CN106449138A - Carbon-coated cobalt molybdate network nanosheet array material, preparation method and application - Google Patents
Carbon-coated cobalt molybdate network nanosheet array material, preparation method and application Download PDFInfo
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- CN106449138A CN106449138A CN201610822600.5A CN201610822600A CN106449138A CN 106449138 A CN106449138 A CN 106449138A CN 201610822600 A CN201610822600 A CN 201610822600A CN 106449138 A CN106449138 A CN 106449138A
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- cobalt molybdate
- chip arrays
- cobalt
- molybdate
- nano chip
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- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002135 nanosheet Substances 0.000 title abstract 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000006260 foam Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 10
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 238000003491 array Methods 0.000 claims description 78
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001720 carbohydrates Chemical class 0.000 claims description 17
- 235000014633 carbohydrates Nutrition 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 238000005253 cladding Methods 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000004087 circulation Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229910018864 CoMoO4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000009392 Vitis Nutrition 0.000 description 2
- 241000219095 Vitis Species 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
Abstract
The invention discloses a carbon-coated cobalt molybdate network nanosheet array material, which comprises a nano carbon film, cobalt molybdate network nanosheets and nickel foam, wherein the cobalt molybdate network nanosheets vertically grow on the nickel foam in an intersecting manner to form a cobalt molybdate network nanosheet array; and the nano carbon film coats the surface of the cobalt molybdate network nanosheet array. The invention further discloses a preparation method of the carbon-coated cobalt molybdate network nanosheet array material. The prepared carbon-coated cobalt molybdate network nanosheet array material can be used as an electrode material of a super-capacitor, so that the specific capacitance and the cycle performance of the super-capacitor can be significantly improved. The method is simple, short in time, green, environment-friendly, low in cost and suitable for industrialized massive production.
Description
Technical field
The present invention relates to a kind of preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating, belong to super capacitor
The preparation field of device electrode material.
Background technology
Ultracapacitor, also known as electrochemical capacitor, is a kind of novel energy-storing device between traditional capacitor and battery
Part, it has the energy density higher than traditional capacitor, the higher power density than secondary cell, also has discharge and recharge simultaneously
Time is short, efficiency for charge-discharge is high, have extended cycle life, memory-less effect and substantially non-maintaining the advantages of, in mobile communication, information
The aspects such as technology, consumer electronics, electric automobile, Aero-Space and science and techniques of defence have important and wide application prospect, become
Focus for countries in the world research.
Store the difference of electric charge mechanism according to electrode material, ultracapacitor can be divided into double electric layers supercapacitor and farad
Fake capacitance ultracapacitor.Double electric layers supercapacitor is to be deposited using the interfacial electric double layer being formed between electrode and electrolyte
Storing up electricity lotus, the number of storing electricity depends on the size of electrode material specific surface area.Pseudocapacitors are using in electrode material table
Face or near surface layer occur the redox reaction of Rapid reversible to realize electric charge storage.Compared with double electric layers supercapacitor, counterfeit
Capacitor can obtain higher ratio electric capacity and energy density, therefore has more preferable development prospect.
The electrode material of pseudocapacitors is mainly all kinds of transition metal oxides, such as NiO, Co3O4、MnO2Deng.Due to these
Transition metal oxide electrical conductivity relatively low it is suppressed that their electrochemical reaction, so the reality of most of transition metal oxide
Border is far below its theoretical values than electric capacity；Most of structural stability in charge and discharge cycles for the transition metal oxide is relatively simultaneously
Difference, leads to that its cyclical stability is poor, and cycle life is limited.
Recent domestic gradually increases to the research of ternary metal oxide, wherein cobalt molybdate (CoMoO4) enjoy pass
Note.Post array material as self-assembly porous in cobalt molybdate nano piece, in electric current density 4mA cm-2Than electric capacity up to 1.92F cm-2
(Materials Letters.164(2016)260-263).But the electrical conductivity of cobalt molybdate material and structural stability be still relatively
Difference, leads to be fully achieved real requirement than electric capacity and cyclical stability, and its structure is carried out with composite design is a solution
Decision-making is omited, such as CoMoO4@MnO2Core-shell type nano chip arrays are reported, in electric current density 3mA cm-2Reach 2159.4F than electric capacity
g-1(J.Power Sources.296(2015)162-168).
