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 PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 119
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 119
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 11
- 229920000297 Rayon Polymers 0.000 claims description 10
- 239000010426 asphalt Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 polyoxyethylene, carboxymethyl Polymers 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910001456 vanadium ion Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 14
- 238000004146 energy storage Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
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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
Technical Field
The invention relates to the field of flow energy storage batteries in the chemical energy storage technology, in particular to an electrode of an all-vanadium flow battery.
Background
The all-vanadium redox flow battery has the advantages that the output power and the capacity are mutually independent, and the system design is flexible; the energy efficiency is high, the service life is long, the operation stability and reliability are high, and the self-discharge is low; the method has the advantages of large site selection freedom degree, no pollution, simple maintenance, low operation cost, high safety and the like, has wide development prospect in the aspect of scale energy storage, is considered as an effective method for solving the randomness and intermittent unsteady state characteristics of a solar energy and wind energy renewable energy power generation system and the like, and has important requirements in the construction of renewable energy power generation and an intelligent power grid.
Currently, the main limitation restricting the commercialization of all-vanadium flow batteries is the cost problem. To reduce the cost, two main solutions are provided: one is to reduce the cost of each key material, such as the cost of ion exchange membrane, electrolyte and electrode bipolar plate; one is to increase the power density of the battery. Because the power density of the battery is improved, the same galvanic pile can be used for realizing larger power output, the occupied area and the space of the energy storage system can be reduced, the environmental adaptability and the mobility of the system are improved, and the application field of the liquid flow energy storage battery is expanded. To increase the power density of a battery, the operating current density is increased. However, an increase in operating current density results in a decrease in voltage efficiency and energy efficiency. In order to increase the operating current density of the cell without reducing energy efficiency, it is necessary to reduce the cell polarization, i.e., ohmic polarization, electrochemical polarization, and concentration polarization, as much as possible and to reduce the voltage loss.
The electrode is one of the key components of the all-vanadium redox flow energy storage battery, and the performance of the electrode has great influence on the redox flow energy storage battery. The all-vanadium redox flow battery electrode material in the prior art is usually prepared by carrying out air pre-oxidation, carbonization and graphitization on a polyacrylonitrile needled felt, so that the production cost is high due to more working procedures, and the prepared graphite felt has poor electrocatalytic activity. The electrocatalytic activity of the electrode directly determines the intrinsic reaction rate of the electrochemical reaction, and greatly influences the working current density and energy efficiency of the battery. Therefore, in order to achieve high operating current density and energy efficiency, a suitable activation method is employed to increase the electrocatalytic activity of the graphite felt as much as possible. The patent documents disclosed so far mainly include methods for reducing electrochemical polarization of a flow energy storage battery:
(1) the method is to perform oxidation modification treatment on electrode materials such as graphite felt, carbon paper and the like, modify oxygen-containing functional groups on the surface of carbon fibers, improve the electrocatalytic activity of an electrode, and reduce the electrochemical polarization of a battery, for example, the method disclosed in patents CN 101465417a and CN101182678A for performing electrochemical oxidation on graphite felt.
(2) Electrode materials such as graphite felt, carbon paper, etc. are metallized by modifying the surface of the carbon fibers with metal ions, such as Sun et al (Sun, B.T.; Skyllas-Kazacos, M.chemical Modification and electrochemical Behavior ofMn is modified on the surface of carbon Fiber by Graphite Fiber in Acidic Vanadiumsolution. Electron. acta 1991,36,513-517.)2+、Te4+、In3+And Ir3+Etc. found Ir3+The method has the most effect on improving the electrocatalytic activity of the electrode material, but is not suitable for large-scale application due to the high cost of the electrode caused by the use of noble metals.
In addition, the carbon felt or graphite felt used at present has larger electrode thickness, which results in larger inter-electrode distance and increases the internal resistance of the battery, namely ohmic polarization. Therefore, in order to obtain a smaller ohmic polarization, it is necessary to use an electrode material having a smaller thickness.
