CN106560944B - Porous carbon fiber paper electrode material used for all-vanadium redox flow battery and its preparation and application - Google Patents

Porous carbon fiber paper electrode material used for all-vanadium redox flow battery and its preparation and application Download PDF

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CN106560944B
CN106560944B CN201510623111.2A CN201510623111A CN106560944B CN 106560944 B CN106560944 B CN 106560944B CN 201510623111 A CN201510623111 A CN 201510623111A CN 106560944 B CN106560944 B CN 106560944B
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carbon fiber
paper
electrode material
carbon
porous carbon
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CN106560944A (en
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刘涛
张华民
李先锋
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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

A kind of porous carbon fiber paper electrode material used for all-vanadium redox flow battery, porous carbon fiber paper thickness of electrode are 50-1000 μm, are made of the carbon fiber that diameter is 5-20 μm, and the porosity of porous carbon fiber paper is 60-90%；Carbon fiber surface is porous structure, and the specific surface area of carbon fiber is 5-50m2/ g, aperture 50-2000nm.The porous carbon fiber paper of preparation has the specific surface area significantly improved and oxygen-containing functional group, can significantly improve carbon fibre material to the electro catalytic activity of vanadium ion redox reaction.This electrode material is suitable for all-vanadium flow battery, can reduce battery pole spacing reduces the internal resistance of cell, and reduce charge transfer resistance, improve the voltage efficiency and energy efficiency of all-vanadium flow battery, to improve its working current density, so that the battery weight of identical output power, volume and cost substantially reduce.

Description

Porous carbon fiber paper electrode material used for all-vanadium redox flow battery and its preparation and application
Technical field
The present invention relates to the liquid flow energy storage battery fields in chemical energy storage technology, the in particular to electricity of all-vanadium flow battery Pole.
Background technique
All-vanadium flow battery is because it is mutually indepedent with output power and capacity, system flexible design；Energy efficiency is high, the longevity Life length, operation stability and high reliablity, self discharge are low；Addressing freedom degree is big, and simply, operation cost is low for pollution-free, maintenance, peace The advantages that Quan Xinggao, has vast potential for future development in terms of scale energy storage, it is considered to be it is renewable to solve solar energy, wind energy etc. The effective ways of energy electricity generation system randomness and intermittent unstable state feature are built in renewable energy power generation and smart grid In have great demand.
Currently, restricting the commercialized major limitation of all-vanadium flow battery is exactly cost problem.It reduces its cost, it is main to solve Certainly there are two methods: one is the cost for reducing each critical material, such as the cost of amberplex, electrolyte, pole dual-pole board；One For the power density for improving battery.Because improving the power density of battery, so that it may realize bigger power with same pile Output, but also can reduce occupied area and the space of energy-storage system, improve the removable of its adaptive capacity to environment and system Property, extend the application field of liquid flow energy storage battery.And the power density of battery is improved it is necessary to improve its working current density. However, the raising of working current density will lead to the reduction of voltage efficiency and energy efficiency.In order to not reduce energy efficiency Under the premise of improve battery working current density, it is necessary to as much as possible reduction battery polarization, i.e. ohmic polarization, activation polarization And concentration polarization, reduce voltage loss.
Critical component one of of the electrode as all-vanadium liquid flow energy storage battery, influence pole of the performance to liquid flow energy storage battery Greatly.Vanadium redox flow battery electrode material in the prior art be usually polyacrylonitrile needle is pierced former felt through air pre-oxidation, carbonization, It is made after graphitization, process is more, leads to high production cost, and the graphite felt electro catalytic activity prepared is poor.And electrode Electro catalytic activity directly determines that the intrinsic reaction rate of electrochemical reaction, the operating current for largely affecting battery are close Degree and energy efficiency.Therefore, in order to obtain high working current density and energy efficiency, again using suitable activation method come The electro catalytic activity of graphite felt is improved as much as possible.It is electrochemical for liquid flow energy storage battery is reduced in current published patent document Learning polarized method mainly has:
(1) oxidation modification processing is carried out to electrode material such as graphite felt, carbon paper etc., modifies oxygen-containing function in carbon fiber surface Group, improves the electro catalytic activity of electrode, reduces the activation polarization of battery, such as patent CN 101465417A and CN The method that electrochemical oxidation is carried out to graphite felt disclosed in 101182678A.