The patent of Publication No. CN103779105A and CN103811189A is proposed cobalt molybdate and is combined with Graphene, by
The high surface area of Graphene and excellent electric conductivity are improving the performance of active material.
The patent of Publication No. CN104821238A adopts oleyl amine as carbon source in cobalt molybdate dusty material surface in situ bag
Cover one layer of carbon.But these research work yet suffer from some shortcomings, such as cobalt molybdate and MnO2Compound can run into MnO2Electrical conductivity is relatively
Low, lead to the problem that composite whole conductivity declines；Although the compound electrical conductivity that can improve cobalt molybdate with Graphene,
But this simple combination is limited to the structural stability of cobalt molybdate and the improvement result of cyclical stability；In molybdic acid cobalt dust material
Need to make electrode using Chemical Felter using slurry-scraping method after material surface in situ carbon coated, nonconducting binding agent increased interior
Resistance, reduces the effect of carbon coating, and the accumulation of the active material of this electrode is dense, also can reduce the electrochemistry of material
Activity, in addition this composite do not control size and the form of cobalt molybdate, also can affect the chemical property of material.
Content of the invention
The invention provides a kind of cobalt molybdate mesh nano chip arrays material of carbon coating, and provide the molybdic acid of carbon coating
The preparation method of cobalt mesh nano chip arrays material, by the cobalt molybdate mesh nano piece of the carbon coating prepared by the inventive method
Array material is used for the electrode material of ultracapacitor, makes ultracapacitor have higher ratio electric capacity and good stable circulation
Property.
A kind of cobalt molybdate mesh nano chip arrays material of carbon coating, by nano-carbon film, cobalt molybdate mesh nano piece and bubble
Foam nickel forms, and the setting that intersects of described cobalt molybdate nano piece is grown in nickel foam, forms cobalt molybdate mesh nano piece battle array
Row；Described nano-carbon film is coated on the surface of cobalt molybdate nano chip arrays.
The thickness of described cobalt molybdate nano piece is 60～80nm.
In the cobalt molybdate mesh nano chip arrays material of described carbon coating, the mass content of carbon is 1%～30%.
A kind of preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating, comprises the following steps that：
(1) carbohydrate is dissolved in deionized water, obtains carbohydrate solutions；
(2) by the nickel foam of superficial growth cobalt molybdate mesh nano chip arrays immersion carbohydrate solutions, and in 110
Hydro-thermal reaction 4～6h at～130 DEG C, obtains the cobalt molybdate mesh nano chip arrays of carbohydrate cladding；
(3) the cobalt molybdate mesh nano chip arrays deionized water that carbohydrate coats is cleaned, at 50～70 DEG C
Dry；
(4) by the cobalt molybdate mesh nano chip arrays of the carbohydrate dried cladding 300～500 DEG C under ar gas environment
Calcining 4～6h, obtains the cobalt molybdate mesh nano chip arrays material of carbon coating.
In step (1), described carbohydrate be in glucose, sucrose, maltose, starch and cellulose extremely
Few one kind, preferably, described carbohydrate is glucose.
In step (1), the mass percent of described carbohydrate solutions is 0.01～1%.
The nickel foam of described superficial growth cobalt molybdate mesh nano chip arrays can be prepared by art methods or
Commercially available prod obtains it is preferable that being prepared by the following method：
A () cobalt nitrate, sodium molybdate are dissolved in deionized water, obtain mixed solution；
B () immerses nickel foam in mixed solution, and hydro-thermal reaction 4～6h at 110～130 DEG C；Obtain superficial growth
The nickel foam of cobalt molybdate mesh nano chip arrays；
C the nickel foam deionized water of superficial growth cobalt molybdate mesh nano chip arrays is cleaned by (), at 50～70 DEG C
Dry.
In step (a), the mol ratio of described cobalt nitrate and sodium molybdate is 0.99～1.01:1.
