CN106549162A - Combination electrode material, its preparation method and its application in all-vanadium flow battery - Google Patents

Combination electrode material, its preparation method and its application in all-vanadium flow battery Download PDF

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CN106549162A
CN106549162A CN201510607684.6A CN201510607684A CN106549162A CN 106549162 A CN106549162 A CN 106549162A CN 201510607684 A CN201510607684 A CN 201510607684A CN 106549162 A CN106549162 A CN 106549162A
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electrode material
battery
carbonate
acid
combination electrode
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CN106549162B (en
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姚川
付华峰
李�浩
孟晶晶
孙红
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Xuchang University
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Xuchang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of combination electrode material, its preparation method and its application in all-vanadium flow battery.The preparation method is comprised the following steps：During organic carbon source presoma is dissolved in water or organic solvent or its mixture；A certain amount of micro-nano spherical granular material is added as hard template；Three-dimensional carbon base material is placed in suspension and is sufficiently impregnated with, be then placed in tube furnace and be carbonized, finally by material pickling to remove the granule as hard template, and washed repeatedly, be dried.Pattern of the surface of the combination electrode material in even porous, duct insertion, aperture size are micro-nano rank, with higher specific surface area and porosity, while a number of oxygen-containing functional group such as hydroxyl, carboxyl, lactone group etc. are contained in surface.The combination electrode material can be used as vanadium redox flow battery electrode material simultaneously, with stronger electro catalytic activity, hence it is evident that reduce VO2+/VO2 +The charge transfer impedance of oxidation-reduction pair electrode reaction and resulting polarization overpotential.

Description

Combination electrode material, its preparation method and its in all-vanadium flow battery Using
Technical field
The present invention relates to extensive energy-storage battery technical field, more particularly to a kind of combination electrode material, its Preparation method and its application in all-vanadium flow battery.
Background technology
With consuming excessively for Fossil fuel and increasingly sharpening for environmental pollution, national governments just constantly add The big investment R＆D intensity to regenerative resources such as wind energy and solar energys, strives exhausting it in fossil energy Before find effective replacer.American energy information administration speculates, to the year two thousand thirty U.S. about 40% Electricity supply will come from renewable energy power generation [Qian Baizhang, U.S.'s renewable energy utilization will be existing Shape and prediction, global energy net, WWW.worldenergy.com.cn, 2007-8.24].2009, The Chinese government exists《The development of New Energy Sources In China industry is planned》It is middle to promise to undertake to the world, will make to the year two thousand twenty Regenerative resource consumption account for whole energy-consumings 15% [National Energy Board announce, www.nea.gov.cn/2012-02/10/c_131402482.htm,2013-03-22].When the time comes, wind-powered electricity generation installation Capacity will rise to 150GW by the 30GW of 2010, and Photovoltaic generation installed capacity is also by 2010 The 1GW in year rises to 20GW.However, by randomness variables such as season, weather, day and night temperatures Impact, the renewable energy power generation such as wind energy, solar energy produce randomness fluctuation and have it is discontinuous, Unstable the characteristics of.If by these low-grade electric energy direct grid-connecteds, it will bring impact to electrical network Harm harmonic pollution, is that its large-scale application brings major obstacles, causes large area " abandoning electricity ", " gives up The phenomenon of the wastings of resources such as electricity ".Data according to incompletely statistics, only 2012, the wind wasted by China Electric resources are more than 20TWh [http://finance.sina.com.cn/roll/20141119/205420864737.shtml].This is supplied in electric power Answer today of growing tension, but cause wind-powered electricity generation and photovoltaic generation extremely irrational " relative surplus " and The operation stagnation of relevant enterprise and large area loss.
The effective scheme for solving the problem is introduced between " renewable energy power generation " and " electrical network " The energy storage technology of regular, smoothing effect is played as intermediary, to change the electric power of traditional " send out and use " Supplying mode.First low-grade power storage is got up, Jing after integrating again with smooth, stable side Formula carries out grid-connected output.In many energy storage technologies, all-vanadium liquid flow energy storage battery (Vanadium Flow Battery, VFB) it is following because having many advantages, such as：1) energy efficiency is high, operation safety and stability, follow Ring life-span length (, up to more than 13000 times, service life was more than 20 years for charge and discharge cycles)；2) addressing Freely, power and capacity are separate, and system design is flexible；3) pollution-free, electrolyte is easily again Raw, maintenance is simple and operation cost is low, it is considered to be renewable for solving solar energy, wind energy etc. The most promising technology of energy electricity generation system randomness and intermittent unstable state defect problem, can be again The raw energy to generate electricity and have great demand [Journal of the Electrochemical with intelligent grid construction Society,2011,158,R55].In addition, the technology is in electrical network " peak load shifting ", uninterrupted Emergency power supply, electric motorcar charging station, communication base station and military field have important potential application Value.In the energy storage technology development plan that the U.S. formulates for 2012, all-vanadium liquid flow energy storage battery name Row first develop the first place of technology.Technique is most earlier than 1985 by New South Wales, Australia The Marria Kacos professors of university and its partner propose that they adopt the vanadium ion of different valence state VO2+/VO2 +, V2+/V3+Respectively as positive and negative electrode active substance, just largely avoid The cross-contamination of negative electrolyte solution.The standard eleotromotive force of battery is 1.26V, and operation principle is：
Positive pole：
Negative pole：
Have at present several demonstrative projects different geographical run, its core technology mainly by Japan, The developed countries such as the U.S., Australia, Canada and Europe are grasped.China catches up from behind, from upper The nineties also began to carry out every research of technique and actively carried out demonstrating running century, and main research is single Research institutions such as Wei You Dalian Chemiclophysics Inst., Chinese Academy of Sciences, Tsing-Hua University, Central South University and big Connect Raycom energy storage, Beijing Pu Nengdeng enterprises.In the recent period, developed by Dalian Chemiclophysics Inst., Chinese Academy of Sciences Scale for 5MW/10MWh Applied D emonstration engineering by Liaoning Prospecting ＆ Designing Inst. of Electric Power examination, Become all vanadium flow energy-storage battery system of maximum-norm global so far.However, business will be realized Change popularization and application, it is urgently to be resolved hurrily that all-vanadium liquid flow energy storage technology battery also has series of problems.Improve complete The charging and discharging currents density of vanadium liquid stream electric current, reduces the size of battery module, and then reduces manufacturing Cost is the highly important research direction in the field in recent years.Current disclosed report all-vanadium flow battery Under conditions of energy conversion efficiency is kept higher than 80%, its charging and discharging currents density is about system 80～120mA/cm2.If the value can be promoted to 160～200mA/cm2And do not reduce energy and turn Efficiency is changed, then can improve the power density of battery module will by about one time, and this will promote full vanadium significantly The commercialization process of liquid flow energy storage battery.
