CN106024403A - Supercapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof - Google Patents

Supercapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof Download PDF

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CN106024403A
CN106024403A CN201610297308.6A CN201610297308A CN106024403A CN 106024403 A CN106024403 A CN 106024403A CN 201610297308 A CN201610297308 A CN 201610297308A CN 106024403 A CN106024403 A CN 106024403A
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molybdenum carbide
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molybdenum
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CN106024403B (en
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夏新辉
詹继烨
锺宇
涂江平
***
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Zhejiang University ZJU
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses a supercapacitor carbon pipe/molybdenum carbide combination electrode material and a preparation method thereof. Through a hydrothermal method, a zinc oxide template is generated, the zinc oxide template is taken as a carrier, through glucose hydrothermal carbonization, a reaction lasts for 2 to 6 hours, a carbon tube is generated at the upper surface of the zinc oxide template, through a cathode electrodeposition method, a reaction lasts for 5 to 25 minutes, high-temperature heat processing is performed under argon protection, and thus the supercapacitor carbon pipe/molybdenum carbide combination electrode material is prepared. The electrode material comprises a substrate, a nanometer carbon tube arranged on the substrate and a molybdenum carbide nanometer layer coating the nanometer carbon tube. The diameter of the nanometer carbon tube is 80 to 500nm, and the thickness of the molybdenum carbide nanometer layer is 50 to 100nm. The combination material provided by the invention has high specific capacitance, long circle life, high energy and high power density, and has wide application prospect in such fields as mobile communication, electric automobiles, solar power generation, aerospace and the like.

Description

A kind of ultracapacitor carbon pipe/molybdenum carbide combination electrode material and preparation method thereof
Technical field
The present invention relates to composite electrode material for super capacitor field, be specifically related to a kind of ultracapacitor carbon Pipe/molybdenum carbide combination electrode material and preparation method thereof.
Background technology
At present, along with global warming and the minimizing of fossil energy, environmental problem and energy problem's day Benefit is prominent, greatly develops renewable and clean energy resource and high-efficiency energy-storage device is extremely urgent.In recent years, super A series of achievements that level capacitor obtains have complied with people's demand to novel energy.Ultracapacitor has High power, good temp characteristic, cycle life high, mobile communication, solar electrical energy generation, The fields such as electric automobile play an important role.Compared with lithium ion battery, ultracapacitor has higher Power density, but energy density is on the low side, only the part of lithium ion battery even tens/ One.Ultracapacitor is mainly made up of, wherein, to its chemical property electrode, electrolyte, barrier film etc. Impact active be electrode material, electrode material mainly has material with carbon element, conducting polymer and gold Belong to oxide.Research for material with carbon element is the most also to be most commonly used, such as activated carbon, carbon nanometer Pipe and Graphene etc..CNT, as a kind of new carbon, has the hollow structure of uniqueness, higher Specific surface area, good electric conductivity, be suitable for the advantage such as hole that electrolyte ion migrates, can be with carbonization Molybdenum is compound to prepare with high-energy-density, high power density and the electrode material of high cycle life.
Application publication number is the Chinese invention of CN104701026A (Application No. 201510043121.9) Patent application discloses a kind of carbon carbon composite electrode material and preparation method thereof, and this material is a kind of at graphite The Graphene of hollow structure and the composite of carbide-derived carbon is constituted between alkene and carbide-derived carbon, This preparation method includes: (1) by the graphite powder (purity 99%) that particle diameter is 2.6 microns, changes known to employing The Hummer method entered prepares graphite oxide (GO), adds 0.5 microlitre hydrazine hydrate by gained by every milligram of GO GO hydrazine hydrate reductase 12~obtain the Graphene RGO of different reducing degree for 6 hours at 80 DEG C;(2) Be about the titanium carbide TiC of 20nm for reaction precursor with particle diameter, use high temperature halogen process, at 400 DEG C~ Carbide-derived carbon CDC is obtained with after chlorine reaction 1 hour at 1000 DEG C;(3) respectively by obtained RGO, CDC are made into the aqueous solution of 2mg/mL, then the RGO solution prepared and CDC solution are existed respectively Supersound process 2 hours in high power 800W ultrasonic vibration instrument;(4) RGO solution is pressed with CDC solution The volume ratio of 1:9~9:1 is then sonicated after being slowly mixed together 2 hours and makes it compound uniformly, and at room temperature stirs Mix 24 hours, 90 DEG C of drying, i.e. obtain carbon carbon composite electrode material.Prepared carbon carbon composite electrode material Showing good power characteristic and higher energy density, specific capacity can reach 220F/g, and its performance has Treat to improve further.