In step (a), the molar concentration of described cobalt nitrate is 0.01～0.1mol L-1, the rubbing of described sodium molybdate
Your concentration is 0.01～0.1mol L-1.
The cobalt molybdate mesh nano chip arrays material of the carbon coating of present invention preparation is a kind of excellent super capacitor electrode
Pole material.
Cobalt molybdate nano piece is grown directly upon in nickel foam, not using binding agent, fax and collector nickel foam between
Lead good；The surface of nanometer sheet is fully exposed to electrolyte, and surface utilisation reaches maximization；The thickness of cobalt molybdate piece is nanometer
Level, be conducive to improving kinetics and the stock utilization of cobalt molybdate.
In cobalt molybdate nano piece Surface coating nano-carbon film, carbon has good electric conductivity, can significantly improve cobalt molybdate
The electrical conductivity of material, thus improve fake capacitance reactivity；The cladding on cobalt molybdate nano piece surface for the carbon film can effectively improve molybdenum
Structural stability in charge and discharge cycles for the sour cobalt nanometer sheet, thus improve its cyclical stability and cycle life；Said structure
Characteristic comprehensive function can significantly improve utilization rate and the ratio electric capacity of cobalt molybdate, and cycle charge discharge electrical property.
The present invention passes through the precise control of hydro-thermal method twice, is prepared for a kind of cobalt molybdate mesh nano chip arrays of carbon coating
Material, this material prepares ultracapacitor as electrode material, and the ratio electric capacity of ultracapacitor and cycle performance are significantly carried
Height, the inventive method is simple, the time is short, environmental protection, with low cost, suitable industrialization scale of mass production.
Brief description
Fig. 1 is the XRD spectrum of the cobalt molybdate mesh nano chip arrays of comparative example 1 preparation；
Fig. 2 is the XRD spectrum of the carbon coating cobalt molybdate mesh nano chip arrays of embodiment 1 preparation；
Fig. 3 is the SEM figure of the cobalt molybdate mesh nano chip arrays of comparative example 1 preparation；
Fig. 4 is the SEM figure of the carbon coating cobalt molybdate mesh nano chip arrays of embodiment 1 preparation；
Fig. 5 is the carbon coating cobalt molybdate mesh nano chip arrays of embodiment 1 preparation and the cobalt molybdate of comparative example 1 preparation is netted
Nano-chip arrays are in electric current density 1A g-1Charging and discharging curve figure；
Fig. 6 be embodiment 1 preparation carbon coating cobalt molybdate mesh nano chip arrays and comparative example 1 preparation cobalt molybdate netted
Nano-chip arrays are in electric current density 1A g-1Cycle performance comparison diagram.
Specific embodiment
In order to more specifically describe the present invention, below in conjunction with the accompanying drawings and specific embodiment is to technical scheme
It is described in detail.
Carbon coating cobalt molybdate mesh nano chip arrays material is prepared using hydro-thermal reaction twice.
Comparative example 1
Take 0.875g cobalt nitrate and 0.725g sodium molybdate to be dissolved in 60mL deionized water, the mixed solution of gained is moved into
In the ptfe autoclave of volume 100mL, by 2 × 2cm2Nickel foam immerse reactor in mixed solution in, and will
Put into air dry oven after reactor sealing and be heated to 120 DEG C of reaction 5h, reactor is naturally cooled to taking-up surface after room temperature
The nickel foam of growth cobalt molybdate mesh nano chip arrays, 60 DEG C of drying after deionized water wash clean.
Embodiment 1
Take 0.875g cobalt nitrate and 0.725g sodium molybdate to be dissolved in 60mL deionized water, the mixed solution of gained is moved into
In the ptfe autoclave of volume 100mL, by 2 × 2cm2Nickel foam immerse reactor in mixed solution in, and will
Put into air dry oven after reactor sealing and be heated to 120 DEG C of reaction 5h, reactor is naturally cooled to taking-up surface after room temperature
The nickel foam of growth cobalt molybdate mesh nano chip arrays, 60 DEG C of drying after deionized water wash clean；
Take 0.119g glucose to be dissolved in 60mL deionized water, the glucose solution of gained is moved into volume 100mL's
In ptfe autoclave, the nickel foam of superficial growth cobalt molybdate mesh nano chip arrays is immersed in glucose solution, and
Put into air dry oven after will be airtight for reactor and be heated to 120 DEG C of reaction 5h, reactor takes out Fructus Vitis viniferae after naturally cooling to room temperature
The cobalt molybdate mesh nano chip arrays of sugar cladding, after deionized water wash clean, 60 DEG C of drying, are then placed in quartz tube furnace, argon
Protect lower 400 DEG C of calcining 5h, obtain the cobalt molybdate mesh nano chip arrays material of carbon coating.