Electrode material is one of critical material in liquid flow energy storage battery, and determines that the power of battery is close The key factor of degree.The main electrode material of VFB is carbon fiber felt or graphite felt at present.It is this Electrode material is mainly characterized by that porosity is high, and active area is relatively large, but which is for VO2+/VO2 + The electrode reaction activity of oxidation-reduction pair and reversibility are poor, and become restriction cell power density and carry One of high principal element [Carbon, 2012,50,2347-2374].In order to improve carbon fibre material Performance, generally need to be surface-treated to which or be modified, conventional method mainly include surface oxidation and Metallic cover [Electrochimica Acta, 1992,37,1253-1269].Oxidation processes are easily reduced carbon The mechanical performance and electric conductivity of fiber, and easily cause electrode material oxygen mistake is analysed in charging process The decline of current potential；Surface coated metal material highly acid, strong oxidizing property electrolyte system it is long-term Operating stability problem is difficult to solve, and metal used great majority be noble metal or its alloy such as Ir, Pt, Ru etc., high cost are also the obstacle of its large-scale application.In recent years, it is several new Material with carbon element such as CNT [Carbon, 2014,9,3463-3470], Graphene [Carbon, 2014,9,6 93-700], nitrating mesoporous carbon [Journal of Power Sources, 2010,195,4375-4379], carbon Nanometer wall [Nano Energy, 2012,1,833-839] is also reported as VFB positive electrodes.But this The preparation process of a little materials is complex, and is in powder, it is difficult to directly utilize (or using a large amount of Binding agent which is supported in carbon fiber felt substrate and is reduced its electronic conductivity).Therefore, open Send out that specific surface area is big, catalysis activity is high a kind of, stable cycle performance and cheap electrode material still It is important research topic in the field.
The content of the invention
It is an object of the invention to provide a kind of specific surface area is big, catalysis activity is high, cyclicity Can stablize and cheap combination electrode material, its preparation method and its application, to improve The energy conversion efficiency and power density of all-vanadium flow battery, so as to solve carbon fibre fabric (such as carbon felt, carbon paper and carbon cloth etc.) is for VO2+/VO2 +The electro-catalysis of oxidation-reduction pair Activity is low；And other modified electrode materials are difficult to the problem of large-scale application.
In order to realize object above, in one aspect, the technical solution used in the present invention is： A kind of method for preparing the combination electrode material for all-vanadium flow battery, the method include with Lower step：
1) organic carbon source presoma is dissolved in into water or organic solvent or water and organic solvent Mixture in；
2) micro-nano granules shape inorganic material is added as hard template in above-mentioned solution, so Afterwards they are placed in megasonic tank and are shaken, until forming finely dispersed suspension Liquid；
3) three-dimensional carbon base material is placed in the suspension and is sufficiently impregnated with, so that three The interior surface for tieing up carbon-based bottom material is uniformly coated, then by the three-dimensional carbon substrate material of cladding Material takes out, and is put in vacuum drying oven and is dried at room temperature；
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to institute Noble gases are passed through in stating stove, furnace temperature is increased to into target temperature then, so as to organic carbon Source presoma is carbonized, and the stove is naturally cooled to room temperature then；
5) pickling is carried out to the material that Jing is carbonized using acid solution, to remove as hard template Micro-nano granules shape material；
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter and be dried in vacuum drying oven at room temperature, in case assembled battery is used.
Further, step 1) in organic carbon source presoma be cellulose, starch, fruit Sugar, maltose, hemicellulose, arabic gum, carrageenan, arabinose, glucose, At least one in sucrose, polyvinyl alcohol, Polyethylene Glycol and POLYPROPYLENE GLYCOL.
Further, step 1) in organic solvent be methanol, ethanol, normal propyl alcohol, different At least one in propanol, acetone, ethylene glycol and dimethyl sulfoxide.
Further, step 2) in die panel material be Calcium Carbonate, Zinc Oxide, carbonic acid Sodium, potassium carbonate, ferric carbonate, brium carbonate, strontium carbonate, zinc carbonate, magnesium carbonate, lithium carbonate, At least one in magnesium hydroxide, zinc hydroxide and ferrum oxide
Further, the three-dimensional carbon base material is carbon fiber felt, graphite fibre felt, carbon At least one in fibrous paper, papyrex, foamy carbon and carbon cloth.
Further, step 4) in the noble gases be nitrogen, argon and helium in At least one.
Further, step 4) in carbonisation heating rate be 1～20 DEG C/min； The target temperature is 600～1500 DEG C；And carbonization time is 0.5～20h.
Further, step 5) in acid solution be by Fluohydric acid., sulphuric acid, phosphoric acid, nitre At least one soluble in water in acid, formic acid, hydrochloric acid, acetic acid and benzenesulfonic acid and obtain it is molten Liquid.
Further, the molar concentration of the acid solution is 0.1～3.0mol/L.
In yet another aspect, the invention provides it is a kind of by the process described above prepare Combination electrode material.
In yet another aspect, the invention provides it is a kind of by the process described above prepare Application of the combination electrode material in the electrode material of all-vanadium flow battery.
In yet another aspect, the invention provides it is a kind of by the process described above prepare Combination electrode material, or other catalysis are further loaded with by carrier of the combination electrode material Application of the material of agent in the electrode material of all-vanadium flow battery.
The combination electrode material prepared by the method for the present invention is had the advantages that：
(1) pattern of the surface of the combination electrode material in even porous, duct insertion, Aperture size is micro-nano rank, with higher specific surface area and porosity, while surface Containing a number of oxygen-containing functional group such as hydroxyl, carboxyl, lactone group etc..
(2) combination electrode material can be used as the electrode material of all-vanadium flow battery, with stronger Electro catalytic activity, hence it is evident that reduce VO2+/VO2 +The charge transfer resistance of oxidation-reduction pair electrode reaction Anti- and resulting polarization overpotential, significantly improves the reversibility of electrode reaction.