Summary of the invention
Present invention aims to the ratio electric capacity that carbon-based material is relatively low, it is provided that a kind of ultracapacitor Carbon pipe/molybdenum carbide combination electrode material and preparation method thereof, this composite carbon pipe is used as electrode of super capacitor material Material is 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 As follows:
(1) hexamethylenetetramine aqueous solution and zinc nitrate aqueous solution mixing, with nickel foam as substrate, enter Row first step hydro-thermal reaction, obtains ZnO template;
(2) by ZnO template obtained in step (1) and second step is carried out with D/W Hydro-thermal reaction, after washing and drying, then carries out heat treatment, obtains growing the nickel foam having CNT;
(3) by sodium molybdate, hydrogen peroxide, water mixing, and with acid for adjusting pH to 2~4, formed containing molybdenum Salt electrolyte;
(4) growth prepared with step (2) has the nickel foam of CNT as working electrode, and platinized platinum is Auxiliary electrode, use prepared by step (3) containing molybdenum salt electrolyte, constitute electrochemistry bipolar electrode system, Apply electric current, nickel foam deposits, makes molybdenum element be coated on CNT surface, afterwards product is washed Wash dry, afterwards 700~900 DEG C of high-temperature process, obtain target product (i.e. ultracapacitor carbon pipe/ Molybdenum carbide combination electrode material).
In step (1), the concentration of described hexamethylenetetramine aqueous solution is 0.025~0.2mol/L, institute The nitric acid zinc concentration stated is 0.025~0.2mol/L.
Hexamethylenetetramine and zinc nitrate in zinc nitrate aqueous solution in described hexamethylenetetramine aqueous solution Mol ratio be 0.5~1.5:1, more preferably 1:1.
The condition of described 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), the concentration of described D/W is 0.1~0.5mol/L, the most excellent Elect 0.2~0.4mol/L as.
The condition of described second step hydro-thermal reaction is: hydrothermal temperature is 170~190 DEG C, and the hydro-thermal time is 2~6 hours.
Described heat treatment is carried out in noble gas, and described noble gas is argon.
The condition of described heat treatment is: temperature is 400~600 DEG C, and the time is 1~3 hour.
In step (3), described sodium molybdate, hydrogen peroxide, the mass ratio of water are 2.5:0.7~1.3: 450~550, further preferred 2.5:0.9:502.1.Described acid uses dilute sulfuric acid, mass percent Less than 70.4%;
In step (4), in described electrochemistry bipolar electrode system, apply negative electrode electricity at working electrode Stream 0.5~2.5mA/cm2, react 5~25min.
Described high-temperature process is carried out in noble gas, and described noble gas is argon.
The time of described high-temperature process is 1~3h.
Described ultracapacitor carbon pipe/molybdenum carbide combination electrode material, including substrate, is arranged on described base CNT at the end and the molybdenum carbide nanometer layer being coated on described CNT.Described nano-sized carbon A diameter of the 80 of pipe~500nm, the thickness of described molybdenum carbide nanometer layer is 50~100nm.According to reality Border needs, and can adjust response time, reaction density and electric current density to control its size and thickness.Institute The substrate stated is nickel foam.
Compared with prior art, present invention have the advantage that
The inventive method with ZnO nano bar (a diameter of the 40 of ZnO nano bar~300nm) as template, Prepare carbon pipe by hydrothermal carbonization method, then prepare ultracapacitor carbon pipe/carbonization by cathodic electrodeposition Molybdenum combination electrode material.This preparation method is simple and convenient, it is easy to control.
