CN113422081A - Electrode material of flow battery and application - Google Patents

Electrode material of flow battery and application Download PDF

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Publication number
CN113422081A
CN113422081A CN202110621313.9A CN202110621313A CN113422081A CN 113422081 A CN113422081 A CN 113422081A CN 202110621313 A CN202110621313 A CN 202110621313A CN 113422081 A CN113422081 A CN 113422081A
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Prior art keywords
electrode
electrode material
flow battery
flow
folding
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CN202110621313.9A
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马相坤
乔琳
李海霞
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Dalian Maritime University
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Dalian Maritime University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a flow battery electrode material and application thereof, wherein the electrode material is reconstructed by a porous carbon material in a filter paper corrugation folding mode, the corrugation folding height is the electrode thickness, the corrugation folding height of the electrode material is 0.1-10mm, the corrugation folding gap is 0-1mm, and a plurality of corrugations are fixed in series by a carbon fiber material. The electrode material reconstructed by using porous materials such as carbon paper, carbon cloth and the like has higher specific surface area, can shorten electron and proton conduction paths and reduce the flow resistance of electrolyte, can adjust the thickness and the local structure of the electrode according to the thickness of an electrode frame, has better convenience for adjusting the thickness and the structure of the electrode in practical application, can effectively improve the performance of the flow battery, and has an important effect on promoting the development of the flow battery.