(3) during combination electrode is prepared using the combination electrode material, it is not necessary to adhesive, And the combination electrode for preparing conducts electricity very well；Preparation process is simple and with low cost, it is easy to Realize industrialized production.
(4) combination electrode prepared using the combination electrode material can be used for all-vanadium flow battery, The energy conversion efficiency and charging and discharging currents density of battery are greatly improved, and then it is close to improve the power of battery Degree, while identical energy storage task is completed, can reduce the volume and manufacturing cost of battery module. May advantageously facilitate the commercialization of all-vanadium flow battery.
Description of the drawings
Fig. 1 (a) and (b) are NEW TYPE OF COMPOSITE electricity prepared in embodiments of the invention 1 The microscopic appearance of pole material.
Fig. 2 is prepared novel composite electrode material in embodiments of the invention 1 0.05 mol/L VO2++0.05mol/L VO2 ++3mol/L H2SO4Circulation in electrolyte solution Volt-ampere curve.
Fig. 3 is using novel composite electrode material group prepared in embodiments of the invention 1 The all-vanadium flow battery of dress is in 80mA/cm2、100mA/cm2、120mA/cm2、140 mA/cm2And 160mA/cm2Electric current density under charging and discharging curve.
Fig. 4 is using novel composite electrode material assembling prepared in embodiments of the invention 2 All-vanadium flow battery is in 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2With 120 mA/cm2Electric current density under charging and discharging curve.
Specific embodiment
In order that objects and advantages of the present invention are clearer, in conjunction with embodiment to the present invention Technical scheme required for protection is described in further detail.It should be appreciated that described herein Specific embodiment be used merely to explain the present invention and be not intended to limit the present invention.
In an embodiment of the invention, the invention provides one kind is prepared for full vanadium The method of the combination electrode material of flow battery, the method comprise the steps：
1) organic carbon source presoma is dissolved in into water or organic solvent or water and organic solvent Mixture in；
2) in above-mentioned solution add micro-nano granules shape material as hard template, and by it Be placed in megasonic tank and shaken, until forming finely dispersed suspension；
3) three-dimensional carbon base material is placed in suspension and is sufficiently impregnated with, and make three-dimensional The interior surface of carbon-based bottom material is uniformly coated, then by the three-dimensional carbon base material of cladding Take out, and be put in vacuum drying oven and be dried at room temperature；
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through noble gases, the temperature of stove is increased to into target temperature then, with to organic carbon source Presoma is carbonized, and the stove is naturally cooled to room temperature then；
5) pickling is carried out to the material that Jing is carbonized using acid solution, to remove as hard template Micro-nano granules shape material；
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter the interior drying for standby at room temperature of vacuum drying oven.
Preferably, step 1) in organic carbon source presoma be cellulose, starch, Fructose, Maltose, hemicellulose, arabic gum, carrageenan, arabinose, glucose, sucrose, At least one in polyvinyl alcohol, Polyethylene Glycol and POLYPROPYLENE GLYCOL.
Preferably, step 1) in organic solvent be methanol, ethanol, normal propyl alcohol, isopropyl At least one in alcohol, acetone, ethylene glycol and dimethyl sulfoxide.
Preferably, step 2) in die panel material be Calcium Carbonate, Zinc Oxide, sodium carbonate, Potassium carbonate, ferric carbonate, brium carbonate, strontium carbonate, zinc carbonate, magnesium carbonate, lithium carbonate, hydrogen At least one in magnesium oxide, zinc hydroxide and ferrum oxide.The die panel material accounts for suspension The 5%～40% of liquid total mass fraction.
Preferably, in the method for the combination electrode material of all-vanadium flow battery is prepared, The three-dimensional carbon base material is carbon fiber felt, graphite fibre felt, carbon fiber paper, graphite fibre At least one in paper, foamy carbon and carbon cloth.
Preferably, in the method for the combination electrode material of all-vanadium flow battery is prepared, Step 4) in the noble gases be nitrogen, argon and helium at least one.
Preferably, in the method for the combination electrode material of all-vanadium flow battery is prepared, Step 4) in carbonisation heating rate be 1～20 DEG C/min；The target temperature is 600～1500 DEG C；And carbonization time is 0.5～20h.
Preferably, step 5) in acid solution be by Fluohydric acid., sulphuric acid, phosphoric acid, nitric acid, At least one soluble in water in formic acid, hydrochloric acid, acetic acid and benzenesulfonic acid and the solution that obtains.
Preferably, in the method for the combination electrode material of all-vanadium flow battery is prepared, The substance withdrawl syndrome of the acid solution is 0.1～3.0mol/L.
In yet another aspect, the invention provides it is a kind of by the process described above prepare Combination electrode material.
In yet another aspect, the invention provides it is a kind of by the process described above prepare Application of the combination electrode material in the electrode material of all-vanadium flow battery.
In yet another aspect, the invention provides it is a kind of by the process described above prepare Combination electrode material, or other catalysis are further loaded with by carrier of the combination electrode material Application of the material of agent in the electrode material of all-vanadium flow battery.
Embodiment 1
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the maltose 10g as organic carbon source presoma is dissolved in cumulative volume for 100mL Water and ethanol in, wherein the volume ratio of water and ethanol is 1:1.
2) the micro-nano granules shape zinc carbonate of 20g is added as hard template in above-mentioned solution, The particle size of zinc carbonate is about 50～100nm, and then they are placed in megasonic tank Shaken, until forming finely dispersed suspension.
3) carbon fiber felt is cut into into 30mm × 30mm × 5mm sizes, then by which Insert and be sufficiently impregnated with the suspension, so that the interior surface of carbon fiber felt is uniformly wrapped Cover, then the carbon fiber felt of cladding is taken out, and be put in vacuum drying oven to enter at room temperature Row drying.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, Ran Houxiang Nitrogen is passed through in stove as shielding gas, first tube furnace is purged to replace before intensification Then the temperature of stove is increased to 1000 DEG C with the heating rate of 5 DEG C/min by the air in pipe And 3h is incubated, to be carbonized to the material, the stove is naturally cooled to into room temperature then.
5) hydrochloric acid solution for preparing substance withdrawl syndrome for 1mol/L is for the material that is carbonized to Jing Material carries out pickling, to remove the micro-nano granules zinc carbonate as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
Novel composite electrode material to preparing carries out morphology characterization：Scanned using Flied emission Electron microscope observation its microscopic appearance, as a result as shown in Fig. 1 (a) and (b).As schemed Shown in 1, in uniform loose structure, aperture size is about 50～100 on the surface of electrode material Nm, and hole wall is only several nanometers, duct insertion.This structure will make electrode material with compared with High specific surface area and porosity, thus it is easy to the transmission and absorption of electrode active material.
