CN109216710A - A kind of kind tree effect construction method of high-ratio surface carbon fiber felt and its application - Google Patents
A kind of kind tree effect construction method of high-ratio surface carbon fiber felt and its application Download PDFInfo
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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
- H01M4/96—Carbon-based electrodes
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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
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- H01M4/88—Processes of manufacture
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to the kind tree effect construction methods and its application of electrochmical power source and electrochemical catalysis field, in particular to a kind of high-ratio surface carbon fiber felt.In the last handling process of carbon fiber felt, typical nano-functional material is modified by the fiber surface to carbon fiber felt by the method for bonding, growth, deposition, forms the carbon fiber felt combination electrode having compared with high-ratio surface.These nano-functional materials are just as " plantation " " tree " in carbon fiber surface, it not only can directly increase the surface area of carbon fiber felt combination electrode, and its surface oxygen-containing group abundant can also improve the wetability of carbon fiber felt, and then improve its electrochemical surface area.The present invention mainly utilizes the kind tree effect of typical nano-functional material, so that the carbon fiber felt combination electrode electrochemical surface area with higher prepared, such electrode is used as vanadium cell positive and negative electrode material, the activation polarization in vanadium cell reaction process can be greatly reduced, and then improve vanadium cell charge-discharge performance.
Description
Technical field
The present invention relates to electrochmical power source and electrochemical catalysis field, in particular to a kind of kinds of high-ratio surface carbon fiber felt
Set effect construction method and its application in vanadium cell.
Background technique
All-vanadium flow battery (Vanadium Flow Battery, VFB) is big, safe and reliable because of its long service life, scale
Equal outstanding advantages, become one of the one preferred technique of scale energy storage, but its higher energy storage price limit vanadium cell technology at this stage
Further genralrlization.In addition to the critical material cost for further decreasing vanadium cell, vanadium cell performance is further increased, and then improve
Single heap power is the important channel for reducing vanadium cell energy storage cost.
The place that electrode occurs as vanadium battery electrode reaction is to determine one of battery performance and the critical material in service life.
Polyacrylonitrile (PAN) base carbon felt has become the preferred material of vanadium energy storage system because of its cheap price and higher stability
Material, however its lower electro-chemical activity and surface area become and further increase vanadium cell performance and reduce its cost restricted
Factor.In recent years, a large amount of researcher is dedicated to the raising of electrode material activity, although obtaining certain achievement, cut-off
It is not the work of vanadium cell to currently, still do not effectively improve the activity of vanadium cell for the modified method of large-scale production
Journeyization, which is promoted, provides economic benefit.
In fact, the specific surface of the PAN base carbon fibre felt of commercialization at present is only 0.05~0.5m2·g-1, and other common carbon
The specific surface of material is several hundred or even thousands of m2·g-1If its surface area can be improved by the means such as kind setting, digging pit
To 50 even 100m2·g-1Left and right, then its current density will be reduced to 1% or less current under same electric current.Consider
To in sizable current density range (40~200mAcm-2) in, it is approximate between vanadium cell energy efficiency and current density to be in
Linear relationship, i.e., every raising 10mAcm-2Energy efficiency can reduce by 1.3% or so, then the lifting theory of surface area nearly a hundred times
On can by energy efficiency improve 10% or more.It is therefore contemplated that perhaps promote electrode area more has the raising of vanadium cell performance
Meaning.
Summary of the invention
The object of the present invention is to provide a kind of kind tree effect construction method of high-ratio surface carbon fiber felt and its in vanadium cell
In application prior art is suitably modified on the basis of carbon fiber felt aftertreatment technology, by bonding, growth, heavy
The typical functionalities group such as carbon nanotube, carbon nanowalls, carbon nano-fiber, nano graphene oxide is planted in carbon by long-pending method
Filament surface forms the carbon fiber felt combination electrode having compared with high-ratio surface, which is applied to vanadium
The activation polarization in vanadium cell reaction process can be greatly reduced in battery electrode, and then improves vanadium cell charge-discharge performance.
