CN106024403B - A kind of ultracapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof - Google Patents
A kind of ultracapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof Download PDFInfo
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- CN106024403B CN106024403B CN201610297308.6A CN201610297308A CN106024403B CN 106024403 B CN106024403 B CN 106024403B CN 201610297308 A CN201610297308 A CN 201610297308A CN 106024403 B CN106024403 B CN 106024403B
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- molybdenum carbide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 239000007772 electrode material Substances 0.000 title claims abstract description 39
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 38
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 26
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract 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 abstract description 9
- 239000008103 glucose Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 239000006260 foam Substances 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 23
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 230000005518 electrochemistry Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000003763 carbonization Methods 0.000 abstract description 10
- 229910052786 argon Inorganic materials 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 9
- 238000010295 mobile communication Methods 0.000 abstract description 3
- 238000010248 power generation Methods 0.000 abstract description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 abstract 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910021401 carbide-derived carbon Inorganic materials 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000219094 Vitaceae Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 235000021021 grapes Nutrition 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The invention discloses a kind of ultracapacitor carbon pipe/molybdenum carbide combination electrode materials and preparation method thereof; pass through hydro-thermal method; zinc oxide template is generated, as carrier, passes through glucose hydrothermal carbonization; reaction 2~6 hours; carbon pipe is generated in zinc oxide template upper surface, by cathodic electrodeposition, reacts 5~25min; and high-temperature heat treatment under protection of argon gas, prepare ultracapacitor carbon pipe and molybdenum carbide combination electrode material.The electrode material includes substrate, the carbon nanotubes being arranged in substrate and the molybdenum carbide nanometer layer being coated in carbon nanotubes.A diameter of 80~500nm of carbon nanotubes, the thickness for changing molybdenum nanometer layer are 50~100nm.Composite material of the present invention has high specific capacitance and high circulation service life, high-energy and high power density and high circulation service life, has broad application prospects in fields such as mobile communication, electric vehicle, solar power generation and aerospaces.
Description
Technical field
The present invention relates to composite electrode material for super capacitor fields, and in particular to a kind of ultracapacitor carbon pipe/carbonization
Molybdenum combination electrode material and preparation method thereof.
Background technology
At present, as the reduction of global warming and fossil energy, environmental problem and energy problem become increasingly conspicuous, greatly
Power develops renewable and clean energy resource and its high-efficiency energy-storage device is extremely urgent.In recent years, ultracapacitor obtain it is a series of into
Fruit has complied with demand of the people to novel energy.Ultracapacitor has the spies such as high power, good temp characteristic, cycle life height
Point plays an important role in fields such as mobile communication, solar power generation, electric vehicles.Compared with lithium ion battery, surpass
Grade capacitor has higher power density, but energy density is relatively low, only the part of lithium ion battery even tens
/ mono-.Ultracapacitor is mainly made of electrode, electrolyte, diaphragm etc., wherein, the influence to its chemical property rises leading
Effect is electrode material, and electrode material mainly has carbon material, conducting polymer and metal oxide.Research for carbon material
It is also most commonly used, activated carbon, carbon nanotube and graphene etc. earliest to be.Carbon nanotube is as a kind of novel carbon materials
Material, the hole migrated with unique hollow structure, higher specific surface area, good electric conductivity, suitable electrolyte ion etc.
Advantage, can with molybdenum carbide it is compound with prepare with high-energy density, high power density and high circulation service life electrode material.
The Chinese invention patent application that application publication number is CN104701026A (application No. is 201510043121.9) is public
A kind of carbon carbon composite electrode material and preparation method thereof is opened, which is one kind structure between graphene and carbide-derived carbon
Into the graphene of hollow structure and the composite material of carbide-derived carbon, which includes：(1) it is 2.6 microns by grain size
Graphite powder (purity 99%), graphite oxide (GO) is prepared using well known improved Hummer methods, 0.5 is added in by every milligram of GO
Reductase 12~6 hour at 80 DEG C obtain the graphene RGO of different reducing degrees by gained GO hydrazine hydrates for microlitre hydrazine hydrate；(2)
Using the titanium carbide TiC that grain size is about 20nm as reaction precursor, using high temperature halogen process, at 400 DEG C~1000 DEG C with chlorine
Reaction obtains carbide-derived carbon CDC after 1 hour；(3) obtained RGO, CDC are made into the aqueous solution of 2mg/mL respectively, then
The RGO solution prepared and CDC solution are ultrasonically treated 2 hours in high power 800W ultrasonic vibration instrument respectively；(4) it is RGO is molten
Liquid presses 1 with CDC solution:9~9:1 volume ratio is then sonicated after being slowly mixed together makes its compound uniformly for 2 hours, and at room temperature
Stirring 24 hours, 90 DEG C of drying, that is, obtain carbon carbon composite electrode material.Prepared carbon carbon composite electrode material shows good
Power characteristic and higher energy density, specific capacity can reach 220F/g, and performance needs to be further improved.
