CN110364372A - A kind of supercapacitor vanadic acid nickel material, preparation method and application - Google Patents
A kind of supercapacitor vanadic acid nickel material, preparation method and application Download PDFInfo
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- CN110364372A CN110364372A CN201910710672.4A CN201910710672A CN110364372A CN 110364372 A CN110364372 A CN 110364372A CN 201910710672 A CN201910710672 A CN 201910710672A CN 110364372 A CN110364372 A CN 110364372A
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- vanadic acid
- acid nickel
- supercapacitor
- nickel material
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 239000000463 material Substances 0.000 title claims abstract description 140
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 96
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000007772 electrode material Substances 0.000 claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229940031098 ethanolamine Drugs 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000110 cooling liquid Substances 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 241000446313 Lamella Species 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 14
- 229910003206 NH4VO3 Inorganic materials 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 8
- 229920006362 Teflon® Polymers 0.000 description 8
- 230000004087 circulation Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000003407 synthetizing effect Effects 0.000 description 2
- VFYFMNCKPJDAPV-UHFFFAOYSA-N 2,2'-(5-oxo-1,3-dioxolan-4,4-diyl)diessigs Chemical compound C1N(C2)CN3CN1CN2C3.OC(=O)CC1(CC(O)=O)OCOC1=O VFYFMNCKPJDAPV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 244000302512 Momordica charantia Species 0.000 description 1
- 235000009811 Momordica charantia Nutrition 0.000 description 1
- 235000009812 Momordica cochinchinensis Nutrition 0.000 description 1
- 235000018365 Momordica dioica Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- HAZNKDJFOOUKJY-UHFFFAOYSA-N [Ni++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ni++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HAZNKDJFOOUKJY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of preparation method of supercapacitor vanadic acid nickel material, step 1: in a solvent by ammonium vanadate dissolution, nickel nitrate is added, obtains reaction precursor liquid;Step 2: reaction precursor liquid alkaline structure directed agents are adjusted into pH value to 7-12, is uniformly mixed, obtains reaction mixture;Step 3: reaction mixture is transferred in autoclave, is reacted 8-15 hours at 100-180 DEG C, is obtained product vanadic acid nickel material.Using one step hydro thermal method, using a variety of alkaline reagents as structure directing agent, and vanadic acid nickel material is obtained by adjusting pH, it is easy to operate and safe, at low cost, product purity is high.A kind of flower-shaped vanadic acid nickel material is also disclosed, and in the flower-like structure that lamella is accumulated, specific surface area is larger, there is good electric conductivity and Surface Permeability, and reactivity site is more.A kind of flower-shaped vanadic acid nickel material is also disclosed as electrode material for super capacitor application, shows high specific capacitance, good capacity retention and high rate performance, electrochemical impedance are low.
Description
Technical field
The present invention relates to bimetallic oxide electrode material technical fields, and in particular to a kind of supercapacitor vanadic acid nickel
Material, preparation method and application.
Background technique
In recent years, there is an urgent need to develop the environmental-friendly energy and energy storage to fill for ever-increasing energy demand and environmental problem
It sets.Supercapacitor is as model electrochemical energy storage device, with its superior power density, quick charging and discharging capabilities and excellent
The chemical property outstanding such as cyclical stability cause the extensive concern of people.According to energy storage mechnism difference, super capacitor
Device is generally divided into two classes, i.e. double layer capacitor (EDLC) and fake capacitance capacitor.The material of EDLC is mostly carbon material, such as activity
Charcoal, carbon nanotube, graphene etc. carry out energy storage by forming electric double layer in electrode and solution interface.And fake capacitance capacitor
The working principle of device is electric energy to be converted into chemical energy storage, and general fake capacitance material has metal oxide and conducting polymer.
Hinder supercapacitor in the widely applied significant challenge of energy storage field first is that its limited energy density.In order to overcome this
Obstacle explores height ratio capacity, the new electrode materials of broad potential window are one of hot spots of supercapacitor research.
