CN114267862A - All-vanadium redox flow battery hybrid energy storage system and galvanic pile formed by same - Google Patents
All-vanadium redox flow battery hybrid energy storage system and galvanic pile formed by same Download PDFInfo
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- CN114267862A CN114267862A CN202111612921.XA CN202111612921A CN114267862A CN 114267862 A CN114267862 A CN 114267862A CN 202111612921 A CN202111612921 A CN 202111612921A CN 114267862 A CN114267862 A CN 114267862A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 108
- 238000004146 energy storage Methods 0.000 title claims abstract description 39
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 22
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960003351 prussian blue Drugs 0.000 claims abstract description 18
- 239000013225 prussian blue Substances 0.000 claims abstract description 18
- 238000006722 reduction reaction Methods 0.000 claims abstract description 18
- BQZFDPZOAJMUIU-UHFFFAOYSA-N iron(3+);hexacyanide Chemical compound [Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BQZFDPZOAJMUIU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000012982 microporous membrane Substances 0.000 claims description 13
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 10
- 229910052924 anglesite Inorganic materials 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- -1 iron ferricyanide Chemical compound 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 239000007790 solid phase Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
The invention relates to the technical field of flow batteries, wherein an all-vanadium flow battery hybrid energy storage system comprises a Prussian positive electrode plate and a lead negative electrode plate, wherein the positive electrolyte adopts a tetravalent vanadium acid solution, the negative electrolyte adopts a trivalent vanadium acid solution, and a Pb electrode gradually participates in an electrochemical flow reaction along with the consumption of trivalent vanadium to generate PbSO 4; during discharging, the reduction reaction from ferric ferricyanide to Prussian blue firstly occurs on the positive electrode, and with the consumption of ferric ferricyanide, pentavalent vanadium gradually participates in the electrochemical flow reaction to generate tetravalent vanadium; the method comprises the steps of adopting Prussian blue positive and lead negative electrodes and electrolyte of the all-vanadium flow battery, combining the electrochemical flow reaction of a solid phase and an all-liquid phase, organically combining the two, and improving the capacity of the battery.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to an all-vanadium flow battery hybrid energy storage system and a galvanic pile formed by the same.
Background
The development and utilization of renewable energy sources are important choices for developing strategic emerging industries and promoting the transition of economic development modes. The large-scale development and utilization of renewable energy can obviously reduce the consumption of economic development on fossil energy resources and reduce the damage to the environment, so that the development mode of seriously depending on resource consumption in China is gradually changed into a scientific development mode with less resource consumption and low environmental pollution. Meanwhile, renewable energy is a rapidly growing strategic emerging industry, the effect of developing renewable energy on the development of industries related to the pulling of high-end equipment manufacturing is remarkable, and the significance of promoting the upgrading of industrial structures is great. Renewable energy has the characteristics of discontinuity and instability, and the large-scale grid connection can cause huge impact on a power grid, so that the power grid is paralyzed. Therefore, a specific energy storage device needs to be configured, so that the electric energy quality of the renewable energy is improved, the output is more stable and smooth, and the internet surfing time of the renewable energy is prolonged. Among the numerous energy storage technologies, chemical energy storage is rapidly evolving in that it is highly efficient to convert, and does not require special geographical requirements. Among them, the flow battery has been developed in recent years to become the most promising energy storage technology due to its characteristics of deep charging and discharging, low environmental load, high cost performance in the life cycle, and high energy conversion rate.
The energy storage medium of the all-vanadium redox flow battery is stored in the electrolyte, but the concentration of the electrolyte is limited, so that the volume energy density of the all-vanadium redox flow battery is low. And the electrode is used as a reaction site of the active material of the traditional flow battery. No energy storage takes place thereon, wasting space inside the battery.
The lead-acid battery has mature technology, has a hundred-year development history, and is widely applied to the fields of vehicles, starting and the like. However, lead-acid batteries have limited applications in large-scale energy storage due to their relatively low capacity. The Prussian blue serving as the positive electrode has good application in the field of a plurality of batteries, and therefore the invention provides an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same.
