CN114744223B - Iron-chromium redox flow battery electrode material and preparation method thereof - Google Patents
Iron-chromium redox flow battery electrode material and preparation method thereof Download PDFInfo
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- CN114744223B CN114744223B CN202210487199.XA CN202210487199A CN114744223B CN 114744223 B CN114744223 B CN 114744223B CN 202210487199 A CN202210487199 A CN 202210487199A CN 114744223 B CN114744223 B CN 114744223B
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- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 65
- 239000010439 graphite Substances 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 35
- 229910001451 bismuth ion Inorganic materials 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
-
- 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
-
- 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
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
- Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to an iron-chromium redox flow battery electrode material and a preparation method thereof, belonging to the technical field of batteries, and comprising the following steps: immersing graphite felt in silicic acid gel under ultrasonic, drying at 80deg.C to obtain silicic acid/graphite felt composite material, and heating the silicic acid/graphite felt composite material under air condition to obtain S i0 2 -graphite felt; will S i0 2 -immersing graphite felt in bismuth ion immersing liquid, adding NaBH 4 And drying the solution in a vacuum oven to obtain the iron-chromium redox flow battery electrode material. In the technical scheme of the invention, the S i O is impregnated with the graphite felt by silicic acid 2 The surface of the graphite felt is introduced, the roughness of the surface of the graphite felt is increased by etching hydroxyl groups in silicic acid, a large amount of oxygen-containing functional groups are introduced, and then the oxygen-containing functional groups are introduced into the graphite felt through the etching of hydroxyl groups in the silicic acid 2 And the metal B i is deposited on the surface of the graphite felt at the same time, so that the high activity of the graphite felt and the inhibition of hydrogen evolution reaction are realized.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an iron-chromium redox flow battery electrode material and a preparation method thereof.
Background
The development of renewable energy sources such as wind energy, solar energy and the like for power generation is an important measure for coping with climate change. However, since renewable energy sources are intermittent, direct grid connection of renewable energy power generation may damage the stability of the grid. The provision of a stationary electrochemical energy storage device enables efficient integration of sustainable electrical energy, but installation and maintenance costs remain a major obstacle to the popularity of electrochemical devices in the power grid. Accordingly, it has been proposed in recent years to solve the problem of continuous power generation of renewable energy sources by using flow batteries. The basic structure of the flow battery comprises: liquid storage tanks, electrochemical reactors and flow systems. The structure can carry out flexible modularized design and large-scale control, has moderate maintenance cost and long cycle life, and has unique decoupling efficiency and capacity. Among the numerous flow battery systems, the iron-chromium flow battery adopts low-cost and environment-friendly iron/chromium hydrochloric acid solution as a cathode and an anode respectively, and is expected to be widely applied to energy storage application.
In the prior art, a graphite felt material is often adopted as an electrode material of the iron-chromium redox flow battery, because the electrode material has stable electrochemical performance, high mechanical strength and large surface area, in order to increase the activity of a graphite felt electrode, oxygen functional groups such as-OH, -COOH and the like are generally introduced into the graphite felt, and then a catalyst is introduced into the graphite felt to reduce the hydrogen evolution reaction of the iron-chromium redox flow battery, but the effect of introducing the oxygen functional groups is poor in increasing the specific surface area of the graphite felt, and meanwhile, more adsorption of the catalyst is limited, so that the activity of the electrode is improved and the hydrogen evolution reaction inhibiting effect is reduced.
Disclosure of Invention
The invention aims to provide an iron-chromium redox flow battery electrode material and a preparation method thereof, wherein SiO is impregnated with graphite felt through silicic acid 2 Introducing a large amount of oxygen-containing functional groups into the surface of the graphite felt by etching hydroxyl groups in silicic acid, increasing the roughness of the surface of the graphite felt, and then forming a silicon oxide film on the surface of SiO 2 And simultaneously depositing metal Bi on the surface of the graphite felt, thereby realizing high activity of the graphite felt and inhibiting hydrogen evolution reaction.
