CN114639835A - Graphite felt electrode etched with flow channel for all-vanadium redox flow battery and etching method - Google Patents
Graphite felt electrode etched with flow channel for all-vanadium redox flow battery and etching method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 94
- 239000010439 graphite Substances 0.000 title claims abstract description 94
- 238000005530 etching Methods 0.000 title claims abstract description 43
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000010892 electric spark Methods 0.000 claims abstract description 11
- 238000003754 machining Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a graphite felt electrode etched with runners for an all-vanadium redox flow battery and an etching method. The etching method comprises the following steps: a. cleaning the graphite felt electrode; b. the graphite felt electrode is horizontally placed on an xy-axis movable processing table; c. setting etching voltage through a server, translating the xy-axis movable processing table at a fixed speed after starting electric spark processing, and etching a flow channel; d. and cleaning the surface of the graphite felt electrode. The flow channel structure designed by the invention not only improves the diffusion speed of the electrolyte in the graphite felt and reduces the concentration polarization of the flow battery, but also has the advantages of simple etching method operation and simple processing, and has the prospect of large-scale production and preparation.
Description
Technical Field
The invention relates to the field of all-vanadium redox flow batteries, in particular to an etched graphite felt electrode with a flow channel for an all-vanadium redox flow battery and an etching method.
Background
In recent years, renewable energy power generation, particularly wind energy and solar energy, is widely developed and utilized, however, both wind energy and solar energy have the problem of difficulty in grid connection, and the fundamental way for solving the problem is a large-scale energy storage technology. The all-vanadium redox flow battery as a novel electrochemical energy storage device has the advantages of high safety, no charge and discharge frequency limitation, high power and capacity design freedom, low cost, long service life, low maintenance cost, environmental protection and the like, and is a large-scale energy storage battery with the most prospect at present.
The electrode is taken as a key material of the all-vanadium flow battery, and although the electrode directly participates in electrochemical reaction, the electrochemical reaction is generated on the surface of the electrode, so that the three-dimensional structure of the electrode has a large influence on the battery performance. At present, the most widely used electrode of the all-vanadium redox flow battery is graphite felt, which has the characteristics of large specific surface area, high temperature resistance, stable chemical properties and the like, and can maintain stable high-current charge-discharge circulation. Electrolyte flows from a lower liquid inlet to an upper liquid outlet along the longitudinal direction of the graphite felt in the battery, and is diffused in the transverse direction by micro-hole diffusion and capillary action of micron-sized pores in the graphite felt.
Because the pore diameter of the untreated graphite felt is too small, the diffusion speed of the electrolyte is not ideal, and the electrode reaction can generate higher concentration polarization in the battery, thereby seriously reducing the energy efficiency of the battery. In order to increase the diffusion speed of the electrolyte in the graphite felt electrode, methods such as arranging a current guide net, splicing and combining graphite felts with different volume densities, forming a straight flow channel on the graphite felt and the like are mainly adopted at the present stage.
Chinese patent document (patent application number: 201711221936.7) discloses a preparation method of a graphite felt electrode material for a self-flow-channel type flow cell, which relates to the field of all-vanadium flow cells. The preparation method effectively reduces the concentration polarization of the graphite felt electrode of the flow battery, but still has the defects of complex operation, difficult processing, inconvenient assembly and the like.
Disclosure of Invention
The invention aims to solve the defects of the background technology, and provides a graphite felt electrode flow channel structure for an all-vanadium redox flow battery, which can improve the diffusion speed of electrolyte in a graphite felt and reduce the concentration polarization of the redox flow battery.
The invention also aims to provide an etching method for preparing the graphite felt electrode runner structure for the all-vanadium redox flow battery, which is simple to operate and process.
The invention comprises the following contents: the utility model provides a graphite felt electrode that is used for etching of all vanadium redox flow battery to have the runner, the surface of graphite felt electrode separates the etching and has many longitudinal runners, and every runner is arborescent, the runner includes the sprue, the sprue both sides are provided with a plurality of runners.
Preferably, every two branch flow channels are symmetrically distributed on two sides of the main flow channel.
Preferably, the branch runners on each side of the main runner are parallel to each other; and the interval e between adjacent branch flow channels is 20-100 mm.
Preferably, the included angle alpha between each branch flow channel and the main flow channel is 30-45 degrees, and the length g of each branch flow channel is 10-50 mm.
Preferably, the intervals c between the main flow channels are all 20-100 mm.