Transiton metal binary oxides (BTMO) are used as a kind of battery material, due to the multiple oxidation state of its crystal structure
With unique electrochemical energy storage mechanism, the extensive concern for causing research field is nearest.It is single by introducing different metal element
The mixed-metal oxides formed in one metal oxide, can synergistically improve the reversible capacity of single metal oxides, electricity
Chemical stability and high rate performance.Barium oxide is as a kind of important mixed-metal oxides, since composite structure is special
The difficulty of barium oxide, is almost forgotten by people.Vanadic acid nickel has significant chemical property, the structures such as nanometer sheet and nanotube
Being produced and being verified can be used as high performance lithium ion battery negative material use.
Vaiyapuri Soundharrajan et al. is simple in one kind that Ceramics International is reported
Metal organic framework-burning (MOF-C) technology one pot process Ni3V2O8(NVO).Its pattern is irregular rodlike, porous
The particle of balsam pear and micro-/ nano hydridization.Using the material as lithium ion battery (LIBS) electrode material, surveyed in cathode of lithium battery
In examination, the discharge capacity for the first time of electrode is 1362 mA h g-1, reversible capacity is 822 mA h g-1.In 2000 mA g-1Under,
After 5000 circulations, it is still able to maintain 724 mA h g-1Reversible capacity.
Ding Shujiang research team reports in J. Mater. Chem. A using simple hydrothermal method and roasting technique,
It is successfully prepared for ordered mesopore carbon (CMK-3) load Ni for the first time3V2O8Novel orderly hybrid nanostructure (Ni3V2O8@CMK-
3).Have benefited from its firm porous structure and excellent conductive characteristic, the stratiform hydridization Ni of preparation3V2O8@CMK-3 composite material
Cyclical stability with higher is 500 mA g in current density-1After lower circulation 200 times, reversible capacity is up to 945.9
mA h g-1, when circulating current density is 20 A g-1When, high-speed capacity is 161.5 mA h g-1。
The Chinese invention patent application that application publication number is CN108101123A discloses a kind of square prism vanadic acid nickel and receives
Rice material and preparation method thereof, can apply in the energy storage fields such as electrode material for super capacitor.
However, square prism vanadic acid nickel is since specific surface area is small, electric conductivity and Surface Permeability are poor, reactivity site
It is few, there are specific capacitances when being used for supercapacitor as electrode material it is low, circulation conservation rate is low the problems such as.Therefore, it is necessary to develop
A kind of vanadic acid nickel electrode material and preparation method thereof more than high surface area, high conductivity and Surface Permeability, reactivity site,
And be applied in supercapacitor as electrode material, and improve the structure and preparation method of vanadic acid nickel material, it realizes high
Specific capacitance and good circulation performance.
Summary of the invention
It is an object of the present invention in view of the above shortcomings of the prior art, propose it is a kind of it is easy to operate, at low cost,
Material morphology is controllable and prepares the preparation method of the supercapacitor vanadic acid nickel material of resulting materials electrochemical performance.
It is another object of the present invention to propose a kind of high surface area, highly conductive for the above-mentioned deficiency of the prior art
Flower-shaped supercapacitor vanadic acid nickel material more than property and Surface Permeability, reactivity site.
It is another object of the present invention to propose a kind of flower-shaped supercapacitor for the above-mentioned deficiency of the prior art
Vanadic acid nickel material is used to show high specific capacitance performance and good cycle performance as the application of electrode material for super capacitor.
The present invention solve technical problem the technical solution adopted is that, propose a kind of system of supercapacitor vanadic acid nickel material
Preparation Method, comprising the following steps:
Step 1: in a solvent by ammonium vanadate dissolution, nickel nitrate is added, obtains reaction precursor liquid;Vanadium in the ammonium vanadate
Additional amount and the nickel nitrate in nickel element additional amount molar ratio be (1-6): 6;The solvent is ethyl alcohol, one in water
Kind is any than mixing;The nickel nitrate includes nickel nitrate hydrate;
Step 2: reaction precursor liquid alkaline structure directed agents are adjusted into pH value to 7-12, is uniformly mixed, it is mixed to obtain reaction
Close liquid;The alkaline structure directed agents are one of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ethanol amine or several any
Than mixing;Preferably, the potassium hydroxide, sodium hydroxide, ammonium hydroxide, ethanol amine be aqueous solution form or ethanol solutions or
(water/ethyl alcohol) mixed solution form;
Step 3: the reaction mixture is transferred in autoclave, is reacted 8-15 hours at 100-180 DEG C, solid after cooling
Liquid separation is dried to obtain product vanadic acid nickel material after solid product washing for several times at 50-100 DEG C.