The invention aims to solve the technical problems: the effect of increasing the specific surface area of the graphite felt by introducing oxygen functional groups is poor, and more adsorption of the catalyst is limited, so that the activity of the electrode is improved and the hydrogen evolution reaction inhibiting effect is reduced.
The aim of the invention can be achieved by the following technical scheme:
an iron-chromium redox flow battery electrode material and a preparation method thereof comprise the following steps:
s1, immersing a graphite felt into silicic acid gel for 30-40min under ultrasonic, drying at 80 ℃ for 24h to obtain a silicic acid/graphite felt composite material, heating the silicic acid/graphite felt composite material to 500 ℃ at a heating rate of 10 ℃/min under air condition, and preserving heat for 5h to obtain Si0 2 -graphite felt, wherein the mass ratio of graphite felt to silicic acid gel is 1:0.25-0.5;
s2, si0 2 -immersing graphite felt in bismuth ion immersing liquid, adding NaBH with concentration of 0.5M 4 Drying the solution in a vacuum oven at 80 ℃ for 24 hours after the reaction is completed to obtain the iron-chromium redox flow battery electrode material, wherein Si0 2 -graphite felt, bismuth ion impregnation liquid and NaBH 4 The dosage ratio of the solution is 4-5g:240-260mL:5-10mL.
Further, the silicic acid gel is prepared by the following steps:
12.2g of sodium silicate was dissolved in 50mL of diluted hydrochloric acid with a concentration of 3M and reacted well. Filtering, washing and drying to obtain silicic acid powder. Then, the silicic acid powder was dissolved in deionized water and ultrasonically dispersed for 30min to obtain silicic acid gel.
Further, the graphite felt is a polyacrylonitrile-based graphite felt, and the thickness is 5mm.
Further, the bismuth ion impregnating solution comprises the following steps:
bi (NO) 3 ) 3 ·5H 2 O is dispersed into glycerin, then the glycerin is transferred into a stainless steel autoclave for heat treatment at 160 ℃ for 12 hours, after the reaction is finished, the glycerin is naturally cooled to room temperature, a solid product is obtained through centrifugation and washing, the solid product is dispersed into a mixed solvent of water and ethanol, and bismuth ion impregnating solution is formed under ultrasound, wherein Bi (NO 3 ) 3 ·5H 2 The dosage ratio of O, glycerol, water and ethanol is 20-25g:70-80mL:40-50mL:190-210mL.
The invention has the beneficial effects that:
in the technical scheme of the invention, the graphite felt is impregnated with silicic acid, under the hot air environment, the-OH functional groups in the silicic acid structure promote the oxidation corrosion of the surface of the polyacrylonitrile-based graphite felt fiber, and the oxygen-containing functional groups are introduced, so that the electrode activity and the wettability of electrolyte to the graphite felt can be obviously enhanced, the hydrogen evolution reaction can be inhibited to a certain extent by the enhancement of the electrode activity, macropores can be formed on the surface of the graphite felt fiber after the oxidation corrosion, the surface roughness of the graphite felt is increased by the macroporous structure, and SiO is utilized 2 And deposition of metallic Bi; in addition, graphite felt fibers and porous SiO containing macropore structures 2 More particularly, the deposition of Bi metal is utilized to deposit on graphite felt fibers and porous SiO 2 On the one hand, the metal Bi in the nano-particle can prevent the agglomeration of the metal Bi nano-particles, and further, the inhibition of hydrogen evolution reaction by the synergistic oxygen-containing functional group is better realized.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The bismuth ion impregnating solution comprises the following steps:
20g Bi (NO) 3 ) 3 ·5H 2 O is dispersed into 70mL of glycerin, then the glycerin is transferred into a stainless steel autoclave for heat treatment for 12h at 160 ℃, after the reaction is finished, the room temperature is naturally cooled, a solid product is obtained through centrifugation and washing, the solid product is dispersed into a mixed solvent of 40mL of water and 190mL of ethanol, and bismuth ion impregnation liquid is formed under ultrasound.