The technical scheme is that
A kind of kind tree effect construction method of high-ratio surface carbon fiber felt, in the last handling process of carbon fiber felt, by carbon
Nanotube, carbon nanowalls, carbon nano-fiber or nano graphene oxide typical functionality group pass through growth, deposition or bonding
Method is planted in the carbon fiber wire surface of carbon fiber felt, forms the carbon fiber felt combination electrode having compared with high-ratio surface；Carbon fiber
Specific surface before felt post-processing is 0.1~1.0m2·g-1, contact angle is 100~120 °, the high-ratio surface carbon fiber being prepared
The specific surface for tieing up felt is 50~100m2·g-1, contact angle is 50~80 °.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, selected carbon fiber felt are polyacrylonitrile-radical
Graphite felt, viscose-based graphite felt, cellulose base graphite felt, any one in pitch based graphite felt；Alternatively, polyacrylonitrile-based carbon
Felt, viscose glue base carbon felt, cellulose base carbon felt, any one in asphaltic base carbon felt, with a thickness of 1~10mm.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, it is preferred that carbon fiber felt is polyacrylonitrile-radical
Graphite felt, with a thickness of 3~6mm.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, the plantation of selected nano-functional group
Method is using one of following three kinds of methods:
(1) it carbon nanotube, the direct bonding of nano graphene oxide: disperses carbon nanotube or graphene oxide in
In Nafion/ ethanol solution, it is configured to the dispersion liquid of nano-functional group, then by soak carbon fibre felt in this dispersion liquid
In, it is dried until being put into baking oven after absorbing completely, obtains carbon nanotube or nano oxidized graphite after carbonization treatment is finally carried out to it
The high-ratio surface carbon fiber felt combination electrode of alkene modification；
(2) chemically grown of carbon nanotube under the action of catalyst: by soak carbon fibre felt in the salting liquid of Fe or Ni,
H is placed it in after drying2The thermal reduction that catalyst is carried out in/Ar gaseous mixture, then passes through chemical gaseous phase in carbon source gaseous mixture
Deposition technique realizes carbon nanotube in the chemically grown of carbon fiber surface, finally it is carried out after carbonization treatment carbon nanotube is repaired
The high-ratio surface carbon fiber felt combination electrode of decorations；
(3) chemical deposition of carbon nanotube, nanofiber and nanometer wall on graphite felt fibres: directly in carbon source gaseous mixture
In the chemical deposition on graphite felt fibres of carbon nanotube, nanofiber and nanometer wall realized by thermolysis process, it is finally right
It obtains the high-ratio surface carbon fiber felt combination electrode that carbon nanotube, nanofiber and nanometer wall are modified after carrying out carbonization treatment.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, in method (1), related Nafion/ second
The weight concentration of alcoholic solution is 0.01%~0.1%, and the dispersion liquid concentration of carbon nanotube or graphene oxide is 1~10mg
mL-1, the temperature of baking oven is 50~150 DEG C in drying course, drying time is 1~for 24 hours, carburizing temperature is 500 in carbonisation
~1500 DEG C, carbonization time is 1~6h；
In method (2), the concentration of related Fe or Ni salting liquid is 0.1~3molL-1；Baking oven in drying course
Temperature be 50~150 DEG C, drying time be 1~for 24 hours；H during metal salt thermal reduction2The molar ratio of/Ar gaseous mixture is 1:
15~1:5, reduction temperature are 500~800 DEG C, and the recovery time is 1~5h；The atmosphere of selected chemical vapor deposition is carbon source
Disulfonic gas, methane or acetylene and H2Gaseous mixture, molar ratio be 1:30~30:1, depositing temperature be 600~1000 DEG C,
Sedimentation time is 0.5~3h；Carburizing temperature is 500~1500 DEG C in carbonisation, and carbonization time is 1~6h；
In method (3), the atmosphere of related thermal decomposition is carbon-source gas toluene, methane or acetylene and H2Gaseous mixture,
Its molar ratio is 1:30~30:1, and depositing temperature is 600~1000 DEG C, and sedimentation time is 1~5h, and be carbonized temperature in carbonisation
Degree is 500~1500 DEG C, and carbonization time is 1~6h.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, it is preferred that related in method (1)
The weight concentration of Nafion/ ethanol solution is 0.02%~0.05%, and the dispersion liquid concentration of carbon nanotube or graphene oxide is 2