(2) to electrode material such as graphite felt, carbon paper etc. carry out metalized, i.e., on carbon fiber surface modified metal from Son, such as Sun (Sun, B.T.；Skyllas-Kazacos,M.Chemical Modification and Electrochemical Behavior of Graphite Fiber in Acidic Vanadium Solution.Electrochim.Acta 1991,36,513-517.) Mn has been modified on carbon fiber surface2+、Te4+、In3+With Ir3+Deng discovery Ir3+Most there is effect to the raising of the electro catalytic activity of electrode material, but since the use of noble metal causes electrode High expensive, so be not appropriate for large-scale application.
In addition, carbon felt used at present or graphite felt electrode thickness are larger, interpolar is caused to increase in battery away from larger Resistance, i.e. ohmic polarization.Therefore, in order to obtain lesser ohmic polarization, it is necessary to use the lesser electrode material of thickness.
Summary of the invention
To solve the problems, such as that vanadium redox flow battery electrode thickness is larger, electro catalytic activity is low, the present invention provides a kind of full vanadium Flow battery high activity porous carbon fiber paper electrode material and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of high activity porous carbon fiber paper electrode material used for all-vanadium redox flow battery, with a thickness of 50-1000 μm, by diameter It is formed for 5-20 μm of carbon fiber, the porosity of porous carbon fiber paper is 60-90%；Carbon fiber surface is porous structure, carbon fiber The specific surface area of dimension is 5-50m2/ g, aperture 50-2000nm.The electrode material can be prepared by following methods:
1) by chopped carbon fiber in acetone soln after degumming process, be put into the aqueous solution dissolved with dispersing agent and beaten Slurry forms carbon fiber slurry；
2) carbon paper presoma is made using wet forming paper technology in carbon fiber slurry described in step 1)；
3) it is dried again after impregnating the carbon paper presoma in the ethanol solution of phenolic resin at 150-280 DEG C Under it is hot-forming；
4) hot-forming carbon paper body paper is risen into assigned temperature A under an inert atmosphere, constant temperature keeps 0.5-3h；
5) it then is adjusted to assigned temperature B, the gaseous mixture constant temperature for being passed through activation gas and inert gas keeps 2-60min；
6) it is then cooled to room temperature under inert atmosphere protection, porous carbon fiber paper electrode material is made；
Wherein,
The chopped carbon fiber is one of polyacrylonitrile-based carbon fibre, asphalt base carbon fiber and viscose base carbon fibre, Length is 5mm-30mm, and diameter is 5-20 μm；
The dispersing agent is one of polyethylene glycol oxide, carboxymethyl cellulose and polyacrylamide or two kinds or more；
The concentration of the dispersing agent in the slurry is 0.01-0.2%；
The concentration of phenolic resin is 0.5-15% in the ethanol solution of the phenolic resin；
The gas of the inert atmosphere is one of nitrogen, argon gas or helium or two kinds or more；
The assigned temperature A is more than or equal to assigned temperature B；
The assigned temperature A is 1000~2300 DEG C；
The assigned temperature B is 700~1500 DEG C；
The activation gas is vapor or CO2One of or two kinds, vapor and/or CO in gaseous mixture2Volumetric concentration It is 2~50%, it is therefore preferable to 2~20%.