Disclosure of Invention
Technical problem to be solved
The energy storage medium of the all-vanadium redox flow battery in the prior art is stored in electrolyte, but the concentration of the electrolyte is limited, so that the volume energy density of the all-vanadium redox flow battery is low. And the electrode is used as a reaction site of the active material of the traditional flow battery. The invention provides an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same, wherein a Prussian blue electrode of a positive electrode is used as a lead electrode of a negative electrode, an electrolyte of the positive electrode adopts an acid solution of tetravalent vanadium, an electrolyte of the negative electrode adopts an acid solution of trivalent vanadium, and solid-phase energy storage and liquid-phase energy storage are combined, so that the battery capacity and the energy density of the battery are improved.
(II) technical scheme
In order to achieve the purpose, the invention adopts the technical scheme that:
a mixed energy storage system of an all-vanadium redox flow battery comprises a Prussian positive electrode plate and a lead negative electrode plate, wherein the positive electrolyte adopts an acid solution of tetravalent vanadium, the negative electrolyte adopts an acid solution of trivalent vanadium, during charging, the positive electrode firstly generates an oxidation reaction from the tetravalent vanadium to the pentavalent vanadium, and with the consumption of the tetravalent vanadium, Prussian blue gradually participates in an electrochemical flow reaction to generate iron ferricyanide; the reduction reaction from trivalent vanadium to divalent vanadium occurs at the negative electrode, and the Pb electrode gradually participates in the electrochemical flow reaction along with the consumption of the trivalent vanadium to generate PbSO 4; during discharging, the reduction reaction from ferric ferricyanide to Prussian blue firstly occurs on the positive electrode, and with the consumption of ferric ferricyanide, pentavalent vanadium gradually participates in the electrochemical flow reaction to generate tetravalent vanadium; the cathode firstly performs a reduction reaction from PbSO4 to Pb, and divalent vanadium gradually participates in an electrochemical flow reaction along with the consumption of PbSO4 to generate trivalent vanadium;
the positive electrode electrolyte includes: 0.1-4mol/L tetravalent vanadium ion or complex, and the acid concentration is 0.5-5 mol/L;
the negative electrode electrolyte includes: 0.1-4mol/L trivalent vanadium ion or complex, and the acid concentration is 0.5-5 mol/L.
The utility model provides a pile that mixed energy storage system of all vanadium redox flow battery constitutes, includes battery case, battery case's lower extreme fixedly connected with battery base, one side fixedly connected with reaction shell of battery case, battery case's last fixed surface is connected with the metal end plate, the top of metal end plate is provided with four end line connectors, four end line connector sets up in the four corners department of metal end plate, every end line connector still fixes and runs through in insulation board and first mass flow copper, first mass flow copper and second mass flow copper electric connection, the equal fixed connection of metal end plate, insulation board, first mass flow copper and second mass flow copper is on battery case's inner wall.
Preferably, the inner wall of the battery shell is further fixedly connected with a first electrode frame and a second electrode frame, and the first electrode frame and the second electrode frame are symmetrically distributed on the diaphragm plate.
Preferably, the diaphragm plate is fixedly connected to the inner wall of the battery shell, the diaphragm plate comprises a cation membrane, a microporous membrane and an anion membrane, and the cation membrane, the microporous membrane and the anion membrane are fixedly connected to the inner wall of the battery shell.
Preferably, the lower end of the cation membrane is fixedly connected with a microporous membrane, and the lower end of the microporous membrane is fixedly connected with an anion membrane.
Preferably, pins are uniformly arranged on one side of the first current collecting copper plate and one side of the second current collecting copper plate, each pin penetrates through the battery shell and is located inside the reaction shell, a conductive rod is arranged on each pin, and two ends of each conductive rod are fixedly connected to the corresponding pins through insulating bolts.
Preferably, the first electrode frame is structurally communicated with the second electrode frame, an electrode cavity for fixing a Prussian positive electrode plate in a matched mode is formed in the first electrode frame, and a lead negative electrode plate is fixed in the second electrode frame in a matched mode.