Novel composite electrode material to preparing carries out Electrochemical Characterization：Construct first By being right with prepared novel composite electrode material as working electrode, with large area graphite cake Electrode, the three-electrode system electrolyzer constituted as reference electrode with saturated calomel electrode；Then Prepare electrolyte solution：0.05mol/L VO2++0.05mol/L VO2 ++3mol/L H2SO4, voltammetric scan is circulated wherein so as to obtain prepared Combined electrode Material is for VO2+/VO2 +The cyclic voltammetry curve of oxidation-reduction pair, as shown in Figure 2. By oxidation and the electricity of the size and ratio, oxidation and reduction peak of the peak point current of reduction process Potential difference and oxidation and reduction peak current with sweep speed variation relation, it can be seen that Novel composite electrode material is for VO2+/VO2 +Oxidation-reduction pair is respectively provided with good electricity and urges Change activity.When scanning speed is 10mV/s, VO2+/VO2 +The oxygen of oxidation-reduction pair Change and the potential difference of reduction peak is for about only 100mV, and with the increase of sweep speed, Oxidation and the position of reduction peak are basically unchanged, and it is good reversible that this shows that its electrode process has Property.
Additionally, in the present embodiment, the novel composite electrode material is applied to assemble full vanadium Flow battery.Battery is suitable according to end plate-collector plate-electrode/membrane/electrode-collector plate-end plate Sequence is assembled in the way of pressure filter.Wherein, barrier film adopts perfluoro sulfonic acid membrane.The battery is existed Charge-discharge test is carried out under different electric current densities, as a result as shown in Figure 3.As a result show, The battery is in 80mA/cm2、100mA/cm2、120mA/cm2、140mA/cm2With 160mA/cm2Electric current density under can carry out normal discharge and recharge, and curve smoothing. 80mA/cm2Electric current density under, the energy conversion efficiency of battery is up to 86.5%；And Even if in 160mA/cm2High magnification under the conditions of, the energy conversion efficiency of battery still close to In 80%.
Comparative example 1
Compare with embodiment 1, using the carbon of undressed same size conventional at present Fiber felt assembles all-vanadium flow battery as electrode material.The assembling mode of the battery and Other materials in addition to working electrode are same as Example 1, and same 80 mA/cm2、100mA/cm2、120mA/cm2、140mA/cm2And 160mA/cm2 Electric current density under charge-discharge test is carried out to battery.As a result show, in 80mA/cm2's Under electric current density, the energy conversion efficiency of battery is 82.2%；And in 160mA/cm2Height Under the conditions of multiplying power, the energy conversion efficiency of battery is only 73.5%.
Embodiment 2
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the 5g Fructose as organic carbon source presoma is dissolved in cumulative volume for 100mL's In water and dimethyl sulfoxide, wherein water and the volume ratio of dimethyl sulfoxide are 5:1.
2) 15g micro-nano granules shape magnesium carbonate is added as hard template in above-mentioned solution, The particle size of magnesium carbonate is about 100～300nm.Then they are placed in into megasonic tank In shaken, until forming finely dispersed suspension.
3) carbon fiber paper is cut into into 30mm × 30mm sizes, its thickness is about 200 μm.Then it is sufficiently impregnated with being put into suspension, so that the interior surface quilt of carbon fiber paper It is uniform to coat, then coated carbon fiber paper is taken out, and is put in vacuum drying oven It is dried under room temperature.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through nitrogen as shielding gas, before intensification tube furnace is purged to replace pipe first In air, the temperature of stove is increased to into 700 DEG C simultaneously with the heating rate of 10 DEG C/min then Stove, so as to be carbonized to the material, is then naturally cooled to room temperature by insulation 4h.
5) preparation substance withdrawl syndrome is the salpeter solution of 0.5mol/L for being carbonized to Jing Material carries out pickling, to remove the micro-nano granules magnesium carbonate as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
In the present embodiment, the novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to battery, as a result as shown in Figure 4.As a result show, the battery exists 40mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2 Electric current density under can carry out normal discharge and recharge, curve smoothing.In 40mA/cm2's Under electric current density, the energy conversion efficiency of battery is up to 81.4%；Even and if 120 mA/cm2High magnification under the conditions of, the energy conversion efficiency of battery remains to reach 70.9%.
Comparative example 2
Compare with embodiment 2, using the carbon of undressed same size conventional at present Fibrous paper assembles all-vanadium flow battery as electrode material.The assembling mode of the battery and Other materials in addition to working electrode are same as Example 1, and same 40 mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electricity Charge-discharge test is carried out under current density.As a result show, in 40mA/cm2Electric current density under, The energy conversion efficiency of battery is 67.0%；And in 120mA/cm2High magnification under the conditions of, Battery cannot complete normal discharge and recharge.
Embodiment 3
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the 12g sucrose as organic carbon source presoma is dissolved in cumulative volume for 100mL Water and acetone in.Water is 4 with the volume ratio of acetone:1.
2) the micro-nano granules shape Calcium Carbonate of 25g is added as hard template in above-mentioned solution, The particle size of Calcium Carbonate is about 50～200nm.Then they are placed in megasonic tank Shaken, until forming finely dispersed suspension.
3) papyrex is cut into into 30mm × 30mm sizes, its thickness is about 250 μm.Then it is sufficiently impregnated with being placed on suspension, so that the interior surface of papyrex Uniformly coated, the papyrex for then just coating takes out, and is put into vacuum drying oven Inside it is dried at room temperature for.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through argon as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 900 DEG C with the heating rate of 15 DEG C/min then and is protected Stove, so as to be carbonized to the material, is then naturally cooled to room temperature by warm 5h.
5) preparation substance withdrawl syndrome is the hydrochloric acid solution of 1.5mol/L for being carbonized to Jing Material carries out pickling, to remove the micro-nano granules Calcium Carbonate as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter and be dried in vacuum drying oven at room temperature, it is standby.
In the present embodiment, the novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, curve smoothing are carried out enough.In 40mA/cm2Under electric current density, battery Energy conversion efficiency be up to 83.1%；And in 120mA/cm2High magnification under the conditions of, The energy conversion efficiency of battery still can reach 72.4%.