Disclosure of Invention
The invention provides a high-activity porous carbon fiber paper electrode material for an all-vanadium redox flow battery and a preparation method thereof, aiming at solving the problems of large thickness and low electrocatalytic activity of an electrode of the all-vanadium redox flow battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-activity porous carbon fiber paper electrode material for an all-vanadium redox flow battery is 50-1000 mu m in thickness and is composed of carbon fibers with the diameter of 5-20 mu m, and the porosity of porous carbon fiber paper is 60-90%; the surface of the carbon fiber is of a porous structure, and the specific surface area of the carbon fiber is 5-50m2The pore diameter is 50-2000 nm. The electrode material can be prepared by the following method:
1) degumming the chopped carbon fibers in an acetone solution, and then pulping the degummed chopped carbon fibers in an aqueous solution dissolved with a dispersant to form carbon fiber slurry;
2) preparing the carbon fiber slurry in the step 1) into a carbon paper precursor by using a wet forming papermaking process;
3) soaking the carbon paper precursor in an ethanol solution of phenolic resin, drying, and hot-press molding at the temperature of 150-280 ℃;
4) heating the hot-press formed carbon paper base paper to a specified temperature A under an inert atmosphere, and keeping the constant temperature for 0.5-3 h;
5) then adjusting to a specified temperature B, and introducing a mixed gas of activated gas and inert gas to keep the constant temperature for 2-60 min;
6) then cooling to room temperature under the protection of inert atmosphere to prepare the porous carbon fiber paper electrode material;
wherein,
the chopped carbon fibers are one of polyacrylonitrile-based carbon fibers, asphalt-based carbon fibers and viscose-based carbon fibers, the length of the chopped carbon fibers is 5-30 mm, and the diameter of the chopped carbon fibers is 5-20 microns;
the dispersing agent is one or more than two of polyoxyethylene, carboxymethyl cellulose and polyacrylamide;
the concentration of the dispersant in the slurry is 0.01-0.2%;
the concentration of the phenolic resin in the ethanol solution of the phenolic resin is 0.5-15%;
the gas of the inert atmosphere is one or more than two of nitrogen, argon or helium;
the specified temperature A is greater than or equal to the specified temperature B;
the specified temperature A is 1000-2300 ℃;
the specified temperature B is 700-1500 ℃;
the activating gas is water vapor or CO2One or two of (1), water vapor and/or CO in the mixed gas2The volume concentration of (A) is 2 to 50%, preferably 2 to 20%.
Alternatively, the electrode material of the present invention can be prepared by a method,
1) degumming the chopped carbon fibers in an acetone solution, and then pulping the degummed chopped carbon fibers in an aqueous solution dissolved with a dispersant to form carbon fiber slurry;
2) preparing the carbon fiber slurry in the step 1) into a carbon paper precursor by using a wet forming papermaking process;
3) soaking the carbon paper precursor in an ethanol solution of phenolic resin, drying, and hot-press molding at the temperature of 150-280 ℃;
4) heating the hot-press formed carbon paper base paper to a specified temperature C under the atmosphere of mixed gas of activated gas and inert gas, and keeping the constant temperature for 2min-2 h;
5) then cooling to room temperature under the protection of inert atmosphere to prepare the porous carbon fiber paper electrode material;
wherein,
the chopped carbon fibers are one of polyacrylonitrile-based carbon fibers, asphalt-based carbon fibers and viscose-based carbon fibers, the length of the chopped carbon fibers is 5-30 mm, and the diameter of the chopped carbon fibers is 5-20 microns;
the dispersing agent is one or more than two of polyoxyethylene, carboxymethyl cellulose and polyacrylamide;
the concentration of the dispersant in the slurry is 0.01-0.2%;
the concentration of the phenolic resin in the ethanol solution of the phenolic resin is 0.5-15%;
the gas of the inert atmosphere is one or more than two of nitrogen, argon or helium;
the activating gas is water vapor or CO2One or two of (1), water vapor and/or CO in the mixed gas2The volume concentration of (a) is 2-50%, preferably 2-20%;
the specified temperature C is 800-1800 ℃.