~5mgmL-1, the temperature of baking oven is 60~100 DEG C in drying course, and drying time is 3~5h, carburizing temperature is 600~
1000 DEG C, carbonization time is 2~4h；
Preferably, in method (2), the concentration of related Fe or Ni salting liquid is 0.5~1molL-1, metal salt heat is also
H during original2The molar ratio of/Ar gaseous mixture be 1:10~1:8, reduction temperature be 600~700 DEG C, the recovery time be 2~
4h, the atmosphere of selected chemical vapor deposition are methane and H2Gaseous mixture, molar ratio be 1:20~1:10, deposition temperature
Degree is 750~850 DEG C, and sedimentation time is 0.5~1h, and carburizing temperature is 600~1000 DEG C in carbonisation, carbonization time 2
~4h；
Preferably, in method (3), the atmosphere of related thermal decomposition is acetylene and H2Gaseous mixture, molar ratio is
1:30~1:20, depositing temperature are 650~750 DEG C, and sedimentation time is 2~3h, and carburizing temperature is 600~1000 in carbonisation
DEG C, carbonization time is 2~4h.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, related carbon nanotube or nano oxygen fossil
Black alkene is the short fibre of nanometer, and string diameter is 10~500nm.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, it is preferred that related carbon nanotube is received
Rice graphene oxide is the short fibre of nanometer, and string diameter is 50~200nm.
The kind tree effect construction method of the high-ratio surface carbon fiber felt, for the high-ratio surface carbon fiber prepared
Felt, nano-functional group are planted in the surface of carbon fiber in the form of " tree ", directly increase the physical area of carbon fiber felt, and
And improve the wetability of carbon fiber felt, and then improve its electrochemical surface area；
For the high-ratio surface carbon fiber felt prepared, the nanometer staple on surface includes carbon nanotube, nano oxidized
Graphene, carbon nano-fiber or carbon nanowalls, they are not stringent Nano grade, and size is between 50~300nm.
The application of the high-ratio surface carbon fiber felt, high-ratio surface carbon fiber felt are applied in vanadium cell, vanadium cell by
Electrode material, electrolyte, diaphragm and bipolar plates composition, the high-ratio surface carbon fiber felt are applied to the electrode material in vanadium cell
Material.
The principle of the invention is as follows:
In the last handling process of carbon fiber felt, using carbon fiber felt as matrix, by carbon nanotube, carbon nanowalls, carbon nanometer
The typical functionalities such as fiber, nano graphene oxide group is planted in carbon fiber silk table by the method for growth, deposition and bonding
Face, these nano-functional groups are planted in the surface of carbon fiber as " tree ", they not only can directly increase carbon fiber
The physical area of felt, and the wetability of carbon fiber felt can be improved, and then improve its electrochemical surface area.Therefore, it prepares
Carbon fiber felt combination electrode specific surface with higher, by the high-ratio surface carbon fiber felt be applied to vanadium battery electrode can be big
Width reduces the activation polarization in vanadium cell reaction process, and then improves vanadium cell charge-discharge performance.
The invention has the advantages and beneficial effects that:
The short fibre of nanometer of the high-ratio surface carbon fiber felt that the present invention is prepared, surface growth not only can directly increase carbon
The specific surface area of fibrofelt can also improve its wetability and then improve its electrochemical surface area, be applied to vanadium battery electrode
Material can be effectively reduced activation polarization, improve battery performance.In addition, the present invention is based on the pre- oxygen of existing carbon fiber felt
Change and carbonisation, it is suitably modified, does not need to increase additional production equipment, it is simple process, low in cost, easily
In the engineering preparation for realizing high-ratio surface carbon fiber felt.
Detailed description of the invention
Fig. 1 is high-ratio surface carbon fiber felt schematic diagram.
Fig. 2 is vanadium cell structural schematic diagram；Wherein, 1- bipolar plates, 2- electrode frame, 3- electrode, 4- diaphragm.
Fig. 3 is the SEM figure of high-ratio surface carbon fiber felt in embodiment 1；Wherein, (b) be (a) partial enlarged view.
Fig. 4 is the contact angle schematic diagram of carbon fiber felt (a) and high-ratio surface carbon fiber felt (b) in embodiment 1.