Comparative example 3
Compare with embodiment 3, using the stone of undressed same size conventional at present Black fibrous paper assembles all-vanadium flow battery as electrode material.The assembling mode of this battery and Other materials in addition to working electrode are same as Example 1, and same 40 mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electricity Charge-discharge test is carried out under current density.As a result show, in 40mA/cm2Electric current density under, The energy conversion efficiency of battery is 65.0%；And in 120mA/cm2High magnification under the conditions of, Battery can not carry out normal discharge and recharge.
Embodiment 4
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the 5g cellulose acetate as organic carbon source presoma is dissolved in cumulative volume for 100 In the water and ethylene glycol of mL.Water is 4 with the volume ratio of ethylene glycol:1.
2) 5g micro-nano granules shape inorganic material lithium carbonate is added as hard in above-mentioned solution Template, the particle size of lithium carbonate are about 300～500nm.Then they are placed in into ultrasound Shaken in ripple washing trough, until forming finely dispersed suspension.
3) foamy carbon is cut into into 30mm × 30mm × 5mm sizes, its internal aperture About 100～200 μm of size, is then placed in foamy carbon in suspension and is sufficiently impregnated with, make Interior surface thereof is uniformly coated, and is then taken out, and is put in vacuum drying oven in room The lower drying of temperature.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through nitrogen as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 1100 DEG C simultaneously with the heating rate of 10 DEG C/min then Stove, so as to be carbonized to the material, is then naturally cooled to room temperature by insulation 2h.
5) sulfuric acid solution for preparing substance withdrawl syndrome for 2mol/L is for the material that is carbonized to Jing Material carries out pickling, to remove the micro-nano granules lithium carbonate as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, and curve smoothing are carried out enough.In 40mA/cm2Electric current density under, The energy conversion efficiency of battery reaches 85.7%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery still can reach 78.2%.
Comparative example 4
Compare with embodiment 4, using the bubble of undressed same size conventional at present Foam carbon assembles all-vanadium flow battery as electrode material.The assembling mode of this battery and remove Other materials beyond working electrode are same as Example 1, and same in 40mA/cm2、 60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under Carry out charge-discharge test.As a result show, in 40mA/cm2Electric current density under, battery Energy conversion efficiency is 70.3%；And in 120mA/cm2High magnification under the conditions of, battery Energy conversion efficiency is only 60.1%.
Embodiment 5
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the starch 5g as organic carbon source presoma is scattered in cumulative volume for 100mL Water and normal propyl alcohol in.Water is 5 with the volume ratio of normal propyl alcohol:1.
2) the addition 20g micro-nano granules shape inorganic material Zinc Oxide conducts in above-mentioned solution Hard template, the particle size of Zinc Oxide are about 500nm～1 μm.Then they are placed in super Shaken in sound wave washing trough, until forming finely dispersed suspension.
3) graphite fibre felt is cut into into 30mm × 30mm × 5mm sizes, then will Which is inserted in suspension and is sufficiently impregnated with, so that the interior surface of graphite fibre felt is uniformly wrapped Cover, then the graphite fibre felt of cladding is taken out, and be put in vacuum drying oven at room temperature It is dried.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through helium as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 1200 DEG C with the heating rate of 2 DEG C/min then and is protected Warm 1h, so as to be carbonized to the material, then naturally cools to room temperature.
5) prepare the material that the phosphoric acid solution that substance withdrawl syndrome is 1.2mol/L is carbonized to Jing Pickling is carried out, to remove the micro-nano granules Zinc Oxide as hard template.
6) deionized water carries out cyclic washing to the material of Jing pickling, is then placed in vacuum It is dried at room temperature in drying baker, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to battery.As a result show, the battery is in 40mA/cm2, 60 mA/cm2, 80mA/cm2, 100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, and curve smoothing are carried out enough.In 40mA/cm2Electric current density under, The energy conversion efficiency of battery reaches 89.6%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery still can reach 82.6%.
Comparative example 5
Compare with embodiment 5, using the stone of undressed same size conventional at present Black fiber felt assembles all-vanadium flow battery as electrode material.The assembling mode of this battery with It is and other materials except for the electrodes are same as Example 1 and same in 40mA/cm2、 60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under Carry out charge-discharge test.As a result show, in 40mA/cm2Under electric current density, the energy of battery Amount conversion efficiency is 81.2%；And in 120mA/cm2High magnification under the conditions of, the energy of battery Amount conversion efficiency is only 75.0%.
Embodiment 6
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the arabic gum 8g as organic carbon source presoma is dissolved in cumulative volume for 100mL Water and acetone in.Water is 4 with the volume ratio of acetone:1.
2) in above-mentioned solution add micro-nano granules shape inorganic material magnesium hydroxide 15g and Potassium carbonate 10g is 100 as the particle size of hard template, magnesium hydroxide and potassium carbonate～ 200nm.Then they are placed in megasonic tank and are shaken, until it is equal to form dispersion Even suspension.
3) carbon cloth is cut into into 30mm × 30mm sizes, about 250 μm of its thickness. Then it is sufficiently impregnated with being put into suspension, so that the interior surface of carbon cloth is uniformly wrapped Cover, then the carbon cloth of cladding is taken out, and is put in vacuum drying oven and is dried at room temperature for.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through helium as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 650 DEG C with the heating rate of 1 DEG C/min then and is protected Stove, so as to be carbonized to the material, is then naturally cooled to room temperature by warm 1.5h.
5) preparation substance withdrawl syndrome is the formic acid solution of 0.5mol/L for being carbonized to Jing Material carries out pickling, to remove the micro-nano granules magnesium hydroxide as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then placed in true It is dried at room temperature in empty drying baker, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to the battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, curve smoothing are carried out enough.In 40mA/cm2Electric current density under, electricity The energy conversion efficiency in pond reaches 75.6%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery is 65.8%.
Comparative example 6
Contrast with embodiment 6, using the carbon cloth of undressed same size conventional at present All-vanadium flow battery is assembled as electrode material.The assembling mode of this battery and remove work Other materials beyond electrode are same as Example 1, and same in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under enter Row charge-discharge test.As a result show, in 40mA/cm2Electric current density under, the energy of battery Amount conversion efficiency is 66.3%；And in 120mA/cm2High magnification under the conditions of, battery cannot Carry out normal discharge and recharge.