The invention has the following advantages:
(1) the electrode material prepared by the preparation method of the invention has a large number of pores on the surface of the carbon fiber, and the specific surface of the electrode material is improvedThe product can obtain a large amount of surface oxygen-containing functional groups, the hydrophilicity is obviously improved, the electrochemical polarization of the liquid flow energy storage battery can be obviously reduced, and the electrode material is greatly improved for VO2+/VO2 +And V2+/V3+The electrocatalytic activity of the redox reaction reduces the charge transfer resistance, and improves the voltage efficiency and the energy efficiency of the all-vanadium redox flow battery, thereby improving the working current density of the all-vanadium redox flow battery, and greatly reducing the weight, the volume and the cost of the battery with the same output power.
(2) Compared with the existing activated carbon fiber, the electrode material prepared by the preparation method of the invention has smaller specific surface area which is only 5-50m2And pores are distributed on the surface of the carbon fiber, so that the body resistance of the carbon paper electrode cannot be greatly improved, and the electrode has small thickness which is less than 1mm, so that the inter-polar distance is greatly reduced, the internal resistance of the battery is reduced, and the working current density of the battery is improved.
(3) The electrode material disclosed by the invention is simple in preparation method, free of special requirements on equipment, convenient to operate, low in cost, high in practical value and easy to produce in batches.
Drawings
FIG. 1 is a scanning electron micrograph of a porous carbon fiber paper prepared in example 1 of the present invention;
FIG. 2 is a plot of cyclic voltammetry for the porous carbon fiber paper prepared in example 1 of the present invention and the carbon paper in comparative example 1 for the V (IV)/V (V) couple, scan rate: 10 mV/s;
FIG. 3 is a plot of cyclic voltammetry for a V (II)/V (III) couple for the porous carbon fiber paper prepared in example 1 of the present invention and for the carbon paper in comparative example 1, scan rates: 10 mV/s;
Detailed Description
The present invention is described in detail below with reference to specific examples.
Example 1
Preparing polyacrylonitrile-based chopped carbon fibers with the length of 10mm, degumming the polyacrylonitrile-based chopped carbon fibers in an acetone solution, pulping the polyacrylonitrile-based chopped carbon fibers in an aqueous solution in which 0.1 percent of polyoxyethylene dispersant is dissolved to form polyacrylonitrile-based carbon fiber pulp, and manufacturing the polyacrylonitrile-based chopped carbon fibers into polyacrylonitrile-based carbon fiber pulp with the unit area weight of 40g/m by wet forming equipment2The carbon paper precursor of (1); then, soaking the carbon paper base paper in 1% ethanol solution of phenolic resin for 30min, drying, and hot-pressing at 200 ℃ to obtain carbon paper base paper under the pressure of 6 MPa; placing the carbon paper base paper into an electric furnace at N2Heating to 1600 ℃ at a heating rate of 10 ℃/min in the atmosphere, and keeping the temperature for 1 h; then cooling to 1300 ℃, introducing CO2And N2Mixed gas of (2), CO2And N2The flow rates of the reaction solution are respectively 40ml/min and 200ml/min, and the reaction is carried out for 30min at constant temperature; and cooling to room temperature to obtain the porous carbon fiber paper.
To test the electrochemical activity of the vanadium redox couple on the surface of the porous carbon fiber paper, cyclic voltammetry was performed on the porous carbon fiber paper prepared in example 1. Porous carbon fiber paper is used as a working electrode, a non-porous graphite plate is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and an adopted electrochemical testing instrument is a CHI604e type electrochemical workstation of Shanghai Chenghua company. The preparation concentration is 0.05M V (II) +0.05M V (III) +3M H2SO4And 0.05M V (IV) +0.05M V (V) +3M H2SO4The electrochemical activity of the V (IV)/V (V) and V (II)/V (III) pairs on the surface of the porous carbon fiber paper is respectively researched, the scanning ranges are respectively-1V to-0.2V and 0.5 to 1.2V, and the scanning speed is 10 mV/s. In the SEM photograph of the porous carbon fiber paper in this example, as shown in fig. 1, it can be observed that a large number of nanopores are distributed on the surface of the carbon fiber. The cyclic voltammograms of this material are shown in FIGS. 2 and 3, comparing the electrochemical oxidation and reduction peak positions of V (IV)/V (V) and V (II)/V (III) on the porous carbon fiber paper and the carbon paper of comparative example 1The peak current is known, and the porous carbon fiber paper prepared by the embodiment has obviously improved electrocatalytic activity and electrochemical reversibility.