Preferably, the alkaline structure directed agents are ethanol amine in step 2.
Preferably, in step 1, the solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is (0.1-1): 1.
Preferably, in step 1, in the ammonium vanadate in the additional amount of vanadium and the nickel nitrate nickel element plus
The molar ratio for entering amount is (3-5): 6.
Preferably, the condition of nickel nitrate is added described in step 1 are as follows: by nickel nitrate under the conditions of 50-90 DEG C of stirring in water bath
It is added in Ammonium Vanadate Solution.
Preferably, the reaction temperature is 150-160 DEG C in step 3.
Preferably, the reaction time is 10-12h in step 3.
Preferably, the method for the separation of solid and liquid is filtering or centrifugation in step 3.
Preferably, dry described in step 3 are as follows: the vacuum drying 12-24h at 60-80 DEG C.
Preferably, the alkaline structure directed agents are ethanol amine in step 2.
Preferably, adjusting pH value to 9 with alkaline structure directed agents in step 2.
Preferably, in step 2, it is described to be uniformly mixed are as follows: to stir 20 min under 80 DEG C of water bath conditions.
Preferably, the reaction time is 10h in step 3.
The present invention also provides the flower-shaped supercapacitor vanadic acid nickel materials that a kind of above-mentioned preparation method is prepared.
The present invention also provides a kind of above-mentioned flower-shaped supercapacitors to use vanadic acid nickel material as electrode of super capacitor material
The application of material.
A kind of flower-shaped supercapacitor provided by the invention is had the following beneficial effects: with the preparation method of vanadic acid nickel material
1, using one step hydro thermal method, using a variety of alkaline reagents as structure directing agent, and vanadic acid nickel material is obtained by adjustment process pH
Material, it is easy to operate and safe, at low cost, product purity is high.
2, the dissolution of ammonium metavanadate is conducive to as solvent using the aqueous solution of ethyl alcohol.
A kind of flower-shaped supercapacitor provided by the invention is had the following beneficial effects: with vanadic acid nickel material
1, vanadic acid nickel material is in the flower-like structure of lamella accumulation, and specific surface area is larger, there is good electric conductivity and Surface Permeability,
For flower-like structure there are a large amount of central hole structure, pore-size distribution is wide, and reactivity site is more.
A kind of flower-shaped supercapacitor provided by the invention uses vanadic acid nickel material as electrode material for super capacitor application
When have the following beneficial effects:
1, high specific capacitance is shown when as single electrode material, in 1 A g-1Under current density, specific capacitance reaches 1054 F g-1;Good capacity retention is shown, is had extended cycle life, specific capacitance conservation rate is up to 89 after 10000 charge and discharge cycles
%;In addition, flower-shaped vanadic acid nickel material electrochemical impedance is low, high rate performance is good.
2, being assembled into supercapacitor has biggish operating potential, biggish power density and energy density and excellent
Cyclical stability.
Detailed description of the invention
Fig. 1 is the XRD diagram of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 3 is the TEM figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 4 is the nitrogen adsorption desorption curve and graph of pore diameter distribution of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 5 is CV and the GCD figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 6 is the long circulating figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 7 is the SEM figure of material 2 in comparative example 2 of the present invention, material 3, material 4, material 5, material 6, material 11.
Fig. 8-13 is that material 2, material 3, material 4, material 5, material 6, material 11 are made in comparative example 2 of the present invention respectively
CV figure after electrode.
Specific embodiment
Following is a specific embodiment of the present invention in conjunction with the accompanying drawings, technical scheme of the present invention will be further described,
However, the present invention is not limited to these examples.
Embodiment 1
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.5:
1;6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O is obtained
Reaction precursor liquid.PH value is adjusted to about 9 with alkaline structure directed agents (aqueous ethanolamine), continues 20 min of stirring in water bath,
Obtain reaction mixture.Reaction mixture is transferred in the stainless steel autoclave of 100 mL Teflon linings.Heat and
After being kept for 10 hours at 150 DEG C, cooled to room temperature.Centrifuge separation, the substance after synthesis is washed with deionized water and ethyl alcohol
It washs for several times, dry 16h obtains vanadic acid nickel solid in 60 DEG C of vacuum drying oven.