Preferably, the etching depth i of the flow channel is 1/2-1/5 of the thickness of the graphite felt electrode, and the etching width j of the flow channel is 1-3 times of the depth of the flow channel.
The etching method for the graphite felt electrode etched with the flow channel for the all-vanadium flow battery comprises the following steps:
a. cleaning the graphite felt electrode, and carrying out surface treatment to be smooth and free of unevenness;
b. flatly placing a graphite felt electrode on an xy-axis movable machining table, wherein the distance between the graphite felt electrode and an electrode wire for electric spark machining is 1-3 mm;
c. translating the xy axis to move the processing table and etching the flow channel;
d. and cleaning the surface of the graphite felt electrode to obtain the graphite felt electrode etched with the flow channel for the all-vanadium redox flow battery.
Preferably, in the step c, the etching voltage is 0.5-3 kV.
Preferably, in the step b, the electrode wire for electric spark machining is made of copper wire or titanium wire, and the diameter of the electrode wire is 0.1-1 mm.
The invention also provides an etching machine used by the etching method, which comprises a server and an xy-axis movable processing table, wherein an electrode wire is vertically arranged below the server.
The invention has the following beneficial effects:
1. by etching the nano-scale dendritic flow channel structure on the graphite felt, the battery electrolyte can be diffused at a higher speed in the graphite felt electrode, so that the concentration polarization of the flow battery is effectively reduced, and the energy efficiency of the flow battery is improved.
2. The millimeter-scale flow channel structure of the graphite felt electrode does not change the electrochemical performance and the main body three-dimensional microstructure of the graphite felt electrode, and the service life of the graphite felt electrode is not influenced; meanwhile, the runner etching method only needs to be operated on one graphite felt, does not need subsequent steps, has the characteristics of high precision, high design freedom degree and low cost, is easy for large-scale processing and has extremely wide application range.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The detailed description of the present invention is given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
fig. 1 is a schematic diagram of a graphite felt electrode etched with flow channels for an all-vanadium flow battery provided by the invention;
FIG. 2 is an enlarged view of area A of FIG. 1;
fig. 3 is a partial front view of an etched graphite felt electrode with flow channels for an all-vanadium flow battery according to the present invention;
fig. 4 is a bottom view of a graphite felt electrode part etched with flow channels for an all-vanadium flow battery provided by the invention;
fig. 5 is a schematic diagram of an experimental implementation of a graphite felt electrode etched with flow channels for an all-vanadium flow battery provided by the invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1. graphite felt; 2. a flow channel; 3. a main flow channel; 4. branch flow channels; 5. a server; 6. an electrode wire; 7. the xy-axis can move the processing table.
Detailed Description
The principles and features of the present invention are described below in conjunction with the accompanying fig. 1-5, which are provided as examples to illustrate the invention and not to limit the scope of the invention.
Example 1
The etching machine shown in fig. 5 comprises a servo 5 and an xy-axis movable processing table 7, wherein an electrode wire 6 is vertically arranged below the servo 5.
Example 2
The graphite felt electrode A etched with runners for the all-vanadium redox flow battery comprises a graphite felt 1 with the length, width and height of 800 x 400 x 6mm, a plurality of longitudinal runners 2 are etched on the surface of the graphite felt 1 at intervals, each runner 2 is dendritic, each runner 2 comprises a main runner 3, a plurality of branch runners 4 are arranged on two sides of each main runner 3, and every two branch runners 4 are symmetrically distributed on two sides of each main runner 3. The distance c between each main runner 3 and the edge of the graphite felt 1 is 50mm, the distance d between each main runner 3 and the edge of the graphite felt is 25mm, and the branch runners 4 on each side of each main runner 3 are parallel to each other; the interval e between the adjacent branch flow channels 4 is 50mm, the distance f between the branch flow channels and the lowest end of the graphite felt 1 is 25mm, the length g of each branch flow channel 4 is 30mm, the included angle alpha between each branch flow channel 4 and the main flow channel 3 is 30 degrees, the depth i of each flow channel 2 is 1mm, and the width j of each flow channel 2 is 1 mm.