Preferably, four corners of the first electrode frame are respectively provided with a first liquid inlet, a first liquid outlet, a second liquid inlet and a second liquid outlet, the first liquid inlet and the first liquid outlet are communicated and diagonally arranged, and the second liquid inlet and the second liquid outlet are communicated and diagonally arranged.
Preferably, the first liquid inlet and the second liquid inlet have the same structure, a main flow channel is arranged at the lower end of the first liquid inlet, the main flow channel is connected with a straight-through pipeline, and the straight-through pipeline is communicated with the first sub flow channel, the second sub flow channel and the third sub flow channel in series.
Preferably, the first subchannel, the second subchannel and the third subchannel are all provided with ion exchange membranes, and the inner walls of the two sides of the first subchannel are both provided with concave-convex surfaces.
Compared with the prior art, the invention has the following beneficial effects:
1. during discharging, the reduction reaction from ferric ferricyanide to Prussian blue firstly occurs on the positive electrode, and with the consumption of ferric ferricyanide, pentavalent vanadium gradually participates in the electrochemical flow reaction to generate tetravalent vanadium; the method comprises the steps that a reduction reaction from PbSO to Pb occurs at a negative electrode, divalent vanadium gradually participates in an electrochemical flow reaction along with the consumption of PbSO to generate trivalent vanadium, and the Prussian blue positive electrode, the lead negative electrode and electrolyte of the all-vanadium flow battery are combined with the electrochemical flow reaction of a solid phase and an all-liquid phase to organically combine the two so as to improve the capacity of the battery.
2. The inlet and the liquid outlet that are equipped with simultaneously are diagonal distribution, prolonged the route of sprue and subchannel, can fully orderly go on in ion reaction for this reason, further through first subchannel, second subchannel and third subchannel series arrangement, make the further dispersion of electrolyte solution, carry out solitary electrochemistry flow reaction, the concave convex surface that is equipped with simultaneously can slow down the speed of electrolyte solution circulation, for electrochemistry flow reaction provides good basis, and then improved battery self battery capacity.
Drawings
FIG. 1 is a schematic structural diagram of an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same;
FIG. 2 is a schematic diagram of the internal structure of an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same;
FIG. 3 is a schematic structural diagram of a galvanic pile layer of a hybrid energy storage system of an all-vanadium redox flow battery and a galvanic pile formed by the same;
FIG. 4 is a schematic structural diagram of an electrode frame of an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same;
FIG. 5 is an enlarged schematic structural diagram of the portion A in FIG. 4 of the all-vanadium redox flow battery hybrid energy storage system and the assembled electric stack according to the present invention;
FIG. 6 is a schematic structural diagram of a sub-runner of an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same;
FIG. 7 is a schematic structural diagram of a diaphragm of an all-vanadium redox flow battery hybrid energy storage system and a galvanic pile formed by the same;
fig. 8 is a schematic structural diagram of an all-vanadium redox flow battery hybrid energy storage system of the invention.