Carbon paper having a size of 4cm × 3cm was cut from the porous carbon fiber paper prepared in example 1 and assembled as a single cell for charge and discharge performance test. The positive electrolyte is 1.5M VO2+3M H2SO440ml of the solution, the negative electrode electrolyte solution was 1.5M V3+3M H2SO440ml of the solution. The Current Efficiency (CE), Voltage Efficiency (VE) and Energy Efficiency (EE) of the porous carbon fiber paper cells at different current densities are summarized in table 1. The voltage efficiency of the single cell of the porous carbon fiber paper in this example was 80mA/cm, compared with the carbon paper in comparative example 12The current density is improved from 75.6% to 90.0%, and the energy efficiency can reach 84.3%; at 120mA/cm2The voltage efficiency under the high current density is improved to 84.9% from 70.7%, the energy efficiency is improved to 80.1%, and the higher the current density is, the more remarkable the improvement effect is.
Table 1 use of CO in each example2Cell efficiency at different current densities for single cells with activated carbon felt as electrode and for single cells in comparative examples
Comparative example
Carbon paper produced by SGL company of germany was used as a comparative example, and carbon paper having a size of 4cm × 3cm was cut out as an electrode to assemble a single cell, and a charge and discharge performance test was performed. The positive electrolyte is 1.5M VO2+3M H2SO440ml of the solution, the negative electrode electrolyte solution was 1.5M V3+3M H2SO440ml of the solution. At different current densitiesThe cell efficiencies at 140mA/cm are shown in Table 12Does not allow efficient charge-discharge cycling at high current densities.
Example 2
Preparing asphalt-based chopped carbon fibers with the length of 15mm, degumming the asphalt-based chopped carbon fibers in an acetone solution, pulping the degummed asphalt-based chopped carbon fibers in an aqueous solution in which 0.05 percent of polyacrylamide dispersant is dissolved to form asphalt-based carbon fiber pulp, and manufacturing the asphalt-based carbon fiber pulp into the asphalt-based carbon fiber pulp with the unit area weight of 50g/m by wet forming equipment2The carbon paper precursor of (1); then, soaking the carbon paper base paper in 1% ethanol solution of phenolic resin for 30min, drying, and hot-pressing at 180 ℃ to obtain carbon paper base paper under the pressure of 5 MPa; placing the carbon paper base paper into an electric furnace at N2Heating to 1400 ℃ at the heating rate of 5 ℃/min under the atmosphere, and keeping the temperature for 1 h; then cooling to 800 ℃, introducing water vapor and N2Mixed gas of (2), steam and N2The flow rates of the reaction solution are respectively 10ml/min and 200ml/min, and the reaction is carried out for 30min at constant temperature; and cooling to room temperature to obtain the porous carbon fiber paper.
The cell assembly evaluation conditions were the same as in example 1, except that: the current density of the all-vanadium redox flow battery adopting the porous carbon fiber paper as the electrode is 80mA/cm2The voltage efficiency and the energy efficiency are 83.8% and 78.3%, respectively; the current density is increased to 120mA/cm2When the voltage efficiency and the energy efficiency were maintained at 76.6% and 73%, the battery performance was greatly improved as compared with comparative example 1.
Example 3
Preparing viscose-based chopped carbon fibers with the length of 10mm, degumming the viscose-based chopped carbon fibers in an acetone solution, pulping the viscose-based chopped carbon fibers in an aqueous solution in which 0.05 percent of polyacrylamide dispersant is dissolved to form viscose-based carbon fiber pulp, and manufacturing the viscose-based carbon fiber pulp into viscose-based carbon fiber pulp with the unit area weight of 50g/m by wet forming equipment2The carbon paper precursor of (1); in-line with the aboveThen, soaking the carbon paper base paper in an ethanol solution with the concentration of phenolic resin being 0.5 percent for 30min, drying, and then carrying out hot press molding at 180 ℃ to obtain carbon paper base paper with the pressure being 5 MPa; placing the carbon paper base paper into an electric furnace at N2Heating to 1300 ℃ at the heating rate of 5 ℃/min under the atmosphere, and keeping the temperature for 1 h; then keeping the temperature constant, and introducing CO2And N2Mixed gas of (2), CO2And N2The flow rates of the reaction solution are respectively 20ml/min and 200ml/min, and the reaction is carried out for 30min at constant temperature; and cooling to room temperature to obtain the porous carbon fiber paper.