Above-mentioned vanadic acid nickel material, acetylene black and the PVDF being prepared is weighed by the mass ratio of 8:1:1, is mixed
Few drops of N-Methyl pyrrolidone reagents are added after grinding, magnetic agitation handles 12 h, and obtained slurry, which is coated on area, is
1cm2Preparation nickel foam substrate on, then at 80 DEG C dry 24 hours in vacuum drying oven.The quality of active material is negative
Lotus is about 2mg cm-1。
The vanadic acid nickel material being prepared using the above method is subjected to X-ray diffraction analysis (abbreviation XRD, similarly hereinafter), it is real
It tests as shown in Figure 1 using the X ' Pert PRO type X-ray diffraction spectra instrument result of PANalytical company, Holland production.From figure
It can be seen that in 1 (122) of the diffraction maximum and vanadic acid nickel at 2 θ=35.84 °, 44.07 °, 58.7 °, 63.9 °, (042),
(442) it is corresponded to well with (162) crystal face.
The vanadic acid nickel being prepared using the above method is subjected to morphology characterization using scanning electron microscope (abbreviation SEM, similarly hereinafter),
Its microscopic appearance is studied, the Hitachi S4700 type scanning electron microscope of Hitachi company, Japan is used in experiment.Fig. 2 is
The SEM characterization result of vanadic acid nickel material, it can be clearly seen that, prepared vanadic acid nickel material shows flower-like structure, lamella
Thickness is uniform, and laminated structure has big contact area.
The vanadic acid nickel being prepared using the above method is characterized using transmission electron microscope (abbreviation TEM, similarly hereinafter), is studied
Its microscopic appearance feature.It is transmitted in experiment using the Tecnai G2 F30 S-Twin high-resolution of Philips-FEI company, Holland
Electron microscope, as a result as shown in Figure 3.Fig. 3 is the TEM characterization result of vanadic acid nickel under different enlargement ratios, it is clearly illustrated
Lamella is accumulated to form pore structure and be self-assembled into flower-like structure.
The vanadic acid nickel material being prepared using the above method is subjected to isothermal N2Adsorption desorption (BET) test, experiment use
The 2010 type Full-automatic physical chemical adsorption instrument of ASAP of Micromeritics company production carries out BET and pore-size distribution analysis,
As a result as shown in Figure 4.Show relative pressure (P/P0) significant hysteresis loop between 0.65-1.0, belong to typical IV
Type thermoisopleth shows that there are central hole structures in vanadic acid nickel material.It can be clearly seen that vanadic acid nickel material from graph of pore diameter distribution
Material has apparent meso-hole structure.It is calculated according to BET and NLDFT model, the specific surface area of vanadic acid nickel is 50 m2 g-1, pore-size distribution
It is concentrated mainly on as 3-6 nm.This high-specific surface area and a high proportion of central hole structure are capable of providing material in enough activity
The heart.Flower-like structure can effectively adjust the volume change in continuous charge and discharge process, this is for improving chemical property very
It is ideal.
Fig. 5 is the cyclic voltammetry (CV) and constant current charge-discharge test (GCD) figure of vanadic acid nickel material.Experiment uses three
Electrode system and CHI760E type electrochemical workstation are tested.The specific capacitance of active material can be calculated according to the following formula by GCD
(three-electrode system):
Wherein: C is specific capacitance (Fg-1), I is current density (Ag-1), Δ t is discharge time (s), and Δ V is electric potential scanning
Range (V).The specific capacitance value under different scanning rates is calculated accordingly.Electrode is respectively in 1 to 20 Ag-1Current density under
Specific capacitance is respectively 1054,966.4,896,780,728 Fg-1.It is obvious that with the increase of current density, specific capacitance subtracts
Small, still, under the high current density of 20 A g-1, vanadic acid nickel material electrode still maintains 64.4% high capacitance.10
A·g-1Current density under study vanadic acid nickel material long circulating performance (Fig. 6).In first 300 circulations, due to electrode material
Polarized state gradually activation and enhancing, the specific capacitance of electrode material increases.Finally, 10, after 000 circulation, specific capacitance
The initial specific capacitance that slightly decays may remain in 89%.Flower-like structure can slow down the volume change of material, keep stable structure
It does not collapse.The result shows that flower-shaped vanadic acid nickel material has excellent cyclical stability.