The material obtaining in comparative example 1 is carried out XRD material phase analysis, analysis result is as shown in figure 1, obtain in comparative example 1
The XRD spectrum of material and β-CoMoO4(JCPDF card number 21-0868) standard diagram coincide, and illustrates to grown in nickel foam
Cobalt molybdate.
The material obtaining in embodiment 1 is carried out XRD material phase analysis, analysis result is as shown in Fig. 2 obtain in embodiment 1
Material XRD spectrum by β-CoMoO4The diffraction maximum composition of (JCPDF card number 21-0868) and C (JCPDF card number 75-2078),
Illustrate that carbon is successfully compound on cobalt molybdate.
The material obtaining in comparative example 1 is carried out SEM observation, result is as shown in Figure 3 it can be seen that cobalt molybdate nano piece is in
Netted setting is grown in nickel foam, nanometer sheet thickness about 70nm, has larger hole to facilitate electrolyte to enter, nanometer between nanometer sheet
Piece is fully exposed to electrolyte, and the fake capacitance reaction that may advantageously facilitate cobalt molybdate is carried out.
The material obtaining in embodiment 1 is carried out SEM observation, result is as shown in fig. 4, it can be seen that cobalt molybdate nano piece net
Shape array structure keeps good, and piece thickness is substantially unchanged, but nanometer sheet surface and edge become more smooth, display surface
Coat layer of substance, i.e. nano-carbon film.Disclosing carbon content by EDS quantitative analyses is 18.6%, is found by EDS Surface scan
Carbon is equally distributed on cobalt molybdate nano piece surface.
Using the cobalt molybdate mesh nano chip arrays material of carbon coating as Electrode, platinum plate electrode is to electrode, saturation
Calomel electrode (SCE) is reference electrode, 2mol L-1KOH aqueous solution is electrolyte, is assembled into three-electrode system, using Lan electricity electricity
Pond tester carries out constant current charge-discharge test to it.
Fig. 5 be embodiment 1 preparation carbon coating cobalt molybdate mesh nano chip arrays and comparative example 1 preparation cobalt molybdate netted
Nano-chip arrays are in electric current density 1A g-1Charging and discharging curve figure.Discharge time after cobalt molybdate mesh nano chip arrays carbon coated
Extend 23%, that is, discharge capacity increased 23%.Meanwhile, charging platform declines, and discharge platform raises.Charging platform declines meaning
Taste charge efficiency and is improved, and discharge platform raises and means that discharge capability strengthens.Charging and discharging curve comparative illustration carbon coating
Improve the fake capacitance activity of cobalt molybdate mesh nano chip arrays and compare electric capacity.
Fig. 6 be embodiment 1 preparation carbon coating cobalt molybdate mesh nano chip arrays and comparative example 1 preparation cobalt molybdate netted
Nano-chip arrays are in electric current density 1A g-1Cycle performance compare.Cobalt molybdate mesh nano chip arrays circulate electric discharge first than electricity
Appearance is 1120F g-1, after 250 circulations, increase to 1490F g-1, it is gradually reduced than electric capacity afterwards, to 1100 recycle ratio electric capacity
It is down to 1000F g-1, and keep circulating to the 2000th, the Average specific capacities of 2000 circulations are 1110F g-1.Carbon coating molybdenum
The electric discharge of circulation first of sour cobalt mesh nano chip arrays is 1380F g than electric capacity-1, after about 250 circulations, increase to 1860F g-1, it is gradually reduced than electric capacity afterwards, be down to 1510F g to 1100 recycle ratio electric capacity-1, slower decline than electric capacity afterwards, to
2000 circulations, than electric capacity 1200F g-1, the Average specific capacities 1480F g of 2000 circulations-1.Test shows that carbon coating is obvious
Improve ratio electric capacity and the cycle performance of cobalt molybdate mesh nano chip arrays.