Invention content
It is an object of the invention to be directed to the relatively low specific capacitance of carbon-based material, a kind of ultracapacitor carbon pipe/carbon is provided
Change molybdenum combination electrode material and preparation method thereof, which is used as electrode material for super capacitor with high power density
And high-energy density.
The preparation method of ultracapacitor carbon pipe/molybdenum carbide combination electrode material of the present invention, its step are as follows：
(1) hexamethylenetetramine aqueous solution and zinc nitrate aqueous solution mixing, using nickel foam as substrate, carry out first step hydro-thermal
Reaction, obtains ZnO templates；
(2) second step hydro-thermal reaction, washing are carried out by ZnO templates obtained in step (1) and with glucose solution
It after drying, then is heat-treated, obtaining growth has the nickel foam of carbon nanotubes；
(3) sodium molybdate, hydrogen peroxide, water are mixed, and is adjusted with acid pH to 2~4, form salt electrolyte containing molybdenum；
(4) growth prepared using step (2) has the nickel foam of carbon nanotubes as working electrode, and platinized platinum is auxiliary electrode, is adopted
The salt electrolyte containing molybdenum prepared with step (3) forms electrochemistry bipolar electrode system, applies electric current, is deposited in nickel foam, make molybdenum
Element is coated on carbon nanotubes surface, and product is washed drying later, later in 700~900 DEG C of high-temperature process, obtains target production
Object (i.e. ultracapacitor carbon pipe/molybdenum carbide combination electrode material).
In step (1), a concentration of 0.025~0.2mol/L of the hexamethylenetetramine aqueous solution, the nitric acid
Zinc concentration is 0.025~0.2mol/L.
The molar ratio of hexamethylenetetramine and zinc nitrate in zinc nitrate aqueous solution in the hexamethylenetetramine aqueous solution
It is 0.5~1.5：1, further preferably 1：1.
The condition of the first step hydro-thermal reaction is：Hydrothermal temperature is 80~100 DEG C, and the hydro-thermal time is 5~11 hours.
In step (2), a concentration of 0.1~0.5mol/L of the glucose solution, further preferably 0.2~
0.4mol/L。
The condition of the second step hydro-thermal reaction is：Hydrothermal temperature is 170~190 DEG C, and the hydro-thermal time is 2~6 hours.
The heat treatment carries out in inert gas, and the inert gas is argon gas.
The condition of the heat treatment is：Temperature is 400~600 DEG C, and the time is 1~3 hour.
In step (3), the sodium molybdate, hydrogen peroxide, water mass ratio be 2.5：0.7~1.3：450~550, into
One step preferably 2.5：0.9：502.1.The acid uses dilute sulfuric acid, and mass percent is less than 70.4%；
In step (4), in the electrochemistry bipolar electrode system, working electrode apply cathode current 0.5~
2.5mA/cm2, react 5~25min.
The high-temperature process carries out in inert gas, and the inert gas is argon gas.
The time of the high-temperature process is 1~3h.
The ultracapacitor carbon pipe/molybdenum carbide combination electrode material, including substrate, setting receiving on the substrate
Rice carbon pipe and the molybdenum carbide nanometer layer being coated in the carbon nanotubes.A diameter of 80~500nm of the carbon nanotubes,
The thickness of the molybdenum carbide nanometer layer is 50~100nm.According to actual needs, can adjust the reaction time, reaction density and
Current density controls its size and thickness.The substrate is nickel foam.
Compared with prior art, the invention has the advantages that：
The method of the present invention for template, passes through hydrothermal carbonization with ZnO nano bar (a diameter of 40~300nm of ZnO nano bar)
Method prepares ultracapacitor carbon pipe/molybdenum carbide combination electrode material to prepare carbon pipe, then by cathodic electrodeposition.The preparation side
Method is simple and convenient, easily controllable.
Ultracapacitor carbon pipe/molybdenum carbide combination electrode material prepared by the present invention, carbon pipe have larger specific surface area,
The contact area of electrolyte and motor can be increased, provide bigger more effective active reaction area, meanwhile, it is carried for electrochemical reaction
For good ion and electrons spread channel, the diffusion length of ion is shortened, improves electrochemical capacitance performance.In the present invention, pass through
Carbon and molybdenum it is compound, the low specific capacitance of single carbon material is overcome, the shortcomings that high magnification attenuation is fast, so as to fulfill high power discharge
High-energy density is kept while energy, to form the Novel super capacitor electrode material with high power, high-energy density.