Embodiment 7
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the arabinose 5g as organic carbon source presoma is dissolved in cumulative volume for 100mL Water and butanone in.Water is 3 with the volume ratio of ethanol:1.
2) 8g micro-nano granules shape zinc hydroxide is added as hard template in above-mentioned solution, Zinc hydroxide particle size is about 10～50nm.Then they are placed in megasonic tank Shaken, until forming finely dispersed suspension.
3) carbon fiber felt is cut into into 30mm × 30mm × 5mm sizes, then by which Insert in suspension and be sufficiently impregnated with, so that the interior surface of carbon fiber felt is uniformly coated, so Afterwards the carbon fiber felt of cladding is taken out, and is put in vacuum drying oven and is dried at room temperature for.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through nitrogen as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 1500 DEG C simultaneously with the heating rate of 20 DEG C/min then Stove, so as to be carbonized to the material, is then naturally cooled to room temperature by insulation 1h.
5) prepare the material that the acetic acid solution that substance withdrawl syndrome is 1.5mol/L is carbonized to Jing Pickling is carried out, to remove the micro-nano granules zinc hydroxide as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to the battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, curve smoothing are carried out enough.In 40mA/cm2Electric current density under, electricity The energy conversion efficiency in pond reaches 88.3%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery still can reach 83.5%.
Comparative example 7
Compare with embodiment 7, using the carbon of undressed same size conventional at present Fiber felt assembles all-vanadium flow battery as electrode material.The assembling mode of this battery and Other materials in addition to working electrode are same as Example 1, and same 40 mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electricity Charge-discharge test is carried out under current density.As a result show, in 40mA/cm2Electric current density under, The energy conversion efficiency of battery is 84.4%；And in 120mA/cm2High magnification under the conditions of, The energy conversion efficiency of battery is only 78.2%.
Embodiment 8
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the 15g glucoses as organic carbon source presoma are dissolved in cumulative volume for 100mL Water and methanol in.Water is 3 with the volume ratio of methanol:1.
2) the addition 38g micro-nano granules shape inorganic material ferrum oxide conducts in above-mentioned solution Hard template, ferric oxide particles size are about 30～80nm.Then they are placed in into ultrasound wave Shaken in washing trough, until forming finely dispersed suspension.
3) carbon cloth is cut into into 30mm × 30mm sizes, about 250 μm of its thickness. Then it is sufficiently impregnated with being put into suspension, the interior surface of carbon cloth is uniformly coated, Then coated carbon cloth is taken out, and is put in vacuum drying oven and is dried at room temperature for.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through helium as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, be then warming up to 700 DEG C with the heating rate of 12 DEG C/min and be incubated 4h, from And the material is carbonized, stove is naturally cooled to into room temperature then.
5) prepare the material that the benzene sulfonic acid solution that substance withdrawl syndrome is 2.5mol/L is carbonized to Jing Material carries out pickling, to remove the micro-nano granules ferrum oxide as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to the battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, curve smoothing are carried out enough.In 40mA/cm2Electric current density under, electricity The energy conversion efficiency in pond reaches 79.5%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery is to 67.6%.
Comparative example 8
Compare with embodiment 8, using the carbon of undressed same size conventional at present Cloth assembles all-vanadium flow battery as electrode material.The assembling mode of this battery and except electricity Other materials beyond pole are same as Example 1, and same in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under enter Row charge-discharge test.As a result show, in 40mA/cm2Electric current density under, the energy of battery Amount conversion efficiency is 66.0%；And in 120mA/cm2High magnification under the conditions of, battery cannot Carry out normal discharge and recharge.
Embodiment 9
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the polyvinyl alcohol 4g as organic carbon source presoma is dissolved in cumulative volume for 100mL Water and ethanol in.Water is 3 with the volume ratio of ethanol:1.
2) 10g micro-nano granules shape brium carbonates are added as hard template in above-mentioned solution, About 7～10 μm of barium carbonate particle size.Then they are placed in megasonic tank is carried out Concussion, until forming finely dispersed suspension.
3) carbon fiber paper is cut into into 30mm × 30mm sizes, its thickness is about 200 μm.Then it is sufficiently impregnated with being put into suspension, so that the interior surface quilt of carbon fiber paper Uniform to coat, the carbon fiber paper for then just coating takes out, and is put in vacuum drying oven It is dried under room temperature.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through nitrogen as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 800 DEG C with the heating rate of 10 DEG C/min then and is protected Warm 3h, so as to be carbonized to the material, then naturally cools to room temperature.
5) prepare the material that the hydrofluoric acid solution that substance withdrawl syndrome is 1.5mol/L is carbonized to Jing Material carries out pickling, to remove the micro-nano granules brium carbonate as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to the battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, curve smoothing are carried out enough.In 40mA/cm2Electric current density under, electricity The energy conversion efficiency in pond reaches 85.2%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery still can reach 77.8%.
Comparative example 9
Compare with embodiment 9, using the carbon of undressed same size conventional at present Fibrous paper assembles all-vanadium flow battery as electrode material.The assembling mode of this battery and Other materials in addition to working electrode are same as Example 1, and same 40 mA/cm2、60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electricity Charge-discharge test is carried out under current density.As a result show, in 40mA/cm2Electric current density under, The energy conversion efficiency of battery is 67.0%；In 120mA/cm2High magnification under the conditions of, electricity Pond cannot carry out normal discharge and recharge.
Embodiment 10
In the present embodiment, when the combination electrode material for all-vanadium flow battery is prepared, Using following steps：
1) the Polyethylene Glycol 7g as organic carbon source presoma is scattered in cumulative volume for 100 In the water and toluene of mL.Water is 3 with the volume ratio of ethanol:1.
2) 15g micro-nano granules shape strontium carbonates are added as hard template in above-mentioned solution, About 1～5 μm of strontium carbonate particle size.Then they are placed in megasonic tank is carried out Concussion, until forming finely dispersed suspension.
3) carbon cloth is cut into into 30mm × 30mm sizes, about 250 μm of its thickness. Then it is sufficiently impregnated with being put into suspension, so that the interior surface of carbon cloth is uniformly wrapped Cover, then coated carbon cloth is taken out, and be put in vacuum drying oven and be dried at room temperature for.