Example 2
The bismuth ion impregnating solution comprises the following steps:
23g Bi (NO) 3 ) 3 ·5H 2 O is dispersed into 75mL of glycerin, then the glycerin is transferred into a stainless steel autoclave for heat treatment for 12h at 160 ℃, after the reaction is finished, the room temperature is naturally cooled, a solid product is obtained through centrifugation and washing, the solid product is dispersed into a mixed solvent of 45mL of water and 200mL of ethanol, and bismuth ion impregnation liquid is formed under ultrasound.
Example 3
The bismuth ion impregnating solution comprises the following steps:
25g Bi (NO) 3 ) 3 ·5H 2 O is dispersed into 80mL of glycerin, then the glycerin is transferred into a stainless steel autoclave for heat treatment for 12h at 160 ℃, after the reaction is finished, the room temperature is naturally cooled, a solid product is obtained through centrifugation and washing, the solid product is dispersed into a mixed solvent of 50mL of water and 210mL of ethanol, and bismuth ion impregnation liquid is formed under ultrasound.
Example 4
An iron-chromium redox flow battery electrode material and a preparation method thereof comprise the following steps:
s1, immersing 1g of graphite felt into 0.25g of silicic acid gel prepared in example 1 under ultrasonic, drying at 80 ℃ for 24 hours to obtain a silicic acid/graphite felt composite material, heating the silicic acid/graphite felt composite material to 500 ℃ at a heating rate of 10 ℃/min under air condition, and preserving heat for 5 hours to obtain Si0 2 -graphite felt;
s2, 4g Si0 2 Graphite felt is immersed in 240mL bismuth ion immersion liquid, 5mL NaBH with concentration of 0.5M is added 4 And after the solution is completely reacted, drying the solution in a vacuum oven at 80 ℃ for 24 hours to obtain the iron-chromium redox flow battery electrode material.
Example 5
An iron-chromium redox flow battery electrode material and a preparation method thereof comprise the following steps:
s1, immersing 1g of graphite felt into 0.35g of silicic acid gel prepared in example 2 under ultrasonic, drying at 80 ℃ for 24 hours to obtain a silicic acid/graphite felt composite material, heating the silicic acid/graphite felt composite material to 500 ℃ at a heating rate of 10 ℃/min under air condition, and preserving heat for 5 hours to obtain Si0 2 -graphite felt;
s2, 4.5g Si0 2 Graphite felt is immersed in 250mL bismuth ion immersion liquid, 8mL NaBH with concentration of 0.5M is added 4 And after the solution is completely reacted, drying the solution in a vacuum oven at 80 ℃ for 24 hours to obtain the iron-chromium redox flow battery electrode material.
Example 6
An iron-chromium redox flow battery electrode material and a preparation method thereof comprise the following steps:
s1, immersing 1g of graphite felt into 0.5g of silicic acid gel prepared in example 3 under ultrasonic, drying at 80 ℃ for 24 hours to obtain a silicic acid/graphite felt composite material, heating the silicic acid/graphite felt composite material to 500 ℃ at a heating rate of 10 ℃/min under air condition, and preserving heat for 5 hours to obtain Si0 2 -graphite felt;
s2, 5g of Si0 2 Graphite felt is immersed in 260mL of bismuth ion immersion liquid, 10mL of NaBH with concentration of 0.5M is added 4 And after the solution is completely reacted, drying the solution in a vacuum oven at 80 ℃ for 24 hours to obtain the iron-chromium redox flow battery electrode material.
Comparative example
In this comparative example, 1g of graphite felt, 0.5g of silicic acid gel and 260mL of bismuth ion impregnation liquid were directly stirred and mixed, and 10mL of NaBH with a concentration of 0.5M was added 4 And after the solution is completely reacted, drying the solution in a vacuum oven at 80 ℃ for 24 hours to obtain the iron-chromium redox flow battery electrode material.
The performance of the iron chromium redox flow battery electrode materials prepared in examples 4-6 and comparative examples was tested.