Embodiment 2
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 1: 1.
6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.With alkalinity
PH value is adjusted to about 7 by structure directing agent (aqueous ethanolamine), continues 20 min of stirring in water bath.By finally obtained mixture
It is transferred in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 10 hours at 150 DEG C, natural cooling
To room temperature.Be separated by solid-liquid separation, by after synthesis substance deionized water and ethanol washing for several times, it is dry in 70 DEG C of vacuum drying oven
12h obtains vanadic acid nickel solid.Solid powder is tested through SEM, and structure is blocky-shaped particle.
Embodiment 3
By 3 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.3:
1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 50 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali
Property structure directing agent (aqueous ethanolamine) pH value is adjusted to about 8, continue 20 min of stirring in water bath.By finally obtained mixing
Object is transferred in the stainless steel autoclave of 100 mL Teflon linings.It is naturally cold after heating and being kept for 10 hours at 150 DEG C
But to room temperature.Be separated by solid-liquid separation, by after synthesis substance deionized water and ethanol washing for several times, in 70 DEG C of vacuum drying oven do
It is dry to obtain vanadic acid nickel solid for 24 hours.Solid powder is tested through SEM, and structure is evenly dispersed lamellar structure.
Embodiment 4
By 5 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.8:
1;.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 60 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali
Property solution (ethanol amine) pH value is adjusted to about 10, continue 20 min of stirring in water bath.Finally obtained mixture is transferred to 100
In the stainless steel autoclave of mL Teflon lining.After heating and being kept for 10 hours at 150 DEG C, cooled to room temperature.Solid-liquid
Separation, by after synthesis substance deionized water and ethanol washing for several times, in 60 DEG C of vacuum drying oven drying obtain vanadic acid for 24 hours
Nickel solid.Solid powder is tested through SEM, and lamellar structure is biggish and random.
Embodiment 5
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.5:
1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali
Property solution (ethanol amine) pH value is adjusted to about 12, continue 20 min of stirring in water bath.Finally obtained mixture is transferred to 100
In the stainless steel autoclave of mL Teflon lining.After heating and being kept for 12 hours at 160 DEG C, cooled to room temperature.Centrifugation
Separation, by after synthesis substance deionized water and ethanol washing for several times, dry 16h obtains vanadic acid in 70 DEG C of vacuum drying oven
Nickel solid.Solid powder is tested through SEM, and structure is in biggish bulk.
Embodiment 6
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.5:
1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 90 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali
Property structure directing agent (potassium hydroxide solution) pH value is adjusted to about 9, continue 20 min of stirring in water bath.Remaining step and process are same
Embodiment 1.
Embodiment 7
By 4 mmol NH4VO3It is completely dissolved in a solvent.Ultrasonic treatment is after 30 minutes, to above-mentioned molten under 80 DEG C of stirring in water bath
6 mmol Ni(NO are added in liquid3)2·6H2O.PH value is adjusted to about 9 with alkaline structure directed agents (sodium hydroxide solution), after
Continuous 20 min of stirring in water bath.Remaining step and process are the same as embodiment 1.
Embodiment 8
By 4 mmol NH4VO3It is completely dissolved in a solvent.Ultrasonic treatment is after 30 minutes, to above-mentioned molten under 80 DEG C of stirring in water bath
6 mmol Ni(NO are added in liquid3)2·6H2O.PH value is adjusted to about 9 with alkaline structure directed agents (ammonia aqueous solution), is continued
20 min of stirring in water bath.Remaining step and process are the same as embodiment 1.
Embodiment 9
By 4 mmol NH4VO3It is completely dissolved in a solvent.Ultrasonic treatment is after 30 minutes, to above-mentioned molten under 80 DEG C of stirring in water bath
6 mmol Ni(NO are added in liquid3)2·6H2O.With mixed-alkali structure directing agent (sodium hydroxide+potassium hydroxide solution) by pH
Value is adjusted to about 9, continues 20 min of stirring in water bath.Remaining step and process are the same as embodiment 1.
Embodiment 10
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 1: 1.
6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.With mixing
PH value is adjusted to about 9 by alkaline structure directed agents (ammonium hydroxide+potassium hydroxide solution), continues 20 min of stirring in water bath.Remaining step
And process is the same as embodiment 1.