Ultracapacitor carbon pipe/molybdenum carbide combination electrode material prepared by the present invention, carbon pipe has bigger ratio Surface area, can increase the contact area of electrolyte and motor, it is provided that bigger more effectively active reaction area, Meanwhile, provide good ion and electrons spread passage for electrochemical reaction, shorten the diffusion of ion away from From, improve electrochemical capacitance performance.In the present invention, compound by carbon and molybdenum, overcome single material with carbon element low Ratio electric capacity, the high magnification fast shortcoming of decay, thus while realizing high power discharge performance, keep high-energy Density, 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 possesses fast electronics and ion transmission channel, leads The best, good cycling stability, the forthright excellence of high power, energy/power density is high, is suitable in big current bar Capacitance energy storage work is carried out under part.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of the CNT grown in nickel foam in embodiment 1;
Fig. 2 is transmission electron microscope (TEM) figure of the CNT grown in nickel foam in embodiment 1;
Fig. 3 is the scanning electron microscope of ultracapacitor carbon pipe/molybdenum carbide combination electrode material in embodiment 1 (SEM) figure;
Fig. 4 is the transmission electron microscope of ultracapacitor carbon pipe/molybdenum carbide combination electrode material in embodiment 1 (TEM) figure.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
Weigh 1.752g hexamethylenetetramine and 3.719g zinc nitrate is placed in two beakers, be separately added into 500ml deionized water, is respectively configured hexamethylenetetramine aqueous solution and the 0.025mol/L of 0.025mol/L Zinc nitrate aqueous solution, respectively take 40ml in empty beaker, after mix homogeneously, solution moved into poly-four In fluorothene autoclave, and put into nickel foam as substrate, autoclave is sealed, at the bar of 80 DEG C Hydro-thermal reaction 5 hours under part.It is cooled to room temperature 25 DEG C after reaction, is washed with deionized, obtains ZnO Template.Weighing 36g glucose and be dissolved in 1000ml deionized water, stirring is to being completely dissolved.Then take 80ml D/W is in politef autoclave, and puts into ZnO template, by high pressure Still seals, hydro-thermal reaction 2 hours under conditions of 170 DEG C.It is cooled to room temperature 25 DEG C after reaction, uses Deionized water wash is dried, and calcines 1 hour under the conditions of 400 DEG C in argon, naturally cools to room temperature 25 DEG C, the nickel foam having CNT must be grown.The CNT of growth in nickel foam is scanned electricity Mirror (SEM) and transmission electron microscope (TEM) are analyzed, as shown in Figure 1-2, it is seen that: carbon pipe vertical-growth and flat All diameters are about 80nm, and surface is the most smooth.
Weigh 2.5g sodium molybdate and 3.0g aqueous hydrogen peroxide solution (wt30%) (weight ratio is 5:6) respectively It is dissolved in 500ml deionized water, stirs to being completely dissolved formation salt electrolyte Han molybdenum, regulate with dilute sulfuric acid PH value is 2.Then the salt electrolyte containing molybdenum being transferred in electrochemistry bipolar electrode system, wherein growth is received The nickel foam of rice carbon pipe is working electrode, and platinized platinum is auxiliary electrode.Apply cathode current on the working electrode (s Density is 0.5mA/cm2, react 5min, nickel foam deposits, makes molybdenum element be coated on nanometer Carbon tube-surface, after being washed with deionized drying, calcines 1 hour under the conditions of 700 DEG C in argon, from So it is cooled to room temperature 25 DEG C, obtains ultracapacitor carbon pipe/molybdenum carbide combination electrode material.To the carbon obtained Pipe/molybdenum carbide combination electrode material is scanned Electronic Speculum (SEM) and transmission electron microscope (TEM) is analyzed, such as Fig. 3-4 Shown in, it is seen that: carbon pipe/molybdenum carbide compound pipeline complex pipeline average diameter is at 130nm, and vertical-growth is in substrate On.Carbon pipe/molybdenum carbide multiple tube outer surface is relatively rough, and molybdenum carbide is supported on outside, and thickness is about 50 nm.Molybdenum carbide is 50:50 with the weight ratio of carbon pipe.