The cell assembly evaluation conditions were the same as in example 1, except that: the current density of the all-vanadium redox flow battery adopting the activated carbon felt as the electrode is 80mA/cm2The voltage efficiency and the energy efficiency are respectively 80.7% and 75.8%; the current density is increased to 120mA/cm2The voltage efficiency and energy efficiency remained at 75.8% and 71.8%.
Claims (11)
1. The porous carbon fiber paper electrode material for the all-vanadium redox flow battery is characterized in that: the thickness of the porous carbon fiber paper electrode is 50-1000 μm, the porous carbon fiber paper electrode is composed of carbon fibers with the diameter of 5-20 μm, and the porosity of the porous carbon fiber paper is 60-90%; the surface of the carbon fiber is of a porous structure, and the specific surface area of the carbon fiber is 5-50m2Per g, the aperture is 50-2000 nm;
the electrode material is prepared by a method comprising the following steps,
1) degumming carbon fibers in an acetone solution, and then pulping the carbon fibers in an aqueous solution dissolved with a dispersing agent to form carbon fiber slurry;
2) preparing the carbon fiber slurry in the step 1) into a carbon paper precursor by using a wet forming papermaking process;
3) soaking the carbon paper precursor in an ethanol solution of phenolic resin, drying, and hot-press molding at the temperature of 150-280 ℃;
4) raising the hot-press formed carbon paper base paper to a specified temperature A of 1000-2300 ℃ in an inert atmosphere, and keeping the temperature for 0.5-3 h;
5) then adjusting to a specified temperature B of 700-1500 ℃, and introducing a mixed gas of activated gas and inert gas to keep the constant temperature for 2-60 min;
6) then cooling to room temperature under the protection of inert atmosphere to prepare the porous carbon fiber paper electrode material;
or, prepared by the following method,
1) degumming the chopped carbon fibers in an acetone solution, and then pulping the degummed chopped carbon fibers in an aqueous solution dissolved with a dispersant to form carbon fiber slurry;
2) preparing the carbon fiber slurry in the step 1) into a carbon paper precursor by using a wet forming papermaking process;
3) soaking the carbon paper precursor in an ethanol solution of phenolic resin, drying, and hot-press molding at the temperature of 150-280 ℃;
4) raising the hot-press formed carbon paper base paper to a specified temperature of 800-1800 ℃ under the atmosphere of mixed gas of activated gas and inert gas, and keeping the constant temperature for 2min-2 h;
5) and then cooling to room temperature under the protection of inert atmosphere to prepare the porous carbon fiber paper electrode material.
2. The method for preparing the porous carbon fiber paper electrode material as claimed in claim 1, wherein: the electrode material is prepared by a method comprising the following steps,
1) degumming carbon fibers in an acetone solution, and then pulping the carbon fibers in an aqueous solution dissolved with a dispersing agent to form carbon fiber slurry;
2) preparing the carbon fiber slurry in the step 1) into a carbon paper precursor by using a wet forming papermaking process;
3) soaking the carbon paper precursor in an ethanol solution of phenolic resin, drying, and hot-press molding at the temperature of 150-280 ℃;
4) raising the hot-press formed carbon paper base paper to a specified temperature A of 1000-2300 ℃ in an inert atmosphere, and keeping the temperature for 0.5-3 h;
5) then adjusting to a specified temperature B of 700-1500 ℃, and introducing a mixed gas of activated gas and inert gas to keep the constant temperature for 2-60 min;
6) and then cooling to room temperature under the protection of inert atmosphere to prepare the porous carbon fiber paper electrode material.
3. The method of claim 2, wherein:
the carbon fiber is one of polyacrylonitrile-based carbon fiber, asphalt-based carbon fiber and viscose-based carbon fiber, the length is 5-30 mm, and the diameter is 5-20 μm.