Alternatively, electrode material of the present invention can also be prepared by following methods,
1) by chopped carbon fiber in acetone soln after degumming process, be put into the aqueous solution dissolved with dispersing agent and beaten Slurry forms carbon fiber slurry；
2) carbon paper presoma is made using wet forming paper technology in carbon fiber slurry described in step 1)；
3) it is dried again after impregnating the carbon paper presoma in the ethanol solution of phenolic resin at 150-280 DEG C Under it is hot-forming；
4) hot-forming carbon paper body paper is risen into assigned temperature C under the gaseous mixture atmosphere of activation gas and inert gas, Constant temperature keeps 2min-2h；
5) it is then cooled to room temperature under inert atmosphere protection, porous carbon fiber paper electrode material is made；
Wherein,
The chopped carbon fiber is one of polyacrylonitrile-based carbon fibre, asphalt base carbon fiber and viscose base carbon fibre, Length is 5mm-30mm, and diameter is 5-20 μm；
The dispersing agent is one of polyethylene glycol oxide, carboxymethyl cellulose and polyacrylamide or two kinds or more；
The concentration of the dispersing agent in the slurry is 0.01-0.2%；
The concentration of phenolic resin is 0.5-15% in the ethanol solution of the phenolic resin；
The gas of the inert atmosphere is one of nitrogen, argon gas or helium or two kinds or more；
The activation gas is vapor or CO2One of or two kinds, vapor and/or CO in gaseous mixture2Volumetric concentration It is 2~50%, it is therefore preferable to 2~20%；
The assigned temperature C is 800~1800 DEG C.
The present invention has the advantage that
(1) electrode material prepared by preparation method of the present invention is used, carbon fiber surface has a large amount of hole, improves electricity The specific surface area of pole material, and a large amount of surface oxygen functional group can be obtained, hydrophily is obviously improved, and can significantly reduce liquid stream The activation polarization of energy-storage battery greatly improves electrode material to VO2+/VO2 +And V2+/V3+The electricity of redox reaction is urged Change activity, reduces charge-transfer resistance, improve the voltage efficiency and energy efficiency of all-vanadium flow battery, to improve its work Make current density, so that the battery weight of identical output power, volume and cost substantially reduce.
(2) use electrode material prepared by preparation method of the present invention, compared with existing activated carbon fibre, specific surface area compared with It is small, only 5-50m2/ g, and hole is all distributed in carbon fiber surface, will not increase substantially the bulk resistance of carbon paper electrode, and Since the thickness of electrode is smaller, only 1mm is hereinafter, significantly reduce interpolar away from the internal resistance of cell being reduced, to improve electricity The working current density in pond.
(3) electrode material preparation method of the invention is simple, to equipment without particular/special requirement, easy to operate, low in cost, tool There is high value of practical, is easy to produce in batches.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of the porous carbon fiber paper prepared in the embodiment of the present invention 1；
Fig. 2 is that carbon paper is electric to V (IV)/V (V) in the porous carbon fiber paper prepared in the embodiment of the present invention 1 and comparative example 1 Pair cyclic voltammetry curve figure, sweep speed: 10mV/s；
Fig. 3 is that carbon paper is electric to V (II)/V (III) in the porous carbon fiber paper prepared in the embodiment of the present invention 1 and comparative example 1 Pair cyclic voltammetry curve figure, sweep speed: 10mV/s；
Specific embodiment
The present invention is described in detail below by specific embodiment.
Embodiment 1
Prepare the polyacrylonitrile-radical chopped carbon fiber that length is 10mm, it is put after degumming process in acetone soln Enter and be beaten in the aqueous solution dissolved with 0.1% polyethylene glycol oxide dispersing agent, forms polyacrylonitrile-based carbon fibre slurry, then pass through It is 40g/m that wet process equipment, which manufactures paper with pulp into weight per unit area,2Carbon paper presoma；Later, it is dipped in phenolic resin concentration For in 1% ethanol solution, 30min is impregnated, then the hot-forming obtained carbon paper body paper at 200 DEG C again after being dried, Pressure is 6MPa；Carbon paper body paper is put into electric furnace, in N21600 DEG C are warming up to the heating rate of 10 DEG C/min under atmosphere, perseverance Warm 1h；Then 1300 DEG C are cooled to, CO is passed through2And N2Gaseous mixture, CO2And N2Flow be respectively 40ml/min and 200ml/ Min, isothermal reaction 30min；It is cooled to room temperature and porous carbon fiber paper is made.