Fig. 5 is the vanadium cell charge-discharge performance curve of carbon fiber felt and high-ratio surface carbon fiber felt in embodiment 1；Wherein,
(a) charging and discharging curve, abscissa Capacity are charge/discharge capacity (mAh), and ordinate Voltage is voltage (V)；(b) energy
Efficiency curve, abscissa Cycle number are cycle-index, and ordinate Energy Efficiency is energy efficiency (%)；
CF is carbon fiber felt, and CF/GO is the high-ratio surface carbon fiber felt of graphene oxide modification.
Specific embodiment
In the specific implementation process, the electro catalytic activity for improving electrode is hot spot in current vanadium battery electrode research, so
And existing modification technology is difficult to realize the engineering preparation of high activity electrode.As shown in Figure 1, the structure of high-ratio surface carbon fiber felt
It is as follows to build process: the present invention is suitably modified prior art on the basis of carbon fiber felt aftertreatment technology, by viscous
Knot, growth, deposition method by the typical functionalities base such as carbon nanotube, carbon nanowalls, carbon nano-fiber, nano graphene oxide
Group is planted in the carbon fiber wire surface of carbon fiber felt, forms the carbon fiber felt combination electrode having compared with high-ratio surface.The compound electric
The size of the short fibre of pole surface nanometer is about between 50~500nm, they are planted in carbon fiber surface as tree, produced by them
Plantation effect by the specific surface of carbon fiber felt by 0.1 original~1.0m2·g-1Increase to 50~100m2·g-1, contact angle
Also 50~80 ° are reduced to by 100~120 °, which, which is applied to vanadium battery electrode, can be greatly reduced vanadium
Activation polarization during cell reaction, and then the energy efficiency of vanadium cell charge and discharge process is improved 5~10 percentage points.
As shown in Fig. 2, vanadium cell structure is as follows: the two sides of diaphragm 4 are followed successively by electrode frame 2, bipolar plates 1 respectively, and electrode 3 is set
It is placed in electrode frame 2.
The present invention is described in further detail below by embodiment.
Embodiment 1
In the present embodiment, Nafion (perfluorinated sulfonic acid)/ethyl alcohol that weight concentration is 0.02% is dispersed by graphene oxide
In solution, being configured to concentration is 2mgmL-1The dispersion liquid of graphene oxide；Then PAN-graphite felt is soaked in this point
It in dispersion liquid, is dried until being put into baking oven after absorbing completely, the temperature of baking oven is 60 DEG C, drying time 6h；To the stone after drying
Black felt is in N2Carbonization treatment is carried out in atmosphere, carburizing temperature is 1000 DEG C, and carbonization time 3h can finally obtain nano oxidized graphite
The high-ratio surface carbon fiber felt combination electrode of alkene modification.
It is found by physical characterization, is bonded in the nano graphene oxide of carbon fiber surface as flaky texture, and big portion
Point with the presence of multi-layer graphene structure, stannic oxide/graphene nano piece has lower contrast and fold abundant, and size is from tens
Nanometer is differed to several hundred nanometers, such as Fig. 3.The stannic oxide/graphene nano piece of these nano-scales is also by the ratio of graphite felt combination electrode
Surface is by original 0.56m2·g-1Increase to 71.3m2·g-1.And the contact angle of contact angle test show electrode and electrolyte
75.3 ° (Fig. 4) are reduced to by original 119.8 °, this also illustrates that the hydrophily of carbon fiber felt is greatly improved.By above-mentioned height
Specific surface carbon fiber felt is used as the electrode material of vanadium cell, carries out the charge-discharge test of vanadium cell, it is possible to find in 100mAcm-2
When electric close lower progress charge and discharge, charging voltage reduces limited extent, and its discharge voltage is sharply increased, and energy efficiency is by original
75% rise to current 82%, as shown in Figure 5.
Embodiment 2
In the present embodiment, disperses multi-walled carbon nanotube in the Nafion/ ethanol solution that weight concentration is 0.02%, match
The dispersion liquid that concentration is 1.5wt.% multi-walled carbon nanotube is made；Then PAN-graphite felt is soaked in this dispersion liquid,
It is put into baking oven and dries to after absorbing completely, the temperature of baking oven is 60 DEG C, drying time 6h；To the graphite felt after drying in N2
Carbonization treatment is carried out in atmosphere, carburizing temperature is 1000 DEG C, carbonization time 3h, can finally obtain the height of multi-walled carbon nanotube modification
Specific surface carbon fiber felt combination electrode.