In the figure: 1. a battery case; 2. a metal end plate; 3. an end wire joint; 4. a reaction housing; 5. a battery base; 6. a first current collecting copper plate; 7. a pin; 8. an insulating bolt; 9. a conductive rod; 10. an insulating plate; 11. a first electrode frame; 1101. a first liquid inlet; 1102. an electrode cavity; 1103. a second liquid inlet; 1104. a first liquid outlet; 1105. a second liquid outlet; 1106. a straight pipeline; 1107. a first shunt passage; 1108. a second branch flow channel; 1109. a third shunting passage; 1110. a concave-convex surface; 1111. a main flow channel; 1112. an ion exchange membrane; 12. a Prussian positive electrode plate; 13. a diaphragm plate; 1301. a cationic membrane; 1302. a microporous membrane; 1303. an anionic membrane; 14. a lead negative plate; 15. a second current collecting copper plate; 16. a second electrode frame.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples
As shown in fig. 8, an all-vanadium redox flow battery hybrid energy storage system comprises a prussian positive electrode plate 12 and a lead negative electrode plate 14, wherein the positive electrolyte adopts an acid solution of tetravalent vanadium, the negative electrolyte adopts an acid solution of trivalent vanadium, during charging, the positive electrode firstly undergoes an oxidation reaction from tetravalent vanadium to pentavalent vanadium, and prussian blue gradually participates in an electrochemical flow reaction along with the consumption of tetravalent vanadium to generate iron ferricyanide; the reduction reaction from trivalent vanadium to divalent vanadium occurs at the negative electrode, and the Pb electrode gradually participates in the electrochemical flow reaction along with the consumption of the trivalent vanadium to generate PbSO 4; during discharging, the reduction reaction from ferric ferricyanide to Prussian blue firstly occurs on the positive electrode, and with the consumption of ferric ferricyanide, pentavalent vanadium gradually participates in the electrochemical flow reaction to generate tetravalent vanadium; the cathode firstly performs a reduction reaction from PbSO4 to Pb, and divalent vanadium gradually participates in an electrochemical flow reaction along with the consumption of PbSO4 to generate trivalent vanadium;
the positive electrode electrolyte includes: 0.1-4mol/L tetravalent vanadium ion or complex, and the acid concentration is 0.5-5 mol/L;
the negative electrode electrolyte includes: 0.1-4mol/L trivalent vanadium ion or complex, and the acid concentration is 0.5-5 mol/L.
As shown in fig. 1 to 7, the galvanic pile formed by the all-vanadium redox flow battery hybrid energy storage system comprises a battery shell 1, wherein a battery base 5 is fixedly connected to the lower end of the battery shell 1, a reaction shell 4 is fixedly connected to one side of the battery shell 1, a metal end plate 2 is fixedly connected to the upper surface of the battery shell 1, four end wire connectors 3 are arranged at the top of the metal end plate 2, the four end wire connectors 3 are arranged at four corners of the metal end plate 2, each end wire connector 3 is further fixedly penetrated through an insulating plate 10 and a first current collecting copper plate 6, the first current collecting copper plate 6 is electrically connected with a second current collecting copper plate 15, and the metal end plate 2, the insulating plate 10, the first current collecting copper plate 6 and the second current collecting copper plate 15 are all fixedly connected to the inner wall of the battery shell 1.
In this embodiment, the inner wall of the battery case 1 is further fixedly connected with a first electrode frame 11 and a second electrode frame 16, the first electrode frame 11 and the second electrode frame 16 are symmetrically distributed by a diaphragm plate 13, the diaphragm plate 13 is fixedly connected to the inner wall of the battery case 1, the diaphragm plate 13 includes a cation membrane 1301, a microporous membrane 1302 and an anion membrane 1303, the cation membrane 1301, the microporous membrane 1302 and the anion membrane 1303 are all fixedly connected to the inner wall of the battery case 1, the lower end of the cation membrane 1301 is fixedly connected with the microporous membrane 1302, the lower end of the microporous membrane 1302 is fixedly connected with the anion membrane 1303, the positive electrolyte adopts 0.5-5 mol/L acid solution of 0.1-4mol/L tetravalent vanadium, and the negative electrolyte adopts 0.5-5 mol/L acid solution of 0.1-4mol/L trivalent vanadium. During charging, the positive electrode firstly generates oxidation reaction from tetravalent vanadium to pentavalent vanadium, and with the consumption of the tetravalent vanadium, the Prussian blue gradually participates in electrochemical flow reaction to generate ferric ferricyanide; the reduction reaction from trivalent vanadium to divalent vanadium occurs at the negative electrode, and the Pb electrode gradually participates in the electrochemical flow reaction along with the consumption of the trivalent vanadium to generate PbSO 4; during discharge, the positive electrode firstly undergoes a reduction reaction from ferric ferricyanide to prussian blue.