The electrode material adopts a traditional flow cell structure, and comprises: the perfluorinated cation exchange membrane is used as a proton exchange membrane; graphite plates as current collectors; graphite felt (30 mm x 30 mm) as cathode and anode; 1.0mol/L FeCl 2 +1.0mol/L CrCl 3 +3.0mol/L HCl (50 mL) was used for anolyte and catholyte. The entire cell system is located in a temperature controlled oven which may further ensure that the actual temperature during cell operation is maintained at 65 ℃. The electrolyte was stored in an external reservoir and pumped into the stack by a magnetic circulation pump at a flow rate of 100 mL/min. The current density of charge-discharge cycle is 60-120mA/cm 2 The voltage was 0.8-1.4V and the test results are shown in Table 1 below.
TABLE 1
| Project | VE(60mA/cm 2 ) | VE(120mA/cm 2 ) | EE(60mA/cm 2 ) | EE(120mA/cm 2 ) |
| Example 4 | 86.27％ | 83.32％ | 85.52％ | 82.46％ |
| Example 5 | 86.74％ | 83.16％ | 85.43％ | 82.32％ |
| Example 6 | 86.55％ | 83.21％ | 85.46％ | 82.15％ |
| Comparative example | 83.24％ | 75.43％ | 75.32％ | 55.54％ |
VE represents voltage efficiency and EE represents energy efficiency.
As can be seen from table 1 above, the iron-chromium redox flow battery prepared in the examples of the present invention has better conductivity and negative reactivity than the comparative examples.
Based on the above experiment, at 60mA/cm 2 -120mA/cm 2 The charge and discharge capacities at the current densities were measured, and the results are shown in table 2 below.
TABLE 2
As can be seen from table 2 above, the iron-chromium redox flow battery prepared in the example of the present invention has better charge-discharge capacity stability than the comparative example.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (6)
1. A preparation method of an iron-chromium redox flow battery electrode material is characterized by comprising the following steps of: the method comprises the following steps:
s1, immersing a graphite felt into silicic acid gel for 30-40min under ultrasonic, drying at 80 ℃ for 24h to obtain a silicic acid/graphite felt composite material, heating the silicic acid/graphite felt composite material to 500 ℃ at a heating rate of 10 ℃/min under air condition, and preserving heat for 5h to obtain Si0 2 -graphite felt;
s2, si0 2 -immersing graphite felt in bismuth ion immersing liquid, adding NaBH with concentration of 0.5M 4 Drying the solution in a vacuum oven at 80 ℃ for 24 hours after the reaction is completed, and obtaining the iron-chromium redox flow battery electrode material;
in the step S1, the mass ratio of the graphite felt to the silicic acid gel is 1:0.25-0.5;
the bismuth ion impregnating solution comprises the following steps:
bi (NO) 3 ) 3 ·5H 2 O is dispersed into glycerin, then the glycerin is transferred into a stainless steel autoclave for heat treatment for 12 hours at 160 ℃, after the reaction is finished, the room temperature is naturally cooled, a solid product is obtained through centrifugation and washing, the solid product is dispersed into a mixed solvent of water and ethanol, and bismuth ion impregnating solution is formed under ultrasound.
2. The method for preparing the iron-chromium redox flow battery electrode material according to claim 1, which is characterized by comprising the following steps: in step S2, si0 2 -graphite felt, bismuth ion impregnation liquid and NaBH 4 The dosage ratio of the solution is 4-5g:240-260mL:5-10mL.
3. The method for preparing the iron-chromium redox flow battery electrode material according to claim 1, which is characterized by comprising the following steps: the silicic acid gel is prepared by the following steps:
dissolving sodium silicate in 3M dilute hydrochloric acid for full reaction, filtering, washing and drying to obtain silicic acid powder, dissolving the silicic acid powder in deionized water, and performing ultrasonic dispersion for 30min to obtain silicic acid gel.
4. The method for preparing the iron-chromium redox flow battery electrode material according to claim 1, which is characterized by comprising the following steps: the graphite felt is polyacrylonitrile-based graphite felt, and the thickness is 5mm.
5. The method for preparing the iron-chromium redox flow battery electrode material according to claim 1, which is characterized by comprising the following steps: bi (NO) 3 ) 3 ·5H 2 The dosage ratio of O, glycerol, water and ethanol is 20-25g:70-80mL:40-50mL:190-210mL.
6. An iron chromium redox flow battery electrode material prepared by the preparation method of any one of claims 1-5.
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