It is found by physical characterization, the fiber surface of combination electrode seems more coarse, and some carbon nanotubes are agglomerated into greatly
The particle of partial size, and most of carbon nanotube is then dispersed relatively uniform, is bonded in carbon fiber surface in dendroid, specific surface
By original 0.56m2·g-1Increase to 85.7m2·g-1.The contact angle of contact angle test show electrode and electrolyte is also by original
119.8 ° be reduced to 61.7 °, equally illustrate that the hydrophily of carbon fiber felt is greatly improved.By above-mentioned high-ratio surface carbon fiber
Felt is used as the electrode material of vanadium cell, carries out the charge-discharge test of vanadium cell, it is possible to find in 100mAcm-2It is filled under electricity is close
When electric discharge, charging voltage reduces limited extent, and its discharge voltage is sharply increased, and energy efficiency rises to 83% left side by 75%
It is right.
Embodiment 3
In the present embodiment, by soak carbon fibre felt in concentration be 1molL-1Ni (NO3)3In solution；Then it is put
Enter in baking oven and dry, the temperature of baking oven is 60 DEG C, drying time 6h；H is placed it in after drying2It is urged in/Ar gaseous mixture
The thermal reduction of agent, the H that thermal reduction atmosphere is molar ratio 1:92/ Ar gaseous mixture, reduction temperature are 600 DEG C, and the recovery time is
3h；Then in the gaseous mixture of acetylene and hydrogen carry out carbon nanotube, the chemical vapor deposition of carbon nano-fiber, wherein acetylene and
Hydrogen molar ratio is 1:25, and depositing temperature is 700 DEG C, sedimentation time 0.5h；Carbonization treatment is carried out to it, carburizing temperature is
1000 DEG C, carbonization time 3h, it can finally obtain carbon nano tube modified high-ratio surface carbon fiber felt combination electrode.
It being found by physical characterization, the carbon fiber surface of combination electrode grows a large amount of carbon nanotubes or carbon nano-fiber,
String diameter is about 50~80nm, and specific surface is by original 0.56m2·g-1Increase to 100.5m2·g-1.Contact angle test display electricity
The contact angle of pole and electrolyte is also reduced to 58.2 ° by original 119.8 °, equally illustrates that the hydrophily of carbon fiber felt obtains greatly
Width improves.Above-mentioned high-ratio surface carbon fiber felt is used as to the electrode material of vanadium cell, the charge-discharge test of vanadium cell is carried out, can send out
Present 100mAcm-2When electric close lower progress charge and discharge, charging voltage reduces limited extent, and its discharge voltage is sharply increased,
Energy efficiency rises to 84% or so by 75%.
Embodiment 4
In the present embodiment, carbon nanotube, nanometer are realized by thermolysis process directly in the gaseous mixture of methane and hydrogen
Chemical deposition of the fiber on graphite felt fibres, wherein methane and hydrogen molar ratio are 1:10, and decomposition temperature is 800 DEG C, are sunk
The product time is 1h；Carbonization treatment is carried out to it, carburizing temperature is 1000 DEG C, carbonization time 3h, can finally obtain carbon nanotube, receive
The fiber-modified high-ratio surface carbon fiber felt combination electrode of rice.
It being found by physical characterization, the carbon fiber surface of combination electrode grows a large amount of carbon nanotubes or carbon nano-fiber,
String diameter is about 100~200nm, and specific surface is by original 0.56m2·g-1Increase to 77.8m2·g-1.Contact angle test is shown
The contact angle of electrode and electrolyte is also reduced to 65.7 ° by original 119.8 °, equally illustrates that the hydrophily of carbon fiber felt obtains
It greatly improves.Above-mentioned high-ratio surface carbon fiber felt is used as to the electrode material of vanadium cell, carries out the charge-discharge test of vanadium cell, it can
It was found that in 100mAcm-2When electric close lower progress charge and discharge, charging voltage reduces limited extent, and its discharge voltage substantially rises
Height, energy efficiency rise to 83% or so by 75%.