Embodiment 11
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.1:
1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali
Property structure directing agent (ethanolamine solutions) pH value is adjusted to about 9, continue 20 min of stirring in water bath.By finally obtained mixture
It is transferred in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 12 hours at 155 DEG C, natural cooling
To room temperature.Filtering, by after synthesis substance deionized water and ethanol washing for several times, the dry 12h in 80 DEG C of vacuum drying oven
Obtain vanadic acid nickel solid.
Embodiment 12
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 1: 1.
6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.With alkalinity
PH value is adjusted to about 9 by structure directing agent (ethanolamine solutions), continues 20 min of stirring in water bath.Finally obtained mixture is turned
It moves on in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 11 hours at 160 DEG C, naturally cool to
Room temperature.Filtering, by after synthesis substance deionized water and ethanol washing for several times, in 70 DEG C of vacuum drying oven it is dry for 24 hours
To vanadic acid nickel solid.
Embodiment 13
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.8:
1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali
Property structure directing agent (ethanolamine solutions) pH value is adjusted to about 9, continue 20 min of stirring in water bath.By finally obtained mixture
It is transferred in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 11 hours at 150 DEG C, natural cooling
To room temperature.Centrifugation, by after synthesis substance deionized water and ethanol washing for several times, the dry 16h in 80 DEG C of vacuum drying oven
Obtain vanadic acid nickel solid.
Comparative example 1
Flower-shaped vanadic acid nickel (abbreviation material 1) that embodiment 1 is prepared, using quiet superfine in International Periodicals
3295-3302 pages of volume 46 of upper 2017 of DaltonTransactions deliver " high-performance super capacitor is with three-dimensional porous
Co3V2O8Nanometer rods and two dimension NiCo2V2O8The easy synthesis of nanometer sheet and its electro-catalysis oxygen evolution reaction performance " method be prepared into
The vanadic acid cobalt material (abbreviation material 2) that arrives, using P. Vishnukumar etc. in International Periodicals Materials Letters
" the supercapacitor NiO/Ni delivered on 114-118 pages of volume 219 in 20183V2O8The synthesis of nanocomposite and table
Sign " the NiO/Ni that is prepared of method3V2O8Material (abbreviation material 3), using K. Thiagarajan etc. in International Periodicals J
" the efficient electrode material for super capacitor delivered on 527-536 pages of volume 22 of Solid State Electrochem 2018
Ni3V2O8The synthesis of@stannic oxide/graphene nano composite material " the Ni that is prepared of method3V2O8Material (abbreviation material 4) is adopted
With Low Wei Hau etc. in International Periodicals Journal of Alloys and Compounds 995- of volume 768 in 2018
" the symmetrical electrode of super capacitor graphene/Ni of high-performance delivered on page 10053V2O8The solvent thermal design of nanocomposite "
The Ni that is prepared of method3V2O8It is material (abbreviation material 5), auspicious etc. in International Periodicals Electrochimica Acta using fourth
" the efficient electrode material for super capacitor Ni delivered on 494-502 pages of volume 107 in 20133V2O8@stannic oxide/graphene nano is multiple
The synthesis of condensation material " the Ni that is prepared of method3V2O8Material (abbreviation material 6), use application publication number for
The square prism vanadic acid nickel nano material that method disclosed in the Chinese invention patent application of CN108101123A is prepared is (referred to as
Material 7).Experiment is compared, specific capacitance, the cycle performance of six kinds of materials are compared.
The parameter comparison of 1 different materials of table
Test condition: above-mentioned vanadic acid nickel material, acetylene black and the PVDF being prepared is weighed by the mass ratio of 8:1:1,
Few drops of N-Methyl pyrrolidone reagents are added after mixed grinding, magnetic agitation handles 8 h, obtains active material slurry.By one
Quantitative slurry is coated uniformly on 1 × 1 cm of area2Nickel foam on.The electrode prepared is done in 80 DEG C of convection ovens
Dry 12 h.Using cyclic voltammetry in 2 mV s-1Current potential sweeps the specific capacitance and cycle performance of test material under speed.
The result shows that the specific capacitance for the vanadic acid nickel material that embodiment 1 is prepared is higher, and there is excellent cyclicity
Energy.