Embodiment 2
Take 0.524g cobalt nitrate and 0.436g sodium molybdate to be dissolved in 60mL deionized water, the mixed solution of gained is moved into
In the ptfe autoclave of volume 100mL, by 2 × 2cm2Nickel foam immerse reactor in mixed solution in, and will
Put into air dry oven after reactor sealing and be heated to 110 DEG C of reaction 6h, reactor is naturally cooled to taking-up surface after room temperature
The nickel foam of growth cobalt molybdate mesh nano chip arrays, 50 DEG C of drying after deionized water wash clean；
Take 0.06g sucrose to be dissolved in 60mL deionized water, the sucrose solution of gained is moved into the polytetrafluoro of volume 100mL
In ethylene reaction kettle, by the nickel foam of superficial growth cobalt molybdate mesh nano chip arrays immersion sucrose solution, and by reactor
Put into air dry oven after airtight and be heated to 110 DEG C of reaction 6h, reactor takes out the molybdenum of sucrose cladding after naturally cooling to room temperature
Sour cobalt mesh nano chip arrays, 50 DEG C of drying after deionized water wash clean, it is then placed in quartz tube furnace, argon protection lower 300
DEG C calcining 6h, obtain the cobalt molybdate mesh nano chip arrays material of carbon coating.
The cobalt molybdate mesh nano chip arrays material of the carbon coating obtaining, cobalt molybdate mesh nano chip arrays are erect and are grown in
In nickel foam, nano-carbon layer is coated on cobalt molybdate nano piece surface, and it is 9.2% that EDS quantitative analyses disclose carbon content.
Charge-discharge test, electric current density 1A g are circulated using identical 3 electrode system to it-1.The molybdic acid of carbon coating
The electric discharge of circulation first of cobalt mesh nano chip arrays is 1250F g than electric capacity-1, after 250 circulations, increase to 1710F g-1, it
It is gradually reduced than electric capacity afterwards, be down to 1410F g to 1000 recycle ratio electric capacity-1, slower decline than electric capacity afterwards, to the 2000th
Circulation, than electric capacity 1110F g-1, the Average specific capacities 1360F g of 2000 circulations-1.
Embodiment 3
Take 1.222g cobalt nitrate and 1.016g sodium molybdate to be dissolved in 60mL deionized water, the mixed solution of gained is moved into
In the ptfe autoclave of volume 100mL, by 2 × 2cm2Nickel foam immerse reactor in mixed solution in, and will
Put into air dry oven after reactor sealing and be heated to 130 DEG C of reaction 4h, reactor is naturally cooled to taking-up surface after room temperature
The nickel foam of growth cobalt molybdate mesh nano chip arrays, 70 DEG C of drying after deionized water wash clean；
Take 0.237g glucose to be dissolved in 60mL deionized water, the glucose solution of gained is moved into volume 100mL's
In ptfe autoclave, the nickel foam of superficial growth cobalt molybdate mesh nano chip arrays is immersed in glucose solution, and
Put into air dry oven after will be airtight for reactor and be heated to 130 DEG C of reaction 4h, reactor takes out Fructus Vitis viniferae after naturally cooling to room temperature
The cobalt molybdate mesh nano chip arrays of sugar cladding, after deionized water wash clean, 70 DEG C of drying, are then placed in quartz tube furnace, argon
Protect lower 500 DEG C of calcining 4h, obtain the cobalt molybdate mesh nano chip arrays material of carbon coating.
The cobalt molybdate mesh nano chip arrays material of the carbon coating obtaining, cobalt molybdate mesh nano chip arrays are erect and are grown in
Foam nickel surface, nano-carbon layer is coated on cobalt molybdate nano piece surface, and it is 24.3% that EDS quantitative analyses disclose carbon content.