Electro-chemical activity for test vanadium ion oxidation-reduction pair on porous carbon fiber paper surface prepares embodiment 1 Porous carbon fiber paper carried out cyclic voltammetry.Using porous carbon fiber paper as working electrode, non-porous graphite plate conduct pair Electrode, saturated calomel electrode is as reference electrode, and the electro-chemical test instrument used is the CHI604e type electricity of Shanghai Chen Hua company Chem workstation.Compound concentration is 0.05M V (II)+0.05M V (III)+3M H2SO4With 0.05M V (IV)+0.05M V (V) +3M H2SO4Electrolyte, to V (IV)/V (V) and V (II)/V (III) electricity to the electro-chemical activity on porous carbon fiber paper surface It is studied respectively, scanning range is respectively -1V~-0.2V and 0.5~1.2V, sweep speed 10mV/s.In the present embodiment The SEM photograph of porous carbon fiber paper is as shown in Figure 1, it can be observed that carbon fiber surface is dispersed with a large amount of nano-pores.The material Cyclic voltammetry curve is as shown in Figures 2 and 3, V (IV)/V (V) and V on carbon paper in relatively porous carbon fiber paper and comparative example 1 (II) electrochemical oxidation, reduction peak position and the peak current size of/V (III) is it is found that porous carbon fiber paper manufactured in the present embodiment With the electro catalytic activity and electrochemical reversibility significantly improved.
The carbon paper having a size of 4cm × 3cm is cut from the porous carbon fiber paper prepared in embodiment 1 as electrode, assembling At monocell, charge-discharge performance test is carried out.Anode electrolyte is 1.5M VO2+3M H2SO4Solution 40ml, electrolyte liquid For 1.5M V3+3M H2SO4Solution 40ml.Current efficiency (CE) of the porous carbon fiber paper monocell under different current densities, Voltage efficiency (VE) and energy efficiency (EE) are summarised in table 1.Compared with carbon paper in comparative example 1, porous carbon fiber in the present embodiment The voltage efficiency of paper monocell is tieed up in 80mA/cm2Current density under from 75.6% be increased to 90.0%, energy efficiency can reach To 84.3%；In 120mA/cm2High current density under voltage efficiency from 70.7% be increased to 84.9%, energy efficiency improves To 80.1%, current density is higher, and improvement effect is more significant.
CO is used in each embodiment of table 12Carbon felt is activated as monocell in the monocell and comparative example of electrode in different electricity Battery efficiency when current density
Comparative example
Using the carbon paper of German SGL company production as comparative example, the carbon paper having a size of 4cm × 3cm is cut as electrode It is assembled into monocell, carries out charge-discharge performance test.Anode electrolyte is 1.5M VO2+3M H2SO4Solution 40ml, negative electricity Solution liquid is 1.5M V3+3M H2SO4Solution 40ml.Its battery efficiency under different current densities is as shown in table 1, 140mA/cm2High current density under not can be carried out effective charge and discharge cycles.
Embodiment 2
Prepare the asphaltic base chopped carbon fiber that length is 15mm to be put into molten by it in acetone soln after degumming process Be beaten in the aqueous solution for having 0.05% polyacrylamide amine dispersant, formed asphalt base carbon fiber slurry, then through wet process at It is 50g/m that type equipment, which manufactures paper with pulp into weight per unit area,2Carbon paper presoma；Later, being dipped in phenolic resin concentration is 1% In ethanol solution, 30min is impregnated, then hot-forming obtained carbon paper body paper, pressure are at 180 DEG C again after being dried 5MPa；Carbon paper body paper is put into electric furnace, in N21400 DEG C are warming up to the heating rate of 5 DEG C/min under atmosphere, constant temperature 1h；So After be cooled to 800 DEG C, be passed through vapor and N2Gaseous mixture, vapor and N2Flow be respectively 10ml/min and 200ml/ Min, isothermal reaction 30min；It is cooled to room temperature and porous carbon fiber paper is made.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition: using the present embodiment porous carbon All-vanadium flow battery of the fibrous paper as electrode, current density 80mA/cm2When, voltage efficiency and energy efficiency are respectively 83.8% and 78.3%；Current density is increased to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 76.6% He 73%, battery performance is greatly improved compared with comparative example 1.