Comparative example 2
Using control variate method, the experiment condition to prepare vanadic acid nickel material in embodiment 1 is basic experimental conditions (that is, if nothing
Specified otherwise, the experiment condition in addition to variable is with the experiment condition for preparing vanadic acid nickel material in embodiment 1), by adjusting alkalinity
11 kinds of vanadic acid nickel materials as shown in table 2 are prepared in structure directing agent type.By comparing experiment, compare different condition
Specific capacitance, cycle performance and the high rate performance of lower obtained vanadic acid nickel material, the results are shown in Table 2, test method and specific capacitance,
Cycle performance and high rate performance calculation method are the same as embodiment 1.
The parameter comparison of material under the conditions of the different alkaline structure directed agents of table 2
The result shows that different alkaline structure directed agents have apparent influence for the pattern and performance of vanadic acid nickel material.Such as Fig. 7
(a) and (b), (c), (d), (e), (f) are the SEM figure of material 2, material 3, material 4, material 5, material 6, material 11 respectively.Fig. 7
(f) shown in, when, without alkaline structure directing agent, vanadic acid nickel material is the non-uniform large area sheet knot of micron order in reaction system
Structure.And pass through the thin slice that the vanadic acid nickel material that structure directing agent precipitates is mostly micro-or nano size, show that alkaline structure is oriented to
Agent is the key factor of synthetizing micro-nano structure vanadic acid nickel material.Fig. 7 (a) is prepared by structure directing agent of potassium hydroxide
Vanadic acid nickel material be mostly graininess, agglomeration is serious.Fig. 7 (b) is prepared using sodium hydroxide as structure directing agent
Vanadic acid nickel material pattern it is similar as the vanadic acid nickel material pattern of structure directing agent with using potassium hydroxide, same agglomeration is tight
Weight is in block structure.The vanadic acid nickel material pattern that Fig. 7 (c) is prepared using ammonium hydroxide as structure directing agent is mostly uniform piece
Layer.
The Analysis on Mechanism that alkaline structure directed agents influence vanadic acid nickel material pattern: under alkaline condition, vanadic acid nickel can be fast
Speed precipitating.Sodium hydroxide and potassium hydroxide show the block structure of aggregation as sample prepared by structure directing agent in the secure execution mode (sem, by
Highly basic is belonged in sodium hydroxide and potassium hydroxide, and when they encounter nickel ion and vanadium ion in solution, ionized
Hydroxide ion can precipitate to form nucleus rapidly.Since crystallization process is relatively fast, cause the growth of crystal grain not specific
The reunion of vanadic acid nickel material easily has occurred in shape.However, since ammonium hydroxide belongs to weak base, hydroxide ion slow release, nucleus
First there are the growths of the side of hydroxide ion.Meanwhile the growth of nucleus becomes slowly form evenly dispersed lamella knot
Structure.
Fig. 8-13 is respectively the circulation of material 2, material 3, material 4, material 5, material 6, material 11 under different scanning rates
Volt-ampere curve figure, different from the rectangular characteristic of double layer capacity, the shape of CV curve clearly illustrates that capacitive property is anti-by faraday
It should control.Redox peaks are mainly due to Ni2+ / Ni3+And V4+ / V5+Two kinds of active redox reaction presence.Root
Each electrode specific capacitance value calculated according to constant current charge-discharge curve, it is known that material 2, material 3 specific capacitance value be not much different, and material
Due to there is the participation of weak base, specific capacitance is big compared with material 2, material 3 for material 4, material 5.Current density is from 1 A g-1 Increase to 20 A
g-1, the specific capacitance of six kinds of materials reduces that amplitude is larger, and capacity retention is not high.This is because expose thoroughly rate when, electrolyte
Ion has little time to cause effective ratio area to reduce into the mesoporous gap of material, and electric double layer interface is reduced.Comparatively, exist
Under same scan speed, the specific capacitance value of the material through structure directing agent precipitating, which is all higher than to precipitate without sour structure directing agent, to be prepared
The specific capacitance value of obtained vanadic acid nickel material shows that alkaline structure directed agents are the key that synthetizing micro-nano structure vanadic acid nickel materials
Factor.