4. The method of claim 2, wherein: the dispersing agent is one or more than two of polyoxyethylene, carboxymethyl cellulose and polyacrylamide;
the concentration of the dispersant in the slurry is 0.01-0.2%;
the concentration of the phenolic resin in the ethanol solution of the phenolic resin is 0.5-15%.
5. The method of claim 2, wherein:
the gas of the inert atmosphere is one or more than two of nitrogen, argon or helium;
the activating gas is water vapor or CO2One or two of (1), water vapor and/or CO in the mixed gas2The volume concentration of (A) is 2-50%;
the specified temperature A is greater than or equal to the specified temperature B.
6. The method of claim 5, wherein: water vapor and/or water vapor in the mixed gasCO2The volume concentration of (A) is 2-20%.
7. The production method according to claim 2 or 5, characterized in that: the specified temperature A is 1400-2300 ℃; the specified temperature B is 800-1400 ℃.
8. The method for preparing the porous carbon fiber paper electrode material as claimed in claim 1, wherein: the electrode material is prepared by a method comprising the following steps,
1) degumming the chopped carbon fibers in an acetone solution, and then pulping the degummed chopped carbon fibers in an aqueous solution dissolved with a dispersant to form carbon fiber slurry;
2) preparing the carbon fiber slurry in the step 1) into a carbon paper precursor by using a wet forming papermaking process;
3) soaking the carbon paper precursor in an ethanol solution of phenolic resin, drying, and hot-press molding at the temperature of 150-280 ℃;
4) raising the hot-press formed carbon paper base paper to a specified temperature of 800-1800 ℃ under the atmosphere of mixed gas of activated gas and inert gas, and keeping the constant temperature for 2min-2 h;
5) and then cooling to room temperature under the protection of inert atmosphere to prepare the porous carbon fiber paper electrode material.
9. The method of claim 8, wherein: the chopped carbon fibers are one of polyacrylonitrile-based carbon fibers, asphalt-based carbon fibers and viscose-based carbon fibers, the length of the chopped carbon fibers is 5-30 mm, and the diameter of the chopped carbon fibers is 5-20 microns;
the dispersing agent is one or more than two of polyoxyethylene, carboxymethyl cellulose and polyacrylamide;
the concentration of the dispersant in the slurry is 0.01-0.2%;
the concentration of the phenolic resin in the ethanol solution of the phenolic resin is 0.5-15%;
the gas of the inert atmosphere is one or more than two of nitrogen, argon or helium;
the activating gas is water vapor or CO2One or two of (1), water vapor and/or CO in the mixed gas2The volume concentration of (A) is 2-50%.
10. The method of claim 9, wherein: water vapor and/or CO in the mixed gas2The volume concentration of (A) is 2-20%.
11. Use of the porous carbon fiber paper electrode material as claimed in claim 1, wherein: the porous carbon fiber paper electrode material can be used in all-vanadium redox flow batteries.
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| CN109216709A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of dig pit effect construction method and its application of high-ratio surface carbon fiber felt |
| CN109671957A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
| CN109671953A (en) * | 2017-10-13 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
| CN109841850A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of positive electrode used for all-vanadium redox flow battery and its preparation and application |
| CN109841851A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of electrode material for all-vanadium flow battery and its preparation and application |
| CN108914681B (en) * | 2018-07-06 | 2020-12-22 | 天津工业大学 | Preparation method of carbon fiber paper |
| CN110129992B (en) * | 2019-06-04 | 2021-04-27 | 缪梦程 | Carbon fiber paper for fuel cell and preparation method thereof |
| CN112709093A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of carbon fiber paper |
| CN111900418B (en) * | 2020-07-31 | 2021-11-30 | 齐鲁工业大学 | Preparation method of carbon paper precursor for gas diffusion layer of fuel cell |
| CN113258081B (en) * | 2021-06-15 | 2021-11-19 | 长沙理工大学 | Modified electrode for flow battery, preparation method of modified electrode and flow battery |
| CN113972024A (en) * | 2021-10-29 | 2022-01-25 | 吉林聚能新型炭材料股份有限公司 | Carbon-based high-length-diameter-ratio flexible conductive material and preparation method thereof |
| CN113943158B (en) * | 2021-12-20 | 2022-07-19 | 杭州德海艾科能源科技有限公司 | Preparation method of graphite felt for flow battery |
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