaked 1-2h is steeped, then industrial autoclave is fully sealed, 10-12h, furnace cooling are incubated under the conditions of 180-200 DEG C After obtain the foam ambrose alloy super capacitor electrode.
- A kind of 5. preparation technology of foam ambrose alloy super capacitor electrode according to claim 4, it is characterised in that the step Rapid 1）Described foam copper sheet is equipped with to electrode in its tow sides, is carried out by the way of double anode plating, anode is preferred For active carbon anode.
- A kind of 6. preparation technology of foam ambrose alloy super capacitor electrode according to claim 4, it is characterised in that the step Rapid 3）It is middle to be placed in foam monel using sealing decompression immersion when being soaked in mixed liquor, by industrial high pressure under air-proof condition Air pressure in reactor is pumped to 0.8atm.
- A kind of 7. preparation technology of foam ambrose alloy super capacitor electrode according to claim 4, it is characterised in that the step Rapid 1）Voltage constant current is 0.04-0.06A/cm during middle plating-2。
- A kind of 8. preparation technology of foam ambrose alloy super capacitor electrode according to claim 4, it is characterised in that the step Rapid 1）Used foam copper thickness is 0.5-2mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710973119.0A CN107658151B (en) | 2017-10-18 | 2017-10-18 | A kind of foam ambrose alloy super capacitor electrode and its preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710973119.0A CN107658151B (en) | 2017-10-18 | 2017-10-18 | A kind of foam ambrose alloy super capacitor electrode and its preparation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107658151A true CN107658151A (en) | 2018-02-02 |
| CN107658151B CN107658151B (en) | 2019-05-14 |
Family
ID=61118722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710973119.0A Active CN107658151B (en) | 2017-10-18 | 2017-10-18 | A kind of foam ambrose alloy super capacitor electrode and its preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107658151B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154695A (en) * | 2011-02-25 | 2011-08-17 | 北京化工大学 | Nickel oxide nano rod array material, method for preparing same and application thereof |
| US20150294799A1 (en) * | 2014-04-15 | 2015-10-15 | Epistar Corporation | Electrode for energy storage device and energy storage device using the same |
| CN105895383A (en) * | 2016-04-11 | 2016-08-24 | 中国工程物理研究院材料研究所 | Supercapacitor-used alloy/amorphous nickel cobalt hydroxide composite electrode and preparation method thereof |
| CN106381506A (en) * | 2016-10-18 | 2017-02-08 | 西安交通大学 | Preparation method of layered ferronickel hydroxide electrode |
| CN106910637A (en) * | 2017-02-28 | 2017-06-30 | 广东工业大学 | A kind of combination electrode material and preparation method thereof and ultracapacitor |
-
2017
- 2017-10-18 CN CN201710973119.0A patent/CN107658151B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154695A (en) * | 2011-02-25 | 2011-08-17 | 北京化工大学 | Nickel oxide nano rod array material, method for preparing same and application thereof |
| US20150294799A1 (en) * | 2014-04-15 | 2015-10-15 | Epistar Corporation | Electrode for energy storage device and energy storage device using the same |
| CN105895383A (en) * | 2016-04-11 | 2016-08-24 | 中国工程物理研究院材料研究所 | Supercapacitor-used alloy/amorphous nickel cobalt hydroxide composite electrode and preparation method thereof |
| CN106381506A (en) * | 2016-10-18 | 2017-02-08 | 西安交通大学 | Preparation method of layered ferronickel hydroxide electrode |
| CN106910637A (en) * | 2017-02-28 | 2017-06-30 | 广东工业大学 | A kind of combination electrode material and preparation method thereof and ultracapacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107658151B (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107904614B (en) | A kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof | |
| WO2021213338A1 (en) | Nickel phosphide composite with multi-level pore structure, preparation method therefor and use thereof | |
| CN110201670B (en) | Ferronickel double-metal hydroxide/foamed nickel catalyst based on ferric trichloride/urea eutectic solvent, and preparation method and application thereof | |
| CN105734606B (en) | A kind of SPE water electrolysis structure of ultra-thin membrane electrode and its preparation and application | |
| CN104894595B (en) | A kind of amorphous metal oxide hydrogen-precipitating electrode of high catalytic activity and preparation method thereof | |
| CN108479813A (en) | A kind of water electrolysis hydrogen production coats the preparation method of seleno catalyst with carbon nanotube | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| CN113718281B (en) | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof | |
| CN108447703A (en) | A kind of ferronickel double-metal hydroxide@ceria heterogeneous structural nanos sheet material, preparation method and applications | |
| CN109092341A (en) | The nitrogen-doped carbon nanocomposite of hollow Copper-cladding Aluminum Bar cobalt oxide nickel coated and preparation | |
| CN107749350B (en) | A kind of super capacitor cupro-nickel combination electrode and its preparation process | |
| CN106971865A (en) | A kind of Polymerization of Polyaniline/carbon Nanotube with high specific capacitance/bafta composite and flexible electrode and its preparation and application | |
| CN105483744A (en) | Porous hydrogen evolution catalyst, preparation method of porous hydrogen evolution catalyst and electrode containing hydrogen evolution catalyst | |
| CN110644016B (en) | Preparation method of nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation | |
| CN113249740B (en) | Method for preparing graphene by electrochemical continuous and synchronous stripping and reduction | |
| CN104928713B (en) | The preparation method and its usage of the Ni-based production hydrogen electrode of conducting polymer cladding | |
| CN106591926B (en) | In the method that steel surface prepares the porous nickel nickel evolving hydrogen reaction catalyst of CNTs- | |
| CN102234814B (en) | Macroporous electrode and preparation method thereof | |
| CN107658151B (en) | A kind of foam ambrose alloy super capacitor electrode and its preparation process | |
| CN111229272A (en) | Ternary lamellar carbide Mo2Ga2C composite flower-shaped MoS2Nanoparticle composite material and preparation method and application thereof | |
| CN107731565B (en) | A kind of NiTi copper multidimensional structure capacitance electrode and its preparation process | |
| CN108640165A (en) | A kind of metal oxide nanostructure composite material and preparation method | |
| CN113584517A (en) | Preparation method of non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode | |
| CN114134531A (en) | General method for preparing self-supporting layered metal hydroxide | |
| CN113604816A (en) | Preparation method and application of high-entropy alloy fiber electrocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A foamed nickel-copper supercapacitor electrode and preparation process thereof Effective date of registration: 20220912 Granted publication date: 20190514 Pledgee: Zhejiang Deqing rural commercial bank Limited by Share Ltd. Pledgor: DEQING DING XING ELECTRONICS CO.,LTD. Registration number: Y2022330002168 |