Description

Electrode material of flow battery and application
Technical Field
The invention relates to the field of flow batteries, in particular to a flow battery electrode material and application thereof.
Background
With the development of economy, the demand for energy is increasing, and environmental problems caused by the large consumption of fossil energy are becoming more prominent. The method utilizes renewable energy resources on a large scale, and realizes energy diversification as an important strategy for energy safety and sustainable development of countries in the world. However, the discontinuity and instability of renewable energy sources such as wind energy and solar energy make their direct utilization difficult, so that the continuous supply of renewable energy sources by using energy storage technology becomes the key to solve the above problems. The redox flow battery is an electrochemical energy storage device which utilizes the valence state change of chemical elements stored in electrolyte to realize energy storage and release, and has the advantages of flexible design (energy and power separated design), good safety and long design life, thus becoming one of the technologies with the best prospects in large-scale energy storage markets.
The electrode is used as a reaction place of the flow battery, and the specific surface area of the electrode needs to be increased, active sites are increased, the catalytic activity of the electrode is improved, and meanwhile, the electrode has smaller electrolyte flow resistance. The commonly used electrode types comprise porous carbon materials such as carbon paper, carbon cloth, carbon fiber felt and the like, wherein the carbon fiber felt is the most commonly used, but the carbon fiber felt has a low specific surface area, a large thickness and is not easy to adjust, and the electron and ion mass transfer resistance and the flow resistance are large, so that the development of a thin electrode material with a high specific surface area and low flow resistance is needed, and the method has important significance for the development of a flow battery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a flow battery electrode material and application thereof.
The purpose of the invention is realized by the following technical scheme: a flow battery electrode material is reconstructed by a filter paper-like corrugated folding mode of porous carbon materials, and the height of the corrugated folding is the thickness of an electrode.
Based on the technical scheme, preferably, the folding height of the corrugations of the electrode material is 0.1-10mm, the folding gaps of the corrugations are 0-1mm, and a plurality of corrugations can be fixed together in series by materials such as carbon fiber wires.
Based on the technical scheme, the porous carbon material is preferably carbon paper, carbon cloth and the like, and is preferably a flexible and foldable material.
Based on the above technical means, it is preferable that the thickness of the porous carbon material is 0.1 to 2mm, and the ratio of the longitudinal fibers in the folding direction is preferably large.
Based on the above technical solution, preferably, the folding and reconstructing process of the porous carbon material may be performed before, after or between the carbonizing or graphitizing and activating processes, that is, the folding and reconstructing process may be performed first, then the carbonizing or graphitizing and activating process may be performed, the carbonizing or graphitizing and activating process may be performed first, then the folding and reconstructing process may be performed, and then the folding and reconstructing process may be performed first, or the carbonizing or graphitizing process may be performed first, and then the activating process may be performed.
Based on the above technical solution, preferably, the carbonization conditions are as follows: calcining for 1-3h at the temperature of 1000-: calcining for 1-3h at the temperature of 2000-3000 ℃ under the protection of inert gas (argon); the activating conditions are as follows: heating for 6-8h at the temperature of 600 ℃ in air at 300-.
Based on the technical scheme, the electrode material ripple gap provides an auxiliary channel for the flow of the electrolyte, the form of the auxiliary channel is not limited, and the flow guide of the electrolyte is realized.
Based on the technical scheme, the electrode corrugated folding gap is used for inserting substances such as auxiliary components, auxiliary materials, catalysts and the like, and specific porous materials such as other carbon paper, carbon cloth, carbon fibers, nano materials and the like or substances such as catalysts and the like can be added in the electrode corrugated gap, so that the adjustment of the specific surface area, the active sites and the catalytic activity of the electrode material local materials is realized.
The invention also relates to an application of the electrode material, wherein the electrode material can be applied to redox flow batteries such as all-vanadium redox flow batteries, iron-chromium redox flow batteries and the like, and the specific application comprises two schemes:
the first scheme is as follows: the electrode material may be placed in the flow field in such a way that the direction of the electrode corrugation gaps is parallel to the electrolyte flow direction, through which electrolyte flows through the electrode material.
Scheme II: the electrode material may be placed in the flow field in such a way that the direction of the electrode corrugation gap is perpendicular to the electrolyte flow direction, the electrolyte flowing perpendicularly through the electrode corrugations and out of the electrode.
The invention has the beneficial effects that:
the electrode material reconstructed by using porous materials such as carbon paper, carbon cloth and the like has higher specific surface area, can shorten electron and proton conduction paths and reduce the flow resistance of electrolyte, can adjust the thickness and the local structure of the electrode according to the thickness of an electrode frame, has better convenience for adjusting the thickness and the structure of the electrode in practical application, can effectively improve the performance of the flow battery, and has an important effect on promoting the development of the flow battery.
Drawings
Fig. 1 is a schematic structural diagram of an electrode material of a flow battery.
Fig. 2 is a schematic structural view of a single cell structure.
In the figure: 1. a corrugation fold height; 2. a corrugated folding gap; 3. the width of the electrode; 4. electrode length.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
1. Preparing an electrode:
firstly, reconstructing an electrode material, wherein the adopted carbon cloth is woven by non-carbonized polyacrylonitrile pre-oxidized fibers, the carbon cloth is woven in a cross-shaped mode, the thickness of the carbon cloth is 0.2mm, and the proportion of longitudinal fibers along the folding direction is preferably more. And (3) performing corrugation folding reconstruction on the carbon cloth, as shown in the attached drawing 1, wherein the corrugation folding height is 3mm, the corrugation folding gap is 0.1mm, and carbon fiber wires are adopted for corrugated serial connection fixation.
And calcining the reconstructed carbon cloth at 1300 ℃ for 3h for carbonization under the protection of argon gas, and then heating the carbon cloth in the air at 350 ℃ for 6h for activation to complete the preparation of the electrode material.
Finally, the electrode material was cut to a size of 3x3cm2(electrode length x electrode width).
2. Assembling the battery:
the single cell was assembled with a positive electrode terminal plate, a positive electrode, a separator (Nafion211), a negative electrode, and a negative electrode terminal plate in this order, as shown in fig. 2, the prepared electrode material was used as the positive and negative electrodes, and the composition of the electrolyte was 0.8mol/L V3+And 0.8mol/L VO2+And 3mol/L of H2SO4The electrodes are placed in the flow field in a mode that the direction of the electrode ripple gaps is parallel to the flowing direction of electrolyte, and the electrolyte flows through the electrode materials through the electrode ripple gaps.
3. And (3) testing the battery:
the flow rate of the electrolyte is 50ml/min, and the charge-discharge current density is 200mA/cm2The average energy efficiency of the battery reaches about 80%, and the cycle life of the battery is more than 10000.
Example 2
1. Preparing an electrode:
firstly, carbonizing and activating the electrode, wherein the adopted carbon cloth is woven by non-carbonized polyacrylonitrile pre-oxidized fibers, the carbon cloth is woven in a cross-shaped mode, the thickness of the carbon cloth is 0.2mm, and the carbon cloth is suitable for the majority of longitudinal fibers along the folding direction. The carbon cloth is calcined at 1300 ℃ for 3h for carbonization under the protection of argon gas, and then heated at 350 ℃ for 6h in the air for activation.
And then, performing corrugation folding reconstruction on the carbonized and activated carbon cloth, wherein the corrugation folding height is 3mm and the corrugation folding gap is 0.1mm as shown in the attached drawing 1, and performing series connection and fixation on corrugations by adopting carbon fiber wires to finish the preparation of the electrode material.
Finally, the electrode material was cut to a size of 3x3cm2(electrode length x electrode width).
2. Assembling the battery:
the single cell was assembled with a positive electrode terminal plate, a positive electrode, a separator (Nafion211), a negative electrode, and a negative electrode terminal plate in this order, as shown in fig. 2, the prepared electrode material was used as the positive and negative electrodes, and the composition of the electrolyte was 0.8mol/L V3+And 0.8mol/L VO2+And 3mol/L of H2SO4The electrodes are placed in the flow field in a mode that the electrode corrugation gap direction is perpendicular to the electrolyte flow direction, and the electrolyte vertically flows through the electrode corrugations and flows out of the electrodes.
3. And (3) testing the battery:
the flow rate of the electrolyte is 50ml/min, and the charge-discharge current density is 200mA/cm2The average energy efficiency of the battery reaches about 80%, and the cycle life of the battery is more than 10000.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims (10)