Embodiment 3
Prepare the viscose base chopped carbon fiber that length is 10mm to be put into molten by it in acetone soln after degumming process Be beaten in the aqueous solution for having 0.05% polyacrylamide amine dispersant, formed viscose base carbon fibre slurry, then through wet process at It is 50g/m that type equipment, which manufactures paper with pulp into weight per unit area,2Carbon paper presoma；Later, being dipped in phenolic resin concentration is 0.5% Ethanol solution in, impregnate 30min, then hot-forming obtained carbon paper body paper, pressure are at 180 DEG C again after being dried 5MPa；Carbon paper body paper is put into electric furnace, in N21300 DEG C are warming up to the heating rate of 5 DEG C/min under atmosphere, constant temperature 1h；So After keep temperature-resistant, be passed through CO2And N2Gaseous mixture, CO2And N2Flow be respectively 20ml/min and 200ml/min, constant temperature React 30min；It is cooled to room temperature and porous carbon fiber paper is made.
With embodiment 1, difference from Example 1 is monocell assembling evaluation and test condition: using the present embodiment active carbon All-vanadium flow battery of the felt as electrode, current density 80mA/cm2When, voltage efficiency and energy efficiency are respectively 80.7% With 75.8%；Current density is increased to 120mA/cm2When, voltage efficiency and energy efficiency still remain in 75.8% He 71.8%.

Claims (11)

1. porous carbon fiber paper electrode material used for all-vanadium redox flow battery, it is characterised in that: porous carbon fiber paper thickness of electrode is 50- It 1000 μm, is made of the carbon fiber that diameter is 5-20 μm, the porosity of porous carbon fiber paper is 60-90%；Carbon fiber surface For porous structure, the specific surface area of carbon fiber is 5-50m2/ g, aperture 50-2000nm；
The electrode material is prepared by following methods,
1) by carbon fiber in acetone soln after degumming process, be put into the aqueous solution dissolved with dispersing agent and be beaten, formed Carbon fiber slurry；
2) carbon paper presoma is made using wet forming paper technology in carbon fiber slurry described in step 1)；
3) it is dried after impregnating the carbon paper presoma in the ethanol solution of phenolic resin again hot at 150-280 DEG C It is molded；
4) hot-forming carbon paper body paper is risen to 1000~2300 DEG C of assigned temperature A under an inert atmosphere, constant temperature keeps 0.5- 3h；
5) 700~1500 DEG C of assigned temperature B then are adjusted to, the gaseous mixture constant temperature for being passed through activation gas and inert gas keeps 2- 60min；
6) it is then cooled to room temperature under inert atmosphere protection, porous carbon fiber paper electrode material is made；
Or, be prepared by following methods,
1) by chopped carbon fiber in acetone soln after degumming process, be put into the aqueous solution dissolved with dispersing agent and be beaten, Form carbon fiber slurry；
2) carbon paper presoma is made using wet forming paper technology in carbon fiber slurry described in step 1)；
3) it is dried after impregnating the carbon paper presoma in the ethanol solution of phenolic resin again hot at 150-280 DEG C It is molded；
4) by hot-forming carbon paper body paper activation gas and inert gas gaseous mixture atmosphere under rise to assigned temperature C800~ 1800 DEG C, constant temperature keeps 2min-2h；
5) it is then cooled to room temperature under inert atmosphere protection, porous carbon fiber paper electrode material is made.