In this embodiment, pins 7 are integrally disposed on one side of the first copper current collecting plate 6 and one side of the second copper current collecting plate 15, each pin 7 penetrates through the battery case 1 and is located inside the reaction case 4, a conductive rod 9 is disposed on each pin 7, two ends of each conductive rod 9 are fixedly connected to the corresponding pin 7 through an insulating bolt 8, the first electrode frame 11 and the second electrode frame 16 are structurally communicated, an electrode cavity 1102 matched and fixed with the prussian positive electrode plate 12 is disposed on the first electrode frame 11, a lead negative electrode plate 14 is matched and fixed on the second electrode frame 16, a first liquid inlet 1101, a first liquid outlet 1104, a second liquid inlet 1103 and a second liquid outlet 1105 are respectively disposed at four corners of the first electrode frame 11, the first liquid inlet 1101 is communicated with the first liquid outlet and is diagonally disposed, the second liquid inlet 1103 is communicated with the second liquid outlet 1105 and is diagonally disposed, with the consumption of ferricyanide, pentavalent vanadium gradually participates in electrochemical flow reaction to generate tetravalent vanadium; the cathode firstly generates a reduction reaction from PbSO4 to Pb, divalent vanadium gradually participates in an electrochemical flow reaction along with the consumption of PbSO4 to generate trivalent vanadium, and the electrochemical flow reaction of a solid phase and an all-liquid phase is combined by adopting Prussian blue positive and lead negative electrodes and an electrolyte of an all-vanadium flow battery.
In this embodiment, the first inlet 1101 and the second inlet 1103 have the same structure, a main channel 1111 is disposed at the lower end of the first inlet 1101, the main channel 1111 is connected to the through pipe 1106, the through pipe 1106 is connected in series to the first sub-channel 1107, the second sub-channel 1108 and the third sub-channel 1109, and the liquid inlets and outlets disposed at the same time are diagonally distributed, so that the paths of the main channel 1111 and the sub-channels are extended, and therefore, the ion reaction can be fully and orderly performed, and further, the electrolyte solution is further dispersed by the series arrangement of the first sub-channel 1107, the second sub-channel 1108 and the third sub-channel 1109.
In this embodiment, the ion exchange membrane 1112 is disposed on each of the first sub-flow channel 1107, the second sub-flow channel 1108 and the third sub-flow channel 1109, concave-convex surfaces 1110 are disposed on inner walls of two sides of the first sub-flow channel 1107 to perform an independent electrochemical flow reaction, and the concave-convex surfaces 1110 disposed on the inner walls of the two sides of the first sub-flow channel 1107 can slow down the circulation rate of the electrolyte solution, thereby providing a good basis for the electrochemical flow reaction and further improving the battery capacity of the battery.
The working principle of the all-vanadium redox flow battery hybrid energy storage system and the galvanic pile formed by the same is as follows: the positive electrolyte adopts 0.5-5 mol/L acid solution of 0.1-4mol/L tetravalent vanadium, and the negative electrolyte adopts 0.5-5 mol/L acid solution of 0.1-4mol/L trivalent vanadium. During charging, the positive electrode firstly generates oxidation reaction from tetravalent vanadium to pentavalent vanadium, and with the consumption of the tetravalent vanadium, the Prussian blue gradually participates in electrochemical flow reaction to generate ferric ferricyanide; the reduction reaction from trivalent vanadium to divalent vanadium occurs at the negative electrode, and the Pb electrode gradually participates in the electrochemical flow reaction along with the consumption of the trivalent vanadium to generate PbSO 4; during discharging, the reduction reaction from ferric ferricyanide to Prussian blue firstly occurs on the positive electrode, and with the consumption of ferric ferricyanide, pentavalent vanadium gradually participates in the electrochemical flow reaction to generate tetravalent vanadium; the method comprises the steps that a reduction reaction from PbSO4 to Pb occurs at the negative electrode, divalent vanadium gradually participates in an electrochemical flow reaction along with the consumption of PbSO4 to generate trivalent vanadium, and the Prussian blue positive electrode, the lead negative electrode and electrolyte of the all-vanadium flow battery are combined with the electrochemical flow reaction of a solid phase and an all-liquid phase to organically combine the two, so that the battery capacity is improved.