The method for etching the graphite felt electrode A by using the etching machine in the embodiment 1 comprises the following steps:
a. cleaning the graphite felt 1, and carrying out surface treatment to be smooth and free of unevenness;
b. flatly placing a graphite felt 1 on an xy-axis movable machining table 7, wherein the distance between the graphite felt 1 and an electrode wire for electric spark machining is 1mm, and the electrode wire 6 is a copper wire and has the diameter of 0.2 mm;
c. setting an etching voltage V to be 0.5-0.6 kV through a server 5, translating an xy-axis movable processing table 7 at a fixed speed after starting electric spark processing, and etching a runner 2;
d. and cleaning the surface to finally obtain the graphite felt electrode A etched with the a-structure flow channel.
The graphite felt electrode A was packed in a pile of 11 cells with the same electrode area and at 200mA/cm2The energy efficiency of the charge and discharge at a high current density of (2) was 76.64%, the coulombic efficiency was 95.61%, and the voltage efficiency was 80.16%.
Example 3
The graphite felt electrode B etched with the runners for the all-vanadium redox flow battery comprises a graphite felt 1 with the length, width and height of 800 x 400 x 6mm, a plurality of longitudinal runners 2 are etched on the surface of the graphite felt 1 at intervals, each runner 2 is dendritic, each runner 2 comprises a main runner 3, a plurality of branch runners 4 are arranged on two sides of each main runner 3, and every two branch runners 4 are symmetrically distributed on two sides of each main runner 3. The distance c between each main runner 3 and the edge of the graphite felt 1 is 50mm, the distance d between each main runner 3 and the edge of the graphite felt is 25mm, and the branch runners 4 on each side of each main runner 3 are parallel to each other; the interval e between the adjacent branch flow channels 4 is 50mm, the distance f between the branch flow channels and the lowest end of the graphite felt 1 is 25mm, the length g of each branch flow channel 4 is 30mm, the included angle alpha between each branch flow channel 4 and the main flow channel 3 is 30 degrees, the depth i of each flow channel 2 is 1mm, and the width j of each flow channel 2 is 2 mm.
The method for etching the graphite felt electrode B by using the etching machine in the embodiment 1 comprises the following steps:
a. cleaning the graphite felt 1, and carrying out surface treatment to be smooth and free of unevenness;
b. flatly placing a graphite felt 1 on an xy-axis movable machining table 7, wherein the distance between the graphite felt 1 and an electrode wire for electric spark machining is 1.5mm, and the electrode wire 6 is a copper wire with the diameter of 0.5 mm;
c. setting an etching voltage V to be 1.0-1.2 kV through a server 5, translating an xy-axis movable processing table 7 at a fixed speed after starting electric spark processing, and etching a runner 2;
d. and cleaning the surface to finally obtain the graphite felt electrode B etched with the B-structure flow channel.
The graphite felt electrode B was packed in a pile of 11 cells with the same electrode area and at 200mA/cm2The energy efficiency of the battery is 76.88 percent when the battery is charged and discharged at high current densityThe coulombic efficiency was 95.63% and the voltage efficiency was 80.39%.
Example 4
The utility model provides a graphite felt C that is used for etching of all vanadium redox flow battery to have runner, includes that length width height is 800 x 400 x 6 mm's graphite felt 1, and graphite felt 1 includes that the surface interval is etched many longitudinal runners 2, and every runner 2 is arborescent, and runner 2 includes sprue 3, and sprue 3 both sides are provided with a plurality of branch runners 4, and every two branch runners 4 symmetric distribution are in sprue 3 both sides. The distance c between each main runner 3 and the edge of the graphite felt 1 is 40mm, the distance d between each main runner 3 and the edge of the graphite felt is 20mm, and the branch runners 4 on each side of each main runner 3 are parallel to each other; the interval e between the adjacent branch flow channels 4 is 20mm, the distance f between the branch flow channels and the lowest end of the graphite felt 1 is 10mm, the length g of each branch flow channel 4 is 30mm, the included angle alpha between each branch flow channel and the main flow channel 3 is 30 degrees, the depth i of each flow channel 2 is 1mm, and the width j of each flow channel 2 is 2 mm.
The method for etching the graphite felt electrode C by using the etching machine of the embodiment 1 comprises the following steps:
a. cleaning the graphite felt 1, and carrying out surface treatment to be smooth and free of unevenness;
b. flatly placing a graphite felt 1 on an xy-axis movable machining table 7, wherein the distance between the graphite felt 1 and an electrode wire for electric spark machining is 1.5mm, and the electrode wire 6 is a copper wire with the diameter of 0.5 mm;
c. setting an etching voltage V to be 1.0-1.2 kV through a server 5, translating an xy-axis movable processing table 7 at a fixed speed after starting electric spark processing, and etching a runner 2;
d. and cleaning the surface to finally obtain the graphite felt electrode C etched with the C-structure flow channel.