Embodiment the result shows that, the present invention in the last handling process of carbon fiber felt, by bonding, growth, deposition side
Typical nano-functional material is modified the fiber surface to carbon fiber felt by method, and being formed, there is the carbon fiber felt compared with high-ratio surface to answer
Composite electrode.These nano-functional materials not only can directly increase carbon fiber just as " plantation " " tree " in carbon fiber surface
The surface area of felt combination electrode is tieed up, and its surface oxygen-containing group abundant can also improve the wetability of carbon fiber felt, Jin Erti
Its high electrochemical surface area.The present invention is mainly using the kind tree effect of typical nano-functional material, so that the carbon fiber prepared
Such electrode is used as vanadium cell positive and negative electrode material, can be greatly reduced by felt combination electrode electrochemical surface area with higher
Activation polarization in vanadium cell reaction process, and then improve vanadium cell charge-discharge performance.This method is based on existing carbon fiber
The pre-oxidation of felt and carbonisation, are suitably modified it, do not need to increase additional production equipment, simple process, at
This is cheap, it is easy to accomplish prepared by the engineering of high-ratio surface carbon fiber felt.
Claims (10)
1. a kind of kind tree effect construction method of high-ratio surface carbon fiber felt, it is characterised in that: in the post-processing of carbon fiber felt
Cheng Zhong, by carbon nanotube, carbon nanowalls, carbon nano-fiber or nano graphene oxide typical functionality group by growing, sinking
The method of product or bonding is planted in the carbon fiber wire surface of carbon fiber felt, forms the carbon fiber felt compound electric having compared with high-ratio surface
Pole；Specific surface before carbon fiber felt post-processing is 0.1~1.0m2·g-1, contact angle is 100~120 °, the height being prepared
The specific surface of specific surface carbon fiber felt is 50~100m2·g-1, contact angle is 50~80 °.
2. the kind tree effect construction method of high-ratio surface carbon fiber felt described in accordance with the claim 1, it is characterised in that: selected
Carbon fiber felt be PAN based graphite felt, it is viscose-based graphite felt, cellulose base graphite felt, any in pitch based graphite felt
It is a kind of；Alternatively, any one in PAN based carbon felt, viscose glue base carbon felt, cellulose base carbon felt, asphaltic base carbon felt, thickness
For 1~10mm.
3. the kind tree effect construction method of high-ratio surface carbon fiber felt described in accordance with the claim 1, it is characterised in that: preferably
, carbon fiber felt is PAN based graphite felt, with a thickness of 3~6mm.
4. the kind tree effect construction method of high-ratio surface carbon fiber felt described in accordance with the claim 1, it is characterised in that: selected
Nano-functional group implantation methods one of using following three kinds of methods:
(1) carbon nanotube, the direct bonding of nano graphene oxide: Nafion/ is dispersed by carbon nanotube or graphene oxide
In ethanol solution, it is configured to the dispersion liquid of nano-functional group, then by soak carbon fibre felt in this dispersion liquid, until absorbing
Be put into baking oven and dry after completely, finally it is carried out after carbonization treatment carbon nanotube or nano graphene oxide modification height
Specific surface carbon fiber felt combination electrode；
(2) chemically grown of carbon nanotube under the action of catalyst: by soak carbon fibre felt in the salting liquid of Fe or Ni, drying
After place it in H2The thermal reduction that catalyst is carried out in/Ar gaseous mixture, then passes through chemical vapor deposition in carbon source gaseous mixture
Technology realizes carbon nanotube in the chemically grown of carbon fiber surface, finally carries out to it after carbonization treatment carbon nano tube modified
High-ratio surface carbon fiber felt combination electrode；
(3) chemical deposition of carbon nanotube, nanofiber and nanometer wall on graphite felt fibres: lead to directly in carbon source gaseous mixture
Cross thermolysis process and realize the chemical deposition on graphite felt fibres of carbon nanotube, nanofiber and nanometer wall, finally to its into
The high-ratio surface carbon fiber felt combination electrode of carbon nanotube, nanofiber and the modification of nanometer wall is obtained after row carbonization treatment.