Carbon pipe/molybdenum carbide combination electrode material prepared by the present invention has a fast electronics and ion transmission channel, good conductivity,
Good cycling stability, high power is forthright excellent, and energy/power density is high, is suitble to carry out capacitive energy storage work under conditions of high current.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of carbon nanotubes grown in nickel foam in embodiment 1；
Fig. 2 is transmission electron microscope (TEM) figure of carbon nanotubes grown in nickel foam in embodiment 1；
Fig. 3 is scanning electron microscope (SEM) figure of ultracapacitor carbon pipe/molybdenum carbide combination electrode material in embodiment 1；
Fig. 4 is transmission electron microscope (TEM) figure of ultracapacitor carbon pipe/molybdenum carbide combination electrode material in embodiment 1.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
Embodiment 1
Weigh 1.752g hexamethylenetetramines and 3.719g zinc nitrates be placed in two beakers, be separately added into 500ml go from
The hexamethylenetetramine aqueous solution of 0.025mol/L and the zinc nitrate aqueous solution of 0.025mol/L is respectively configured, then respectively in sub- water
40ml is taken in empty beaker, is after mixing moved into solution in polytetrafluoroethylene (PTFE) autoclave, and be put into nickel foam conduct
Substrate seals autoclave, hydro-thermal reaction 5 hours under conditions of 80 DEG C.Postcooling is reacted to 25 DEG C of room temperature, uses deionized water
Washing, obtains ZnO templates.It weighs 36g glucose and is dissolved in 1000ml deionized waters, stirring is to being completely dissolved.Then 80ml grapes are taken
Sugar aqueous solution is put into ZnO templates in polytetrafluoroethylene (PTFE) autoclave, and autoclave is sealed, the water under conditions of 170 DEG C
Thermal response 2 hours.Postcooling is reacted to 25 DEG C of room temperature, drying is washed with deionized, and calcined under the conditions of 400 DEG C in argon gas
1 hour, 25 DEG C of cooled to room temperature must grow the nickel foam for having carbon nanotubes.To the carbon nanotubes that is grown in nickel foam into
Row scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis, as shown in Figs. 1-2, it is seen that：Carbon pipe vertical-growth and average diameter is about
For 80nm, surface is more smooth.
2.5g sodium molybdates and 3.0g aqueous hydrogen peroxide solutions (wt30%) (weight ratio 5 are weighed respectively:6) it is dissolved in 500ml
Deionized water, stirring to form salt electrolyte containing molybdenum to being completely dissolved, and it is 2 to adjust pH value with dilute sulfuric acid.Then salt containing molybdenum is electrolysed
Liquid is transferred in electrochemistry bipolar electrode system, wherein the nickel foam that growth has carbon nanotubes is working electrode, platinized platinum is auxiliary electricity
Pole.It is 0.5mA/cm to apply cathode-current density on the working electrode (s2, 5min is reacted, is deposited in nickel foam, makes molybdenum element packet
Carbon nanotubes surface is overlayed on, after drying is washed with deionized, calcines 1 hour, naturally cools under the conditions of 700 DEG C in argon gas
25 DEG C of room temperature obtains ultracapacitor carbon pipe/molybdenum carbide combination electrode material.To obtained carbon pipe/molybdenum carbide combination electrode material
Electronic Speculum (SEM) and transmission electron microscope (TEM) analysis are scanned, as shown in Figure 3-4, it is seen that：Carbon pipe/molybdenum carbide compound pipeline complex pipeline is averaged
Diameter is in 130nm, and vertical-growth is in substrate.Carbon pipe/compound tube outer surface of molybdenum carbide is relatively rough, and molybdenum carbide is supported on outer
Portion, thickness are about 50nm.The weight ratio of molybdenum carbide and carbon pipe is 50:50.
Embodiment 2
Weigh 7.008g hexamethylenetetramines and 14.876g zinc nitrates be placed in two beakers, be separately added into 500ml go from
Sub- water is respectively configured the hexamethylenetetramine aqueous solution of 0.1mol/L and the zinc nitrate aqueous solution of 0.1mol/L, then respectively takes
40ml after mixing moves into solution in polytetrafluoroethylene (PTFE) autoclave, and be put into nickel foam as base in empty beaker
Bottom seals autoclave, hydro-thermal reaction 8 hours under conditions of 90 DEG C.Postcooling is reacted to 25 DEG C of room temperature, is washed with deionized water
It washs, obtains ZnO templates.It weighs 54g glucose and is dissolved in 1000ml deionized waters, stir to being completely dissolved, obtain glucose solution.
