CN106558704A - A kind of flow battery gradient electrode and its application - Google Patents
A kind of flow battery gradient electrode and its application Download PDFInfo
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- CN106558704A CN106558704A CN201510621446.0A CN201510621446A CN106558704A CN 106558704 A CN106558704 A CN 106558704A CN 201510621446 A CN201510621446 A CN 201510621446A CN 106558704 A CN106558704 A CN 106558704A
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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
- H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
- H01M4/8642—Gradient in composition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
A kind of flow battery gradient electrode is laminated by body density from low to high and is constituted by the graphite fibre or carbon fiber felt that at least two-layer has different body density, and is formed integrally by the longitudinal acupuncture perpendicular to electrode surface.This electrode can effectively reduce electrode body resistance, and reduce the flow resistance of electrolyte and provide more reacting environment, the final ohmic polarization for reducing flow battery, activation polarization and concentration polarization.The present invention improves the energy efficiency and voltage efficiency of flow battery, so as to improve its working current density so that the battery weight of identical output, volume and cost are substantially reduced.
Description
Technical field
The present invention relates to the flow battery field in chemical energy storage technology, the more particularly to electrode of all-vanadium flow battery.
Background technology
Output and capacity are separate because which has for all-vanadium flow battery, and system design is flexible；Energy efficiency is high, life-span length,
Operation stability and reliability are high, and self discharge is low；Addressing degree of freedom is big, and pollution-free, maintenance is simple, and operation cost is low, safety
Property it is high the advantages of, there is vast potential for future development, it is considered to be solve solar energy, the renewable energy such as wind energy in terms of scale energy storage
The effective ways of source electricity generation system randomness and intermittent unstable state feature, have in renewable energy power generation and intelligent grid construction
Great demand.
Different from the function of general chemistry power electrode, the electrode of flow battery is the place of chemical energy storage system charge and discharge reaction,
The electrode of this kind of battery is not involved in electrochemical reaction in itself, and the active substance in electrolyte solution receives in electrode surface or provides electricity
Son come complete battery chemistries reaction, carry out the transformation between electric energy and chemical energy and realize the storage or release of energy.
Critical component one of of the electrode as flow battery, impact of its performance to flow battery is very big.Its electrical conductivity is directly affected
The ohmic internal resistance of battery；Its porosity and pore structure influence whether transfer rate of the active substance in electrode interface；Its electricity
Chemical catalysis activity is also directly determined the intrinsic reaction rate of electrochemical reaction, and in a word, electrode material affects the electrification of battery
Polarization, concentration polarization and ohmic polarization are learned, has been related to whole elements of battery electrochemical impedance.These key elements are very big
The working current density and energy efficiency of battery are affected in degree.
At present, the working current density of flow battery operation is relatively low, causes battery module volume big, and materials demand amount is big, cost
It is high.The cost of whole system and the raising of working current density can improve the power density of battery, is reduced, energy-storage system is reduced
Floor space and space, improve the mobility of its adaptive capacity to environment and system, extend the application of flow battery.
Improve flow battery working current density need to reduce as much as possible battery polarization, i.e. ohmic polarization, activation polarization and
Concentration polarization, reduces voltage loss.
Method in published patent documentation for reducing flow battery polarization mainly has at present：
(1) electrode material such as graphite felt, carbon paper etc. are metallized or oxidation modification is processed, the gold in carbon fiber surface modification
Category ion or oxygen-containing functional group, improve the electro catalytic activity of electrode, reduce the activation polarization of battery, such as patent CN
The method that electrochemical oxidation is carried out to graphite felt disclosed in 101465417A and CN 101182678A.But this kind of method simply subtracts
The little activation polarization of battery, the ohmic polarization to reducing battery are not helped.And the reduction of ohmic polarization is for raising battery
Working current density for it is more important because activation polarization is directly proportional to the logarithm of electric current, and ohmic voltage drop then and electricity
The size of stream is directly proportional.Therefore, with the raising of working current density, the impact of battery ohmic internal resistance can be increasing.
(2) research and develop the electrode combination electrode integrated with bipolar plates, i.e. integrated pole dual-pole board to reduce electrode bipolar
Contact resistance between plate.As disclosed in CN 101009376A, bipolar plates are bondd by conductive bonding material with porous electrode
Integrated pole dual-pole board is formed together.However, the ohmic internal resistance of all-vanadium flow battery mainly includes electrode, bipolar plates, electricity
Contact resistance between the bulk resistance and electrode and bipolar plates of solution liquid and barrier film.The method is simply reduced between pole dual-pole board
Contact resistance, has no impact to the bulk resistance for accounting for the larger electrode of internal resistance of cell proportion and electrolyte, therefore for voltage efficiency
With the raising limitation of energy efficiency.