The inlet and the liquid outlet that are equipped with simultaneously are diagonal distribution, the route of sprue 1111 and subchannel has been prolonged, can be fully orderly go on for this reason in ionic reaction, further through first minute runner 1107, second minute runner 1108 and third minute runner 1109 series arrangement, make further the scattering of electrolyte solution, carry out solitary electrochemistry flow reaction, the speed that electrolyte solution circulated can be slowed down to the unsmooth face 1110 that is equipped with simultaneously, good basis is provided for electrochemistry flow reaction, and then the battery capacity of battery self has been improved.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. An all-vanadium redox flow battery hybrid energy storage system comprises a Prussian positive electrode plate (12) and a lead negative electrode plate (14), and is characterized in that: the positive electrolyte adopts an acid solution of tetravalent vanadium, the negative electrolyte adopts an acid solution of trivalent vanadium, during charging, the positive electrode firstly undergoes an oxidation reaction from tetravalent vanadium to pentavalent vanadium, and with the consumption of tetravalent vanadium, prussian blue gradually participates in an electrochemical flow reaction to generate iron ferricyanide; the reduction reaction from trivalent vanadium to divalent vanadium occurs at the negative electrode, and the Pb electrode gradually participates in the electrochemical flow reaction along with the consumption of the trivalent vanadium to generate PbSO 4; during discharging, the reduction reaction from ferric ferricyanide to Prussian blue firstly occurs on the positive electrode, and with the consumption of ferric ferricyanide, pentavalent vanadium gradually participates in the electrochemical flow reaction to generate tetravalent vanadium; the cathode firstly performs a reduction reaction from PbSO4 to Pb, and divalent vanadium gradually participates in an electrochemical flow reaction along with the consumption of PbSO4 to generate trivalent vanadium;
the positive electrode electrolyte includes: 0.1-4mol/L tetravalent vanadium ion or complex, and the acid concentration is 0.5-5 mol/L;
the negative electrode electrolyte includes: 0.1-4mol/L trivalent vanadium ion or complex, and the acid concentration is 0.5-5 mol/L.
2. An all-vanadium redox flow battery hybrid energy storage system electric stack according to claim 1, comprising a battery housing (1), characterized in that: the lower extreme fixedly connected with battery base (5) of battery case (1), one side fixed connection of battery case (1) has reaction shell (4), the last fixed surface of battery case (1) is connected with metal end plate (2), the top of metal end plate (2) is provided with four end line connectors (3), four end line connectors (3) set up in the four corners department of metal end plate (2), every end line connector (3) still fixed run through in insulation board (10) and first mass flow copper (6), first mass flow copper (6) and second mass flow copper (15) electric connection, the equal fixed connection of metal end plate (2), insulation board (10), first mass flow copper (6) and second mass flow copper (15) is on the inner wall of battery case (1).
3. The electric stack composed of the all-vanadium redox flow battery hybrid energy storage system according to claim 2, characterized in that: the inner wall of the battery shell (1) is further fixedly connected with a first electrode frame (11) and a second electrode frame (16), and the first electrode frame (11) and the second electrode frame (16) are symmetrically distributed through a diaphragm plate (13).
4. The galvanic pile formed by the all-vanadium redox flow battery hybrid energy storage system according to claim 3, characterized in that: the diaphragm plate (13) is fixedly connected to the inner wall of the battery shell (1), the diaphragm plate (13) comprises a cation membrane (1301), a microporous membrane (1302) and an anion membrane (1303), and the cation membrane (1301), the microporous membrane (1302) and the anion membrane (1303) are fixedly connected to the inner wall of the battery shell (1).
5. The galvanic pile formed by the all-vanadium redox flow battery hybrid energy storage system according to claim 4, characterized in that: the lower end of the cation membrane (1301) is fixedly connected with a microporous membrane (1302), and the lower end of the microporous membrane (1302) is fixedly connected with an anion membrane (1303).