2. the preparation method of porous carbon fiber paper electrode material as described in claim 1, it is characterised in that: the electrode material is logical Following methods are crossed to be prepared,
1) by carbon fiber in acetone soln after degumming process, be put into the aqueous solution dissolved with dispersing agent and be beaten, formed Carbon fiber slurry；
2) carbon paper presoma is made using wet forming paper technology in carbon fiber slurry described in step 1)；
3) it is dried after impregnating the carbon paper presoma in the ethanol solution of phenolic resin again hot at 150-280 DEG C It is molded；
4) hot-forming carbon paper body paper is risen to 1000~2300 DEG C of assigned temperature A under an inert atmosphere, constant temperature keeps 0.5- 3h；
5) 700~1500 DEG C of assigned temperature B then are adjusted to, the gaseous mixture constant temperature for being passed through activation gas and inert gas keeps 2- 60min；
6) it is then cooled to room temperature under inert atmosphere protection, porous carbon fiber paper electrode material is made.
3. preparation method according to claim 2, it is characterised in that:
The carbon fiber is one of polyacrylonitrile-based carbon fibre, asphalt base carbon fiber and viscose base carbon fibre, and length is 5mm-30mm, diameter are 5-20 μm.
4. preparation method according to claim 2, it is characterised in that: the dispersing agent is polyethylene glycol oxide, carboxymethyl fibre Tie up one of element and polyacrylamide or two kinds or more；
The concentration of the dispersing agent in the slurry is 0.01-0.2%；
The concentration of phenolic resin is 0.5-15% in the ethanol solution of the phenolic resin.
5. preparation method according to claim 2, it is characterised in that:
The gas of the inert atmosphere is one of nitrogen, argon gas or helium or two kinds or more；
The activation gas is vapor or CO2One of or two kinds, vapor and/or CO in gaseous mixture2Volumetric concentration be 2 ~50%；
The assigned temperature A is more than or equal to assigned temperature B.
6. preparation method according to claim 5, it is characterised in that: vapor and/or CO in the gaseous mixture2Volume Concentration is 2~20%.
7. according to preparation method described in claim 2 or 5, it is characterised in that: the assigned temperature A is 1400~2300 DEG C； The assigned temperature B is 800~1400 DEG C.
8. the preparation method of porous carbon fiber paper electrode material as described in claim 1, it is characterised in that: the electrode material is logical Following methods are crossed to be prepared,
1) by chopped carbon fiber in acetone soln after degumming process, be put into the aqueous solution dissolved with dispersing agent and be beaten, Form carbon fiber slurry；
2) carbon paper presoma is made using wet forming paper technology in carbon fiber slurry described in step 1)；
3) it is dried after impregnating the carbon paper presoma in the ethanol solution of phenolic resin again hot at 150-280 DEG C It is molded；
4) by hot-forming carbon paper body paper activation gas and inert gas gaseous mixture atmosphere under rise to assigned temperature C800~ 1800 DEG C, constant temperature keeps 2min-2h；
5) it is then cooled to room temperature under inert atmosphere protection, porous carbon fiber paper electrode material is made.
9. preparation method according to claim 8, it is characterised in that: the chopped carbon fiber is polyacrylonitrile-radical carbon fiber One of dimension, asphalt base carbon fiber and viscose base carbon fibre, length 5mm-30mm, diameter are 5-20 μm；
The dispersing agent is one of polyethylene glycol oxide, carboxymethyl cellulose and polyacrylamide or two kinds or more；
The concentration of the dispersing agent in the slurry is 0.01-0.2%；
The concentration of phenolic resin is 0.5-15% in the ethanol solution of the phenolic resin；
The gas of the inert atmosphere is one of nitrogen, argon gas or helium or two kinds or more；
The activation gas is vapor or CO2One of or two kinds, vapor and/or CO in gaseous mixture2Volumetric concentration be 2 ~50%.
10. preparation method according to claim 9, it is characterised in that: vapor and/or CO in the gaseous mixture2Volume Concentration is 2~20%.
11. the application of porous carbon fiber paper electrode material as described in claim 1, it is characterised in that: the porous carbon fiber paper Electrode material can be used in all-vanadium flow battery.
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