5. the kind tree effect construction method of high-ratio surface carbon fiber felt according to claim 4, it is characterised in that: method
(1) in, the weight concentration of related Nafion/ ethanol solution is 0.01%~0.1%, carbon nanotube or graphene oxide
Dispersion liquid concentration is 1~10mgmL-1, the temperature of baking oven is 50~150 DEG C in drying course, drying time is 1~for 24 hours, carbon
Carburizing temperature is 500~1500 DEG C during change, and carbonization time is 1~6h；
In method (2), the concentration of related Fe or Ni salting liquid is 0.1~3molL-1；The temperature of baking oven in drying course
Be 50~150 DEG C, drying time be 1~for 24 hours；H during metal salt thermal reduction2The molar ratio of/Ar gaseous mixture be 1:15~
1:5, reduction temperature are 500~800 DEG C, and the recovery time is 1~5h；The atmosphere of selected chemical vapor deposition is carbon-source gas
Toluene, methane or acetylene and H2Gaseous mixture, molar ratio be 1:30~30:1, depositing temperature be 600~1000 DEG C, deposition
Time is 0.5~3h；Carburizing temperature is 500~1500 DEG C in carbonisation, and carbonization time is 1~6h；
In method (3), the atmosphere of related thermal decomposition is carbon-source gas toluene, methane or acetylene and H2Gaseous mixture, mole
Ratio is 1:30~30:1, and depositing temperature is 600~1000 DEG C, and sedimentation time is 1~5h, and carburizing temperature is in carbonisation
500~1500 DEG C, carbonization time is 1~6h.
6. the kind tree effect construction method of high-ratio surface carbon fiber felt according to claim 4, it is characterised in that: preferably
, in method (1), the weight concentration of related Nafion/ ethanol solution is 0.02%~0.05%, carbon nanotube or oxidation
The dispersion liquid concentration of graphene is 2~5mgmL-1, the temperature of baking oven is 60~100 DEG C in drying course, drying time is 3~
5h, carburizing temperature are 600~1000 DEG C, and carbonization time is 2~4h；
Preferably, in method (2), the concentration of related Fe or Ni salting liquid is 0.5~1molL-1, metal salt heat-treated
H in journey2The molar ratio of/Ar gaseous mixture is 1:10~1:8, and reduction temperature is 600~700 DEG C, and the recovery time is 2~4h, institute
The atmosphere of the chemical vapor deposition of selection is methane and H2Gaseous mixture, molar ratio is 1:20~1:10, and depositing temperature is
750~850 DEG C, sedimentation time is 0.5~1h, and carburizing temperature is 600~1000 DEG C in carbonisation, and carbonization time is 2~4h；
Preferably, in method (3), the atmosphere of related thermal decomposition is acetylene and H2Gaseous mixture, molar ratio be 1:30~
1:20, depositing temperature are 650~750 DEG C, and sedimentation time is 2~3h, and carburizing temperature is 600~1000 DEG C in carbonisation, carbon
The change time is 2~4h.
7. the kind tree effect construction method of high-ratio surface carbon fiber felt according to claim 4, it is characterised in that: involved
Carbon nanotube or nano graphene oxide be the short fibre of nanometer, string diameter be 10~500nm.
8. the kind tree effect construction method of high-ratio surface carbon fiber felt according to claim 4, it is characterised in that: preferably
, related carbon nanotube or nano graphene oxide are the short fibre of nanometer, and string diameter is 50~200nm.
9. the kind tree effect construction method of high-ratio surface carbon fiber felt described in accordance with the claim 1, it is characterised in that: for system
The high-ratio surface carbon fiber felt got ready, nano-functional group are planted in the surface of carbon fiber in the form of " tree ", directly increase
The physical area of carbon fiber felt, and improve the wetability of carbon fiber felt, and then improve its electrochemical surface area；
For the high-ratio surface carbon fiber felt prepared, the nanometer staple on surface includes carbon nanotube, nano oxidized graphite
Alkene, carbon nano-fiber or carbon nanowalls, they are not stringent Nano grade, and size is between 50~300nm.
10. the application of high-ratio surface carbon fiber felt described in a kind of claim 1 to 9, it is characterised in that: high-ratio surface carbon fiber
Felt is applied in vanadium cell, and vanadium cell is made of electrode material, electrolyte, diaphragm and bipolar plates, the high-ratio surface carbon fiber
Felt is applied to the electrode material in vanadium cell.
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