6. The electric stack composed of the all-vanadium redox flow battery hybrid energy storage system according to claim 2, characterized in that: pins (7) are uniformly arranged on one side of the first current collecting copper plate (6) and one side of the second current collecting copper plate (15), each pin (7) penetrates through the battery shell (1) and is located inside the reaction shell (4), a conducting rod (9) is arranged on each pin (7), and two ends of each conducting rod (9) are fixedly connected to the corresponding pins (7) through insulating bolts (8).
7. The electric stack composed of the all-vanadium redox flow battery hybrid energy storage system according to claim 2, characterized in that: the structure of the first electrode frame (11) is communicated with that of the second electrode frame (16), an electrode cavity (1102) matched and fixed with a Prussian positive electrode plate (12) is formed in the first electrode frame (11), and a lead negative electrode plate (14) is matched and fixed with the second electrode frame (16).
8. The electric stack composed of the all-vanadium redox flow battery hybrid energy storage system according to claim 7, characterized in that: first inlet (1101), first liquid outlet (1104), second inlet (1103) and second liquid outlet (1105) have been seted up respectively to the four corners of first electrode frame (11), first inlet (1101) and first liquid outlet (1104) communicate with each other and diagonal angle sets up, second inlet (1103) and second liquid outlet (1105) communicate with each other and diagonal angle sets up.
9. The electric stack composed of the all-vanadium redox flow battery hybrid energy storage system according to claim 8, characterized in that: the structure of the first liquid inlet (1101) is the same as that of the second liquid inlet (1103), a main flow channel (1111) is arranged at the lower end of the first liquid inlet (1101), the main flow channel (1111) is connected with a straight-through pipeline (1106), and the straight-through pipeline (1106) is communicated with a first branch flow channel (1107), a second branch flow channel (1108) and a third branch flow channel (1109) in series.
10. The electric stack composed of the all-vanadium redox flow battery hybrid energy storage system according to claim 9, characterized in that: the ion exchange membrane (1112) is arranged on each of the first sub-flow passage (1107), the second sub-flow passage (1108) and the third sub-flow passage (1109), and concave-convex surfaces (1110) are arranged on the inner walls of the two sides of the first sub-flow passage (1107).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842730A (en) * | 2012-09-27 | 2012-12-26 | 北京金能世纪科技有限公司 | All-vanadium flow battery |
| CN104143660B (en) * | 2013-05-09 | 2017-02-08 | 中国科学院大连化学物理研究所 | Plumbic acid-all vanadium mixed energy storage battery |
| CN109713322A (en) * | 2018-11-22 | 2019-05-03 | 长沙理工大学 | Preparation method of Prussian blue modified electrode |
| CN209447939U (en) * | 2019-01-26 | 2019-09-27 | 杭州德海艾科能源科技有限公司 | A kind of tandem electrode of liquid flow cell frame and its battery stack |
| US20210249656A1 (en) * | 2018-10-17 | 2021-08-12 | Contemporary Amperex Technology Co., Limited | Negative electrode sheet and battery |
-
2021
- 2021-12-27 CN CN202111612921.XA patent/CN114267862A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842730A (en) * | 2012-09-27 | 2012-12-26 | 北京金能世纪科技有限公司 | All-vanadium flow battery |
| CN104143660B (en) * | 2013-05-09 | 2017-02-08 | 中国科学院大连化学物理研究所 | Plumbic acid-all vanadium mixed energy storage battery |
| US20210249656A1 (en) * | 2018-10-17 | 2021-08-12 | Contemporary Amperex Technology Co., Limited | Negative electrode sheet and battery |
| CN109713322A (en) * | 2018-11-22 | 2019-05-03 | 长沙理工大学 | Preparation method of Prussian blue modified electrode |
| CN209447939U (en) * | 2019-01-26 | 2019-09-27 | 杭州德海艾科能源科技有限公司 | A kind of tandem electrode of liquid flow cell frame and its battery stack |
Non-Patent Citations (1)
| Title |
|---|
| 李华: "普鲁士蓝对钒电池中V（V）/V（IV）的电催化", 《电源技术》, vol. 28, no. 3, 31 March 2004 (2004-03-31), pages 167 - 169 * |
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