The specific capacitance for the flower-shaped vanadic acid nickel material that embodiment 1 is prepared is apparently higher than obtained material under the conditions of others
Material, and there is good circulation and high rate performance.This is attributed to:
(1) weakly alkaline ethanol amine is as structure directing agent, so that the growth of nucleus becomes slowly form even sheet layer heap
Long-pending flower-like structure.
(2) high-specific surface area and a high proportion of central hole structure are capable of providing flower-shaped vanadic acid nickel material in enough activity
The heart.
(3) flower-shaped vanadic acid nickel material has loose porous structure, is conducive to the infiltration of electrolyte and quickly moving for ion
It moves.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of supercapacitor preparation method of vanadic acid nickel material, it is characterised in that the following steps are included:
Step 1: in a solvent by ammonium vanadate dissolution, nickel nitrate is added, obtains reaction precursor liquid;Vanadium in the ammonium vanadate
Additional amount and the nickel nitrate in nickel element additional amount molar ratio be (1-6): 6;The solvent is ethyl alcohol, one in water
Kind is any than mixing;
Step 2: reaction precursor liquid alkaline structure directed agents are adjusted into pH value to 7-12, is uniformly mixed, it is mixed to obtain reaction
Close liquid;The alkaline structure directed agents are one of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ethanol amine or several any
Than mixing;
Step 3: the reaction mixture is transferred in autoclave, is reacted 8-15 hours at 100-180 DEG C, solid after cooling
Liquid separation is dried to obtain product vanadic acid nickel material after solid product washing for several times at 50-100 DEG C.
2. a kind of preparation method of supercapacitor vanadic acid nickel material as described in claim 1, it is characterised in that:
In step 2, the alkaline structure directed agents are ethanol amine.
3. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 2, it is characterised in that:
In step 1, the solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is (0.1-1): 1.
4. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 3, it is characterised in that:
In step 1, the additional amount of vanadium and the molar ratio of the additional amount of nickel element in the nickel nitrate are in the ammonium vanadate
(3-5): 6.
5. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 4, it is characterised in that step 1
The condition that nickel nitrate is added are as follows:
Nickel nitrate is added in Ammonium Vanadate Solution under the conditions of 50-90 DEG C of stirring in water bath.
6. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 5, it is characterised in that:
In step 3, the reaction temperature is 150-160 DEG C.
7. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 6, it is characterised in that:
In step 3, the reaction time is 10-12h.
8. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 7, it is characterised in that:
In step 3, the method for the separation of solid and liquid is filtering or centrifugation, the drying are as follows: the vacuum drying 12- at 60-80 DEG C
24h。
9. the flower-shaped supercapacitor vanadic acid nickel material that method according to claim 1 to 8 is prepared.
10. flower-shaped supercapacitor according to claim 9 uses vanadic acid nickel material as electrode material for super capacitor
Using.
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CN112186168A (en) * | 2020-10-10 | 2021-01-05 | 宁波大学 | Zinc ion battery electrode material and preparation method and application thereof |
CN112186168B (en) * | 2020-10-10 | 2021-10-19 | 宁波大学 | Zinc ion battery electrode material and preparation method and application thereof |
CN113149085A (en) * | 2021-02-23 | 2021-07-23 | 北京科技大学 | Positioning synthesis method and application of mixed metal vanadate with two-dimensional structure |
CN113023793A (en) * | 2021-03-24 | 2021-06-25 | 浙江工业大学 | Cobalt-nickel-vanadium-oxygen electrode material and preparation method thereof |
CN113023793B (en) * | 2021-03-24 | 2022-09-02 | 浙江工业大学 | Cobalt-nickel-vanadium-oxygen electrode material and preparation method thereof |
CN113171746A (en) * | 2021-04-26 | 2021-07-27 | 内江师范学院 | Flaky nickel vanadate nano material for adsorbing VB and preparation method thereof |
CN115096956A (en) * | 2022-06-29 | 2022-09-23 | 西北工业大学 | Hollow spherical nickel vanadate-nickel oxide heterogeneous material, preparation method and application thereof, and triethylamine gas sensor |
CN115096956B (en) * | 2022-06-29 | 2024-10-01 | 西北工业大学 | Hollow spherical nickel vanadate-nickel oxide heterogeneous material, preparation method and application thereof, and triethylamine gas sensor |
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