Then 80ml glucose solutions are taken in polytetrafluoroethylene (PTFE) autoclave, and are put into ZnO templates, autoclave is sealed,
Hydro-thermal reaction 4 hours under conditions of 180 DEG C.Postcooling is reacted to 25 DEG C of room temperature, drying is washed with deionized, and in argon gas
It is calcined 2 hours under the conditions of 500 DEG C, 25 DEG C of cooled to room temperature must grow the nickel foam for having carbon nanotubes.
2.5g sodium molybdates and 3.0g aqueous hydrogen peroxide solutions (wt30%) (weight ratio 5 are weighed respectively:6) it is dissolved in 500ml
Deionized water, stirring to form salt electrolyte containing molybdenum to being completely dissolved, pH value 3.Then salt electrolyte containing molybdenum is transferred to electrification
It learns in bipolar electrode system, is working electrode by the nickel foam that growth has carbon nanotubes, platinized platinum is auxiliary electrode.On the working electrode (s
Application cathode-current density is 1.0mA/cm2, 15min is reacted, is deposited in the nickel foam, molybdenum element is made to be coated on carbon pipe
Surface after drying is washed with deionized, is calcined 2 hours, cooled to room temperature obtains super in argon gas under the conditions of 800 DEG C
Capacitor carbon pipe/molybdenum carbide combination electrode material.
Embodiment 3
It weighs 14.016g hexamethylenetetramines and 29.752g zinc nitrates is placed in two beakers, be separately added into 500ml and go
Ionized water is configured the hexamethylenetetramine aqueous solution of 0.2mol/L and the zinc nitrate aqueous solution of 0.2mol/L, then takes respectively
40ml after mixing moves into solution in polytetrafluoroethylene (PTFE) autoclave, and be put into nickel foam as base in empty beaker
Bottom seals autoclave, hydro-thermal reaction 11 hours under conditions of 100 DEG C.Postcooling is reacted to 25 DEG C of room temperature, uses deionized water
Washing, obtains ZnO templates.It weighs 72g glucose and is dissolved in 1000ml deionized waters, stirring is to being completely dissolved.Then 80ml grapes are taken
Sugar aqueous solution is put into ZnO templates in polytetrafluoroethylene (PTFE) autoclave, and autoclave is sealed, the water under conditions of 190 DEG C
Thermal response 6 hours.Postcooling is reacted to 25 DEG C of room temperature, drying is washed with deionized, and calcined under the conditions of 600 DEG C in argon gas
3 hours, 25 DEG C of cooled to room temperature must grow the nickel foam for having carbon nanotubes.
5.0g sodium molybdates and 6.0g aqueous hydrogen peroxide solutions (wt30%) (weight ratio 5 are weighed respectively:6) it is dissolved in 500ml
Deionized water, stirring to form salt electrolyte containing molybdenum to being completely dissolved, pH value 4.Then salt electrolyte containing molybdenum is transferred to electrification
It learns in bipolar electrode system, wherein it is working electrode that growth, which has the nickel foam of carbon nanotubes, platinized platinum is auxiliary electrode.In working electrode
Upper application cathode-current density is 2.5mA/cm2, 25min is reacted, it is deposited in the nickel foam, is coated on molybdenum element
Carbon pipe surface after drying is washed with deionized, is calcined 3 hours, cooled to room temperature obtains in argon gas under the conditions of 900 DEG C
Ultracapacitor carbon pipe/molybdenum carbide combination electrode material.
Performance test
Using ultracapacitor carbon pipe/carbonization molybdenum composite material made of above-described embodiment 1~3 as anode, foam
Nickel makees cathode, and mercury/mercuric oxide electrode is reference electrode, tests electrochemical capacitance performance respectively in three-electrode system.Electrolyte is
1mol/M KOH aqueous solutions, charging/discharging voltage are -0.1~0.9V, and cycle measures ultracapacitor carbon in 25 ± 1 DEG C of environment
Reversible charge and discharge specific capacitance, charge-discharge performance and the high-rate characteristics of pipe/carbonization molybdenum composite material.