Embodiment 2
Weigh 7.008g hexamethylenetetramine and 14.876g zinc nitrate is placed in two beakers, add respectively Enter 500ml deionized water, be respectively configured hexamethylenetetramine aqueous solution and the 0.1mol/L of 0.1mol/L Zinc nitrate aqueous solution, respectively take 40ml in empty beaker, after mix homogeneously, solution moved into poly-four In fluorothene autoclave, and put into nickel foam as substrate, autoclave is sealed, at the bar of 90 DEG C Hydro-thermal reaction 8 hours under part.It is cooled to room temperature 25 DEG C after reaction, is washed with deionized, obtains ZnO Template.Weighing 54g glucose and be dissolved in 1000ml deionized water, stirring, to being completely dissolved, obtains Fructus Vitis viniferae Sugar aqueous solution.Then take 80ml D/W in politef autoclave, and put into ZnO template, seals autoclave, hydro-thermal reaction 4 hours under conditions of 180 DEG C.After reaction cold But to room temperature 25 DEG C, it is washed with deionized drying, and it is little to calcine 2 in argon under the conditions of 500 DEG C Time, naturally cool to room temperature 25 DEG C, the nickel foam having CNT must be grown.
Weigh 2.5g sodium molybdate and 3.0g aqueous hydrogen peroxide solution (wt30%) (weight ratio is 5:6) respectively Being dissolved in 500ml deionized water, stir to being completely dissolved formation salt electrolyte Han molybdenum, pH value is 3.So Afterwards the salt electrolyte containing molybdenum is transferred to, in electrochemistry bipolar electrode system, growth has the nickel foam of CNT For working electrode, platinized platinum is auxiliary electrode.Applying cathode-current density on the working electrode (s is 1.0 mA/cm2, react 15min, described nickel foam deposit, makes molybdenum element be coated on carbon tube-surface, After being washed with deionized drying, calcine 2 hours under the conditions of 800 DEG C in argon, naturally cool to room Temperature, obtains ultracapacitor carbon pipe/molybdenum carbide combination electrode material.
Embodiment 3
Weigh 14.016g hexamethylenetetramine and 29.752g zinc nitrate is placed in two beakers, add respectively Enter 500ml deionized water, the hexamethylenetetramine aqueous solution of configuration 0.2mol/L and the nitre of 0.2mol/L Acid zinc aqueous solution, takes 40ml the most respectively in empty beaker, after mix homogeneously, solution is moved into polytetrafluoro In ethylene high pressure reactor, and put into nickel foam as substrate, autoclave is sealed, at the bar of 100 DEG C Hydro-thermal reaction 11 hours under part.It is cooled to room temperature 25 DEG C after reaction, is washed with deionized, obtains ZnO Template.Weighing 72g glucose and be dissolved in 1000ml deionized water, stirring is to being completely dissolved.Then take 80ml D/W is in politef autoclave, and puts into ZnO template, by high pressure Still seals, hydro-thermal reaction 6 hours under conditions of 190 DEG C.It is cooled to room temperature 25 DEG C after reaction, uses Deionized water wash is dried, and calcines 3 hours under the conditions of 600 DEG C in argon, naturally cools to room temperature 25 DEG C, the nickel foam having CNT must be grown.
Weigh 5.0g sodium molybdate and 6.0g aqueous hydrogen peroxide solution (wt30%) (weight ratio is 5:6) respectively Being dissolved in 500ml deionized water, stir to being completely dissolved formation salt electrolyte Han molybdenum, pH value is 4.So Afterwards the salt electrolyte containing molybdenum being transferred in electrochemistry bipolar electrode system, wherein growth has the foam of CNT Nickel is working electrode, and platinized platinum is auxiliary electrode.Applying cathode-current density on the working electrode (s is 2.5 mA/cm2, react 25min, described nickel foam deposits, makes molybdenum element be coated on carbon tube-surface, After being washed with deionized drying, calcine 3 hours under the conditions of 900 DEG C in argon, naturally cool to room Temperature, obtains ultracapacitor carbon pipe/molybdenum carbide combination electrode material.
Performance test
The ultracapacitor carbon pipe/molybdenum carbide composite made by above-described embodiment 1~3 is as just Pole, nickel foam makees negative pole, and hydrargyrum/mercuric oxide electrode is reference electrode, and in three-electrode system, test is super respectively Capacitive property.Electrolyte is 1mol/M KOH aqueous solution, and charging/discharging voltage is-0.1~0.9V, In 25 ± 1 DEG C of environment, the reversible discharge and recharge ratio of ultracapacitor carbon pipe/molybdenum carbide composite is measured in circulation Electric capacity, charge-discharge performance and high-rate characteristics.