4) the fully dry material of above Jing is placed in temperature programming tube furnace, and to stove In be passed through helium as shielding gas, before intensification first tube furnace is purged to replace in pipe Air, the temperature of stove is increased to into 1400 DEG C simultaneously with the heating rate of 12 DEG C/min then Stove, so as to be carbonized to the material, is then naturally cooled to room temperature by insulation 3h.
5) prepare the material that the hydrochloric acid solution that substance withdrawl syndrome is 0.8mol/L is carbonized to Jing Pickling is carried out, to remove the micro-nano granules strontium carbonate as hard template.
6) cyclic washing is carried out to the material of Jing pickling using deionized water, is then put Enter in vacuum drying oven and be dried at room temperature for, it is standby.
In the present embodiment, this novel composite electrode material is applied to assemble all-vanadium flow electricity Pond.Battery is according to the order of end plate-collector plate-electrode/membrane/electrode-collector plate-end plate pressing The mode of filter is assembled.Wherein, barrier film adopts perfluoro sulfonic acid membrane.In different electric current densities Under charge-discharge test is carried out to the battery.As a result show, the battery is in 40mA/cm2、60 mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under energy Normal discharge and recharge, curve smoothing are carried out enough.In 40mA/cm2Electric current density under, electricity The energy conversion efficiency in pond reaches 80.1%；And in 120mA/cm2High magnification condition Under, the energy conversion efficiency of battery is 70.3%.
Comparative example 10
Compare with embodiment 10, using undressed same size conventional at present Carbon cloth assembles all-vanadium flow battery as electrode material.The assembling mode of this battery and remove Other materials beyond working electrode are same as Example 1, and same in 40mA/cm2、 60mA/cm2、80mA/cm2、100mA/cm2And 120mA/cm2Electric current density under Carry out charge-discharge test.As a result show, in 40mA/cm2Electric current density under, battery Energy conversion efficiency is 67.4%；And in 120mA/cm2High magnification under the conditions of, battery without Method carries out normal discharge and recharge.
Above example is only some preferred implementations of the present invention, but protection scope of the present invention is simultaneously It is not limited only to this.It should be appreciated by those skilled in the art that all without departing from spirit and scope of the invention Any modification, replacement are all within protection scope of the present invention.

Claims (10)

1. a kind of method for preparing the combination electrode material for all-vanadium flow battery, it is characterised in that The method comprising the steps of：
1) organic carbon source presoma is dissolved in into water or organic solvent or water and organic solvent Mixture in；
2) in above-mentioned solution add micro-nano granules shape material as hard template, then will They are placed in megasonic tank is shaken, until forming finely dispersed suspension；
3) three-dimensional carbon base material is placed in the suspension and is sufficiently impregnated with, so that The interior surface of the three-dimensional carbon base material is uniformly coated, then by coated three-dimensional Carbon-based bottom material takes out, and is put in vacuum drying oven and is dried at room temperature；
4) material of above drying is placed in temperature programming tube furnace, and to the stove In be passed through noble gases, the temperature of the stove is increased to into target temperature then, will be described Organic carbon source presoma is carbonized, and the stove is naturally cooled to room temperature then；
5) pickling is carried out to the material that Jing is carbonized using acid solution, to remove as hard template The micro-nano granules shape material；
6) cyclic washing is carried out to the material of Jing pickling using deionized water, to remove material The acid of remained on surface and salt impurity, then putting it in vacuum drying oven is carried out at room temperature Drying for standby.
2. method according to claim 1, it is characterised in that step 1) in the organic carbon Source presoma be cellulose, starch, Fructose, maltose, hemicellulose, arabic gum, Carrageenan, arabinose, glucose, sucrose, polyvinyl alcohol, Polyethylene Glycol and polypropylene At least one in alcohol.
3. method according to claim 1, it is characterised in that step 1) in it is described organic molten During agent is methanol, ethanol, normal propyl alcohol, isopropanol, acetone, ethylene glycol and dimethyl sulfoxide It is at least one.
4. method according to claim 1, it is characterised in that step 2) in it is described micro-nano Granular material be Calcium Carbonate, Zinc Oxide, sodium carbonate, potassium carbonate, ferric carbonate, brium carbonate, Strontium carbonate, zinc carbonate, magnesium carbonate, lithium carbonate, magnesium hydroxide, zinc hydroxide and ferrum oxide In at least one.
5. method according to claim 4, it is characterised in that the micro-nano granules shape material Size between 10nm～10 μm, and its consumption accounts for the suspension total mass fraction 5%～40%.
6. method according to claim 1, it is characterised in that step 3) in the three-dimensional carbon Base material is carbon fiber felt, graphite fibre felt, carbon fiber paper, papyrex, foam At least one in carbon and carbon cloth.
7. method according to claim 1, it is characterised in that step 4) in carbonisation Heating rate is 1～20 DEG C/min, and the target temperature is 600～1500 DEG C, and is carbonized Time is 0.5～20h.
8. method according to claim 1, it is characterised in that step 5) in the acid solution It is by Fluohydric acid., sulphuric acid, phosphoric acid, nitric acid, formic acid, hydrochloric acid, acetic acid and benzenesulfonic acid It is at least one soluble in water and obtain solution.
9. the combination electrode material that prepared by a kind of method by according to any one of claim 1-8 Material.
10. the combination electrode material that prepared by a kind of method by according to any one of claim 1-8 Material, or the material for being further loaded with other catalyst with the combination electrode material as carrier Application in the electrode material of all-vanadium flow battery.