The performance test results are as follows：
Under the ultracapacitor carbon pipe of embodiment 1, embodiment 2 and embodiment 3/carbonization molybdenum composite material 2A/g current densities
Electric discharge specific capacitance is respectively 450F/g, 480F/g and 460F/g, and after 10000 cycles electric discharge specific capacitance conservation rate up to 92% with
On.As it can be seen that ultracapacitor carbon pipe obtained above/carbonization molybdenum composite material charge/discharge capacity is high, good cycling stability.
The ultracapacitor carbon pipe of embodiment 1, embodiment 2 and embodiment 3/carbonization molybdenum composite material 20A/g current densities
Lower electric discharge specific capacitance is respectively 430F/g, 456F/g and 435F/g, corresponding energy and power density be respectively 32Wh/kg and
7kW/kg, 38Wh/kg and 10kW/kg, 33Wh/kg and 9kW/kg.As it can be seen that ultracapacitor carbon pipe/molybdenum carbide obtained above
Composite material high rate capability is good, and energy and power density are high.
This is because the incorporation of transition metal molybdenum element improves the electric conductivity of entire composite material, carbon pipe/carbonization molybdenum tube
Shape structure is conducive to increase the contact area of electrode and electrolyte, and provides bigger effective active reaction area, is simultaneously
Electrochemical reaction provides good ion and electrons spread channel, shortens the diffusion length of ion, improves electrochemical capacitance performance.
Therefore, ultracapacitor carbon pipe/carbonization molybdenum composite material of the present invention has high specific capacitance and high circulation service life, high energy
Amount and power density feature have wide application in fields such as mobile communication, electric vehicle, solar power generation and aerospaces
Prospect.
Claims (9)
1. a kind of ultracapacitor carbon pipe/molybdenum carbide combination electrode material, which is characterized in that including substrate, be arranged on the base
Carbon nanotubes on bottom and the molybdenum carbide nanometer layer being coated in the carbon nanotubes, a diameter of the 80 of the carbon nanotubes
~500nm, the thickness of the molybdenum carbide nanometer layer is 50~100nm；
The ultracapacitor carbon pipe/molybdenum carbide combination electrode material is prepared according to following methods：
(1) hexamethylenetetramine aqueous solution and zinc nitrate aqueous solution mixing, using nickel foam as substrate, it is anti-to carry out first step hydro-thermal
Should, obtain ZnO templates；
(2) ZnO templates obtained in step (1) and glucose solution are subjected to second step hydro-thermal reaction, after washing and drying,
It is heat-treated again, obtaining growth has the nickel foam of carbon nanotubes；
(3) sodium molybdate, hydrogen peroxide, water are mixed, and is adjusted with acid pH to 2~4, form salt electrolyte containing molybdenum；
(4) growth prepared using step (2) has the nickel foam of carbon nanotubes as working electrode, and platinized platinum is auxiliary electrode, using step
Suddenly the salt electrolyte containing molybdenum that prepared by (3) forms electrochemistry bipolar electrode system, applies electric current, is deposited in nickel foam, make molybdenum element
Carbon nanotubes surface is coated on, product is washed into drying later, later in 700~900 DEG C of high-temperature process, obtains ultracapacitor
Carbon pipe/molybdenum carbide combination electrode material.
2. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (1)
In, a concentration of 0.025~0.2mol/L of the hexamethylenetetramine aqueous solution, the zinc nitrate aqueous solution it is a concentration of
0.025~0.2mol/L.
3. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (1)
In, the molar ratio of hexamethylenetetramine and zinc nitrate in zinc nitrate aqueous solution is 0.5 in the hexamethylenetetramine aqueous solution
~1.5：1.
4. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (1)
In, the condition of the first step hydro-thermal reaction is：Hydrothermal temperature is 80~100 DEG C, and the hydro-thermal time is 5~11 hours.
5. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (2)
In, the condition of the second step hydro-thermal reaction is：Hydrothermal temperature is 170~190 DEG C, and the hydro-thermal time is 2~6 hours.
6. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (2)
In, the condition of the heat treatment is：Temperature is 400~600 DEG C, and the time is 1~3 hour.
7. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (3)
In, the sodium molybdate, hydrogen peroxide, water mass ratio be 2.5：0.7~1.3：450~550.
8. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (4)
In, in the electrochemistry bipolar electrode system, apply 0.5~2.5mA/cm of cathode current in working electrode2, reaction 5~
25min。
9. ultracapacitor carbon pipe/molybdenum carbide combination electrode material according to claim 1, which is characterized in that step (4)
In, the time of the high-temperature process is 1~3h.
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| US11328877B2 (en) * | 2019-10-21 | 2022-05-10 | Imam Abdulrahman Bin Faisal University | Redox-mediated poly(vinylphosphonic acid) useful in capacitors |
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