Graphite felt electrode C was packed in a stack of 11 cells having the same electrode area and at 200mA/cm2The energy efficiency of the charge and discharge at a high current density of (1) was 77.23%, the coulombic efficiency was 95.60%, and the voltage efficiency was 80.78%.
Comparative example 1
In this comparative example, the same graphite felt 1 as in examples 2 to 4, which had not been subjected to channel etching and had a length, width and height of 800 x 400 x 6mm, was used as an electrode, and a stack of 11 cells having the same electrode area was placed in the stack at 200mA/cm2Is charged and discharged at a high current density, which canThe dose efficiency was 75.16%, the coulombic efficiency was 95.19%, and the voltage efficiency was 78.96%.
Examples 2-4 showed improvements in energy efficiency, coulombic efficiency, and voltage efficiency over comparative example 1.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention may be readily implemented by those of ordinary skill in the art as illustrated in the accompanying drawings and described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A graphite felt electrode etched with flow channels for an all-vanadium flow battery comprises a graphite felt (1), and is characterized in that: the graphite felt (1) surface interval etch have many longitudinal runner (2), and every runner (2) are arborescent, the runner includes sprue (3), sprue (3) both sides are provided with a plurality of branch runner (4).
2. The graphite felt electrode etched with flow channels for an all-vanadium flow battery according to claim 1, wherein: every two branch flow channels (4) are symmetrically distributed on two sides of the main flow channel (3).
3. The graphite felt electrode etched with flow channels for an all-vanadium flow battery according to claim 1 or 2, wherein: the branch runners (4) on each side of the main runner (3) are parallel to each other; and the interval e between the adjacent branch flow passages (4) is 20-100 mm.
4. The graphite felt electrode etched with flow channels for an all-vanadium flow battery according to claim 1 or 2, wherein: the included angle alpha between the branch flow channel (4) and the main flow channel (3) is 30-45 degrees, and the length g of the branch flow channel is 10-50 mm.
5. The graphite felt electrode etched with flow channels for an all-vanadium flow battery according to claim 1 or 2, wherein: the distance c between the main flow channels (3) is 20-100 mm.
6. The graphite felt electrode etched with the flow channels for the all-vanadium flow battery as claimed in claim 1, wherein the etching depth i of the flow channels (2) is 1/2-1/5 of the thickness of the graphite felt (1), and the etching width j of the flow channels (2) is 1-3 times of the depth of the flow channels.
7. An etching method for graphite felt electrodes etched with flow channels for all-vanadium flow batteries is characterized by comprising the following steps:
a. cleaning the graphite felt (1), and carrying out surface treatment to be smooth and free of unevenness;
b. flatly placing the graphite felt (1) on an xy-axis movable machining table (7), wherein the distance between the graphite felt (1) and an electrode wire (6) for electric spark machining is 1-3 mm;
c. the xy-axis translation movable processing table (4) is used for etching the flow channel (2);
d. and cleaning the surface of the graphite felt (1) to obtain the graphite felt electrode etched with the flow channel for the all-vanadium flow battery.
8. The etching method for the graphite felt electrode etched with the flow channel for the all-vanadium flow battery as claimed in claim 6, wherein in the step c, the etching voltage is 0.5-3 kV.
9. The etching method for the graphite felt electrode with the flow channel etched for the all-vanadium flow battery according to claim 6, wherein in the step b, the material of the electrode wire (6) subjected to electric spark machining is a copper wire or a titanium wire, and the diameter of the electrode wire is 0.1-1 mm.
10. An etching machine for use in the method of claim 6, wherein: the device comprises a server (5) and an xy-axis movable machining table (7), wherein an electrode wire (6) is vertically arranged below the server (5).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210265317.2A CN114639835A (en) | 2022-03-17 | 2022-03-17 | Graphite felt electrode etched with flow channel for all-vanadium redox flow battery and etching method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210265317.2A CN114639835A (en) | 2022-03-17 | 2022-03-17 | Graphite felt electrode etched with flow channel for all-vanadium redox flow battery and etching method |
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2022
- 2022-03-17 CN CN202210265317.2A patent/CN114639835A/en active Pending
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| CN1632974A (en) * | 2003-12-22 | 2005-06-29 | 中国科学院大连化学物理研究所 | Surface treating method for graphite bipolar plate |
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