1. A flow battery electrode material, characterized in that: the electrode material is reconstructed from a porous carbon material in a corrugated folding mode, and the corrugated folding height is the thickness of the electrode.
2. The flow battery electrode material of claim 1, wherein: the folding height of the corrugations of the electrode material is 0.1-10mm, the folding gaps of the corrugations are 0-1mm, and the plurality of corrugations are fixed in series by carbon fiber materials.
3. The flow battery electrode material of claim 1, wherein: the porous carbon material is carbon paper or carbon cloth, and the thickness of the porous carbon material is 0.1-2 mm.
4. The flow battery electrode material of claim 1, wherein: the folding and restructuring process of the porous carbon material can be performed before, after or between carbonization or graphitization and activation processes.
5. The electrode material according to claim 4, wherein: the carbonization conditions are as follows: calcining for 1-3h at the temperature of 1000-2000 ℃ under the protection of inert gas; the graphitization conditions are as follows: calcining for 1-3h at 3000 ℃ under the protection of inert gas at 2000-; the activating conditions are as follows: heating for 6-8h at the temperature of 600 ℃ in air at 300-.
6. The flow battery electrode material of claim 1, wherein: the corrugated gap is an electrolyte flow auxiliary channel.
7. The flow battery electrode material of claim 1, wherein: the electrode corrugated folding gap is used for inserting auxiliary components, auxiliary materials or catalysts.
8. Use of the electrode material of any one of claims 1-7 in a flow battery.
9. Use according to claim 8, characterized in that: the electrode material is placed in the flow field in a mode that the electrode ripple gap direction is parallel to the electrolyte flow direction, and the electrolyte flows through the electrode material through the electrode ripple gap.
10. Use according to claim 8, characterized in that: the electrode material can be placed in the flow field in a mode that the electrode corrugation gap direction is perpendicular to the electrolyte flow direction, and the electrolyte vertically flows through the electrode corrugations and flows out of the electrode.
CN202110621313.9A 2021-06-03 2021-06-03 Electrode material of flow battery and application Pending CN113422081A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116072907A (en) * 2022-12-09 2023-05-05 大连海事大学 Electrode bipolar plate integrated material of flow battery and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162496A (en) * 1997-11-25 1999-06-18 Sumitomo Electric Ind Ltd Carbon felt dipole plate and its forming method
CN1510776A (en) * 2002-12-25 2004-07-07 中国科学技术大学 Battery device with foldable electrodes
US20090042097A1 (en) * 2007-08-09 2009-02-12 Masato Fujikawa Negative electrode current collector for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery
CN103972514A (en) * 2014-04-21 2014-08-06 江西师范大学 Novel three-dimensional nano carbon/stainless steel mesh compound biological anode as well as preparation method and application thereof
CN204558585U (en) * 2015-03-16 2015-08-12 中国科学院宁波材料技术与工程研究所 A kind of metal air battery cathodes structure
US20170025698A1 (en) * 2014-04-11 2017-01-26 Showa Denko K.K. Redox flow battery
WO2021045614A1 (en) * 2019-09-05 2021-03-11 Technische Universiteit Delft Compact electrochemical stack using corrugated electrodes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162496A (en) * 1997-11-25 1999-06-18 Sumitomo Electric Ind Ltd Carbon felt dipole plate and its forming method
CN1510776A (en) * 2002-12-25 2004-07-07 中国科学技术大学 Battery device with foldable electrodes
US20090042097A1 (en) * 2007-08-09 2009-02-12 Masato Fujikawa Negative electrode current collector for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery
US20170025698A1 (en) * 2014-04-11 2017-01-26 Showa Denko K.K. Redox flow battery
CN103972514A (en) * 2014-04-21 2014-08-06 江西师范大学 Novel three-dimensional nano carbon/stainless steel mesh compound biological anode as well as preparation method and application thereof
CN204558585U (en) * 2015-03-16 2015-08-12 中国科学院宁波材料技术与工程研究所 A kind of metal air battery cathodes structure
WO2021045614A1 (en) * 2019-09-05 2021-03-11 Technische Universiteit Delft Compact electrochemical stack using corrugated electrodes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116072907A (en) * 2022-12-09 2023-05-05 大连海事大学 Electrode bipolar plate integrated material of flow battery and preparation method and application thereof

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