Charge-discharge test, electric current density 1A g are circulated using identical 3 electrode system to it-1.Carbon coating cobalt molybdate
The electric discharge of circulation first of mesh nano chip arrays is 1200F g than electric capacity-1, after 250 circulations, increase to 1640F g-1, afterwards
It is gradually reduced than electric capacity, be down to 1330F g to 1000 recycle ratio electric capacity-1, slower decline than electric capacity afterwards, follow to the 2000th
Ring, than electric capacity 1070F g-1, the Average specific capacities 1250F g of 2000 circulations-1.
Above-described specific embodiment has been described in detail to technical scheme and beneficial effect, Ying Li
Solution is to the foregoing is only presently most preferred embodiment of the invention, is not limited to the present invention, all principle models in the present invention
Enclose interior done any modification, supplement and equivalent etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of cobalt molybdate mesh nano chip arrays material of carbon coating is it is characterised in that by nano-carbon film, cobalt molybdate is netted receives
Rice piece and nickel foam composition, the setting that intersects of described cobalt molybdate nano piece is grown in nickel foam, forms cobalt molybdate netted
Nano-chip arrays；Described nano-carbon film is coated on the surface of cobalt molybdate nano chip arrays.
2. the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 1 is it is characterised in that described molybdenum
The thickness of sour cobalt nanometer sheet is 60～80nm.
3. the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 1 is it is characterised in that described carbon
In the cobalt molybdate mesh nano chip arrays material of cladding, the mass content of carbon is 1%～30%.
4. the preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 1, its feature exists
In comprising the following steps that：
(1) carbohydrate is dissolved in deionized water, obtains carbohydrate solutions；
(2) by the nickel foam of superficial growth cobalt molybdate mesh nano chip arrays immersion carbohydrate solutions, and in 110～
Hydro-thermal reaction 4～6h at 130 DEG C, obtains the cobalt molybdate mesh nano chip arrays of carbohydrate cladding；
(3) the cobalt molybdate mesh nano chip arrays deionized water that carbohydrate coats is cleaned, dry at 50～70 DEG C；
(4) 300～500 DEG C of calcinings under ar gas environment by the cobalt molybdate mesh nano chip arrays of the carbohydrate dried cladding
4～6h, obtains the cobalt molybdate mesh nano chip arrays material of carbon coating.
5. the preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 4, its feature exists
In, in step (1), described carbohydrate is at least in glucose, sucrose, maltose, starch and cellulose
Kind.
6. the preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 4, its feature exists
In, in step (1), the mass percent of described carbohydrate solutions is 0.01～1%.
7. the preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 4, its feature exists
In the preparation method of the described nickel foam of superficial growth cobalt molybdate mesh nano chip arrays is as follows：
A () cobalt nitrate, sodium molybdate are dissolved in deionized water, obtain mixed solution；
B () immerses nickel foam in mixed solution, and hydro-thermal reaction 4～6h at 110～130 DEG C；Obtain superficial growth molybdic acid
The nickel foam of cobalt mesh nano chip arrays；
C the nickel foam deionized water of superficial growth cobalt molybdate mesh nano chip arrays is cleaned by (), dry at 50～70 DEG C.
8. the preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 7, its feature exists
In, in step (a), the mol ratio of described cobalt nitrate and sodium molybdate is 0.99～1.01:1.
9. the preparation method of the cobalt molybdate mesh nano chip arrays material of carbon coating according to claim 7, its feature exists
In, in step (a), in described mixed solution, the molar concentration of cobalt nitrate is 0.01～0.1mol L-1, described mixing is molten
In liquid, the molar concentration of sodium molybdate is 0.01～0.1mol L-1.
10. super electricity is being prepared according to the cobalt molybdate mesh nano chip arrays material of the arbitrary described carbon coating of claims 1 to 3
The application of container electrode material.
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Application publication date: 20170222 Assignee: Xinchang China Metrology University Enterprise Innovation Research Institute Co.,Ltd. Assignor: China Jiliang University Contract record no.: X2021330000071 Denomination of invention: Carbon coated cobalt molybdate network nano sheet array material, preparation method and Application Granted publication date: 20181225 License type: Common License Record date: 20210816 |
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