The performance test results is as follows:
The ultracapacitor carbon pipe of embodiment 1, embodiment 2 and embodiment 3/molybdenum carbide composite 2A/g Discharge under electric current density and be respectively 450F/g, 480F/g and 460F/g, and 10000 circulations than electric capacity Rear electric discharge reaches more than 92% than capacity retention.Visible, above-mentioned prepared ultracapacitor carbon pipe/carbonization Molybdenum composite material charge/discharge capacity is high, good cycling stability.
The ultracapacitor carbon pipe of embodiment 1, embodiment 2 and embodiment 3/molybdenum carbide composite 20A/g Discharge under electric current density and be respectively 430F/g, 456F/g and 435F/g, corresponding energy and merit than electric capacity Rate density is respectively 32Wh/kg and 7kW/kg, 38Wh/kg and 10kW/kg, 33Wh/kg and 9 kW/kg.Visible, above-mentioned prepared ultracapacitor carbon pipe/molybdenum carbide composite high rate capability is good, Energy and power density are high.
This is because the incorporation of transition metal molybdenum element improves the electric conductivity of whole composite, carbon pipe/ Molybdenum carbide tubular structure is conducive to the contact area increasing electrode with electrolyte, and provides bigger effective Active reaction area, provides good ion and electrons spread passage for electrochemical reaction simultaneously, shortens The diffusion length of ion, improves electrochemical capacitance performance.
Therefore, ultracapacitor carbon pipe/molybdenum carbide composite of the present invention has high specific capacitance and high circulation longevity Life, high-energy and power density feature, navigate in mobile communication, electric automobile, solar electrical energy generation and aviation It etc. field have broad application prospects.

Claims (10)

1. ultracapacitor carbon pipe/molybdenum carbide combination electrode material, it is characterised in that include substrate, It is arranged on described suprabasil CNT and the molybdenum carbide nanometer layer being coated on described CNT, A diameter of the 80 of described CNT~500nm, the thickness of described molybdenum carbide nanometer layer is 50~100 nm。
The preparation of ultracapacitor carbon pipe/molybdenum carbide combination electrode material the most according to claim 1 Method, it is characterised in that comprise the following steps:
(1) hexamethylenetetramine aqueous solution and zinc nitrate aqueous solution mixing, with nickel foam as substrate, enter Row first step hydro-thermal reaction, obtains ZnO template;
(2) by ZnO template obtained in step (1) and second step is carried out with D/W Hydro-thermal reaction, after washing and drying, then carries out heat treatment, obtains growing the nickel foam having CNT;
(3) by sodium molybdate, hydrogen peroxide, water mixing, and with acid for adjusting pH to 2~4, formed containing molybdenum Salt electrolyte;
(4) growth prepared with step (2) has the nickel foam of CNT as working electrode, and platinized platinum is Auxiliary electrode, use prepared by step (3) containing molybdenum salt electrolyte, constitute electrochemistry bipolar electrode system, Apply electric current, nickel foam deposits, makes molybdenum element be coated on CNT surface, afterwards product is washed Wash dry, afterwards 700~900 DEG C of high-temperature process, obtain ultracapacitor carbon pipe/molybdenum carbide combination electrode Material.
Preparation method the most according to claim 2, it is characterised in that in step (1), described The concentration of hexamethylenetetramine aqueous solution be 0.025~0.2mol/L, described nitric acid zinc concentration is 0.025~0.2mol/L.
Preparation method the most according to claim 2, it is characterised in that in step (1), described Hexamethylenetetramine aqueous solution in the mol ratio of zinc nitrate in hexamethylenetetramine and zinc nitrate aqueous solution It is 0.5~1.5:1.
Preparation method the most according to claim 2, it is characterised in that in step (1), described The condition of first step hydro-thermal reaction be: hydrothermal temperature is 80~100 DEG C, and the hydro-thermal time is 5~11 hours.
Preparation method the most according to claim 2, it is characterised in that in step (2), described The condition of second step hydro-thermal reaction be: hydrothermal temperature is 170~190 DEG C, and the hydro-thermal time is 2~6 little Time.
Preparation method the most according to claim 2, it is characterised in that in step (2), described The condition of heat treatment be: temperature is 400~600 DEG C, and the time is 1~3 hour.
Preparation method the most according to claim 2, it is characterised in that in step (3), described Sodium molybdate, hydrogen peroxide, the mass ratio of water be 2.5:0.7~1.3:450~550.
Preparation method the most according to claim 2, it is characterised in that in step (4), in institute In the electrochemistry bipolar electrode system stated, apply cathode current 0.5~2.5mA/cm at working electrode2, instead Answer 5~25min.
Preparation method the most according to claim 2, it is characterised in that in step (4), institute The time of the high-temperature process stated is 1~3h.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107425185A (en) * 2017-07-17 2017-12-01 济南大学 A kind of preparation method of carbon nanotube loaded carbonization Mo and its application in lithium sulfur battery anode material
CN111210998A (en) * 2020-02-25 2020-05-29 济南大学 3D multifunctional flexible material and application thereof
US11328877B2 (en) * 2019-10-21 2022-05-10 Imam Abdulrahman Bin Faisal University Redox-mediated poly(vinylphosphonic acid) useful in capacitors
US11682531B1 (en) * 2022-01-20 2023-06-20 Imam Abdulrahman Bin Faisal University Nanocomposite electrodes and method of preparation thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005038818A (en) * 2003-06-30 2005-02-10 Junji Nakamura Carbonized molybdenum catalyst and its manufacturing method, as well as electrode for fuel cell and fuel cell utilizing the catalyst
CN103259025A (en) * 2013-02-28 2013-08-21 华南师范大学 Microorganism fuel cell, anode, and anode catalyst and preparation method thereof
CN103904293A (en) * 2014-04-04 2014-07-02 中国工程物理研究院电子工程研究所 Molybdenum trioxide in-situ cladding nitrogen-doped carbon nanotube composite electrode material as well as preparation method thereof and application
CN105148959A (en) * 2015-09-23 2015-12-16 厦门理工学院 Molybdenum carbide-carbon nanotube composite particles and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005038818A (en) * 2003-06-30 2005-02-10 Junji Nakamura Carbonized molybdenum catalyst and its manufacturing method, as well as electrode for fuel cell and fuel cell utilizing the catalyst
CN103259025A (en) * 2013-02-28 2013-08-21 华南师范大学 Microorganism fuel cell, anode, and anode catalyst and preparation method thereof
CN103904293A (en) * 2014-04-04 2014-07-02 中国工程物理研究院电子工程研究所 Molybdenum trioxide in-situ cladding nitrogen-doped carbon nanotube composite electrode material as well as preparation method thereof and application
CN105148959A (en) * 2015-09-23 2015-12-16 厦门理工学院 Molybdenum carbide-carbon nanotube composite particles and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高娇阳: ""高比表面积碳化钼/碳复合体的电化学性能研究"", 《功能材料》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107425185A (en) * 2017-07-17 2017-12-01 济南大学 A kind of preparation method of carbon nanotube loaded carbonization Mo and its application in lithium sulfur battery anode material
CN107425185B (en) * 2017-07-17 2020-03-24 济南大学 Preparation method of carbon nanotube-loaded molybdenum carbide material and application of carbon nanotube-loaded molybdenum carbide material in lithium-sulfur battery positive electrode material
US11328877B2 (en) * 2019-10-21 2022-05-10 Imam Abdulrahman Bin Faisal University Redox-mediated poly(vinylphosphonic acid) useful in capacitors
US11551880B2 (en) 2019-10-21 2023-01-10 Imam Abdulrahman Bin Faisal University Gel electrolyte capacitor
US11749468B2 (en) 2019-10-21 2023-09-05 Imam Abdulrahman Bin Faisal University Method for storing energy in a hydrogel supercapacitor
US11810717B2 (en) 2019-10-21 2023-11-07 Imam Abdulrahman Bin Faisal University Method for charging polymer-reinforced capacitor
CN111210998A (en) * 2020-02-25 2020-05-29 济南大学 3D multifunctional flexible material and application thereof
CN111210998B (en) * 2020-02-25 2022-02-11 济南大学 3D multifunctional flexible material and application thereof
US11682531B1 (en) * 2022-01-20 2023-06-20 Imam Abdulrahman Bin Faisal University Nanocomposite electrodes and method of preparation thereof

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