The content of the invention
The present invention is intended to provide a kind of flow battery gradient electrode, density, surface area and porosity which has Gradient distribution,
The good mobility of electrolyte can be ensured, activation polarization and the concentration polarization of flow battery can be reduced, improve the work of battery
Electric current density, to reach the purpose for improving cell power density.
For achieving the above object, the technical solution used in the present invention is：
A kind of gradient electrode used for all-vanadium redox flow battery, gradient electrode have the graphite fibre or carbon of different body density fine by least two-layer
Dimension felt is laminated composition from low to high by body density, and is formed integrally by the longitudinal acupuncture perpendicular to electrode surface.
Gradient electrode presses body density stacking group from low to high by the graphite fibre or carbon fiber felt that two-layer has different body density
Into, wherein, graphite fibre felt or carbon fiber felt are diffusion layer, and thickness accounts for the 30～90% of thickness of electrode, preferably 40～75%；Carbon
Fiber felt is Catalytic Layer, and the body density of Catalytic Layer is higher than the body density of diffusion layer.
The diffusion layer is 0.05～0.17gcm of body density-3Graphite fibre felt or carbon fiber felt, porosity 90-97%, preferably
92-96%.
The Catalytic Layer is 0.15～0.8gcm of body density-3Carbon fiber felt, porosity 50-90%, preferably 70-90%.
When flow battery is assembled into, diffusion layer and bipolar plates are contacted, and Catalytic Layer and film are contacted.
As shown in figure 1, the gradient electrode that the present invention is provided is had at least two chopped carbon fibers of different body density by least two-layer
Felt is constituted, and is formed integrally by longitudinal acupuncture, wherein, diffusion layer E1 is graphite fibre felt or carbon fiber felt, and thickness accounts for electrode
The 30～90% of thickness, preferably 40～75%；Catalytic Layer E2 is carbon fiber felt.When being assembled into battery, diffusion layer E1 and bipolar plates
Contact, as diffusion layer E1 has high porosity, it is ensured that the good mobility of electrolyte, ensures the supply of active goods and materials,
Reduce the concentration polarization of battery；Catalytic Layer E2 and film contact, due to its low porosity, can cause higher density i.e. bigger
Surface area, provides more reacting environment for electrochemical reaction, it is possible to decrease the activation polarization of battery.
The invention has the advantages that：
(1) using the gradient electrode of the present invention, as the diffusion layer in electrode has high porosity, it is ensured that electrolyte is good
Good mobility, has ensured the supply of active goods and materials, has reduced the concentration polarization of battery.Acupuncture all-in-one-piece gradient electrode is compared
The electrode of simple superposition has the little advantage of longitudinal electrical resistance, it is possible to decrease the ohmic polarization of battery.
(2) using the gradient electrode of the present invention, as the Catalytic Layer in electrode has low porosity and high body density, can lead
Bigger surface area is caused, and more reacting environment is provided for electrochemical reaction, it is possible to decrease the activation polarization of battery.
(3) using the flow battery of gradient electrode of the present invention, on the premise of energy efficiency is maintained at more than 80%, operating current
Density can bring up to 140mA/cm2More than so that the battery weight of identical output, volume and cost are substantially reduced.
(4) gradient electrode of the invention is easy to batch preparation, and the material for being used is carbon materials cheap and easy to get, with business
Industry application value.
Description of the drawings
Fig. 1 is the gradient electrode structural representation of flow battery of the present invention
Wherein：E1 diffusion layers；E2 Catalytic Layers
Fig. 2 is the discharge and recharge in the embodiment of the present invention 1 using the all-vanadium flow monocell of gradient electrode of the present invention under different electric current densities
Curve chart.
Specific embodiment
Below by specific embodiment in detail the present invention is described in detail.
Embodiment 1
It is 0.08gcm to choose 2.5mm thickness, body density-3Graphite fibre felt as diffusion layer, choose that 2mm is thick, body density is
0.16gcm-3Carbon fiber felt as Catalytic Layer, then two-layer felt is superimposed, with needing machine will it is its acupuncture integral be obtained
There is the gradient electrode of different densities in the vertical, needling density is 100 pins/cm2.During assemble, the expansion of the gradient electrode
, near bipolar plates, Catalytic Layer is near film for scattered layer.All-vanadium flow monocell is assembled under the compression of end plate, rear electrode thickness is compressed
About 3mm, electrode area are 48cm2.Anode electrolyte is 1.5M VO2+3M H2SO4Solution 60ml, electrolyte liquid
For 1.5M V3+3M H2SO4Solution 60ml.Charging and discharging curve of the battery under different electric current densities is as shown in Figure 2.Using
The monocell of gradient electrode of the present invention, electric current density are 80mA/cm