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CN108923026A (en) * 2018-06-19 2018-11-30 大连理工大学 A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere
CN111268716A (en) * 2020-04-01 2020-06-12 昂星新型碳材料常州有限公司 Carbon material-coated tetrapod-like zinc oxide, carbon material with hollow tetrapod-like structure, filling mold and preparation method thereof
CN113003701A (en) * 2021-02-08 2021-06-22 哈尔滨工业大学 Lead-zinc mine tailing pond wastewater deep purification device with electric coupling biological filter
CN113574707A (en) * 2019-03-13 2021-10-29 东洋纺株式会社 Carbon electrode material and redox battery
CN113735191A (en) * 2021-08-24 2021-12-03 南通金通储能动力新材料有限公司 Porous structure ternary precursor and preparation method thereof
CN115403041A (en) * 2022-09-15 2022-11-29 中国地质大学（北京） Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device
CN115911411A (en) * 2022-11-24 2023-04-04 寰泰储能科技股份有限公司 All-vanadium redox flow battery electrode containing active carbon nanofiber layer and preparation method thereof
CN117543026A (en) * 2024-01-10 2024-02-09 山西国润储能科技有限公司 Novel all-vanadium redox flow battery electrode and treatment method

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09167621A (en) * 1995-08-28 1997-06-24 Mitsubishi Chem Corp Carbon electrode
CN1595691A (en) * 2003-09-08 2005-03-16 中国科学院大连化学物理研究所 Method for preparing porous carbon radical electrode of sodium polysulfate / bromine energy storage cell
CN101012057A (en) * 2007-01-19 2007-08-08 华东师范大学 Method of synthesizing mesoporous carbon material
CN102912670A (en) * 2012-10-08 2013-02-06 南京工业大学 Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper
CN103050713A (en) * 2011-10-17 2013-04-17 中国科学院大连化学物理研究所 Electrode material modified by carbon nanofiber for vanadium redox flow battery and application thereof
US20140234753A1 (en) * 2010-09-28 2014-08-21 Battelle Memorial Institute Redox flow batteries based on supporting solutions containing chloride
CN104058423A (en) * 2014-06-27 2014-09-24 武汉理工大学 Method for synthesizing ordered macroporous-mesoporous-microporous hierarchical-pore molecular sieve by using hard template
CN104157861A (en) * 2013-05-14 2014-11-19 深圳华粤宝电池有限公司 Mesoporous carbon material, elemental sulfur and preparation method for mesoporous carbon composite material
CN104759252A (en) * 2015-03-23 2015-07-08 江苏大学 A method of preparing porous carbon by adopting spherical zinc oxide as a template and applications of the porous carbon

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09167621A (en) * 1995-08-28 1997-06-24 Mitsubishi Chem Corp Carbon electrode
CN1595691A (en) * 2003-09-08 2005-03-16 中国科学院大连化学物理研究所 Method for preparing porous carbon radical electrode of sodium polysulfate / bromine energy storage cell
CN101012057A (en) * 2007-01-19 2007-08-08 华东师范大学 Method of synthesizing mesoporous carbon material
US20140234753A1 (en) * 2010-09-28 2014-08-21 Battelle Memorial Institute Redox flow batteries based on supporting solutions containing chloride
CN103050713A (en) * 2011-10-17 2013-04-17 中国科学院大连化学物理研究所 Electrode material modified by carbon nanofiber for vanadium redox flow battery and application thereof
CN102912670A (en) * 2012-10-08 2013-02-06 南京工业大学 Carbon fiber paper preparing method capable of controlling aperture size of carbon fiber paper
CN104157861A (en) * 2013-05-14 2014-11-19 深圳华粤宝电池有限公司 Mesoporous carbon material, elemental sulfur and preparation method for mesoporous carbon composite material
CN104058423A (en) * 2014-06-27 2014-09-24 武汉理工大学 Method for synthesizing ordered macroporous-mesoporous-microporous hierarchical-pore molecular sieve by using hard template
CN104759252A (en) * 2015-03-23 2015-07-08 江苏大学 A method of preparing porous carbon by adopting spherical zinc oxide as a template and applications of the porous carbon

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
NICOLAS BRUN ET AL: "Design of Hierarchical Porous Carbonaceous Foams form a Dual-Template Approach and Their Use as Electrochemical Capacitor and Li Ion Battery Negative Electrodes", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *
XIAORU WEN ET AL: "Three-dimensional hierarchical porous carbon with a bimodal pore arrangement for capacitive deionization", 《JOURNAL OF MATERIALS CHEMISTRY》 *
ZHENG TIAN ET AL: "Hard Templating of Symmetric and Asymmetric Carbon Thin Films with Tree-Dimensionally Ordered Mesoporousity", 《LANGMUIR》 *
吴雄伟等: "全钒液流电池碳电极材料的研究进展", 《中国科学：化学》 *
李俊等: "无机硬模板HMS制备介孔碳工艺", 《东华大学学报（自然科学版）》 *

Cited By (14)

* Cited by examiner, † Cited by third party
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CN108493450A (en) * 2018-03-30 2018-09-04 珠海格力电器股份有限公司 Carbon material and the method and lithium cell negative pole electrode slice and lithium ion battery that carbon material is generated using residual oil as raw material
CN108923026A (en) * 2018-06-19 2018-11-30 大连理工大学 A kind of preparation method of the rich nitrogen material of porous carbon nanosheet filling hollow carbon sphere
CN108923026B (en) * 2018-06-19 2021-02-19 大连理工大学 Preparation method of nitrogen-rich material with hollow carbon spheres filled with porous carbon nanosheets
CN113574707A (en) * 2019-03-13 2021-10-29 东洋纺株式会社 Carbon electrode material and redox battery
CN113574707B (en) * 2019-03-13 2024-01-12 东洋纺Mc株式会社 Carbon electrode material and redox cell
CN111268716B (en) * 2020-04-01 2023-02-21 昂星新型碳材料常州有限公司 Carbon material-coated tetrapod-like zinc oxide, carbon material with hollow tetrapod-like structure, filling mold and preparation method thereof
CN111268716A (en) * 2020-04-01 2020-06-12 昂星新型碳材料常州有限公司 Carbon material-coated tetrapod-like zinc oxide, carbon material with hollow tetrapod-like structure, filling mold and preparation method thereof
CN113003701A (en) * 2021-02-08 2021-06-22 哈尔滨工业大学 Lead-zinc mine tailing pond wastewater deep purification device with electric coupling biological filter
CN113735191A (en) * 2021-08-24 2021-12-03 南通金通储能动力新材料有限公司 Porous structure ternary precursor and preparation method thereof
CN115403041B (en) * 2022-09-15 2023-11-21 中国地质大学（北京） Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device
CN115403041A (en) * 2022-09-15 2022-11-29 中国地质大学（北京） Hemicellulose-based hollow porous carbon, preparation method thereof and application thereof in zinc ion energy storage device
CN115911411A (en) * 2022-11-24 2023-04-04 寰泰储能科技股份有限公司 All-vanadium redox flow battery electrode containing active carbon nanofiber layer and preparation method thereof
CN115911411B (en) * 2022-11-24 2023-09-01 寰泰储能科技股份有限公司 All-vanadium redox flow battery electrode containing active nano carbon fiber layer and preparation method thereof
CN117543026A (en) * 2024-01-10 2024-02-09 山西国润储能科技有限公司 Novel all-vanadium redox flow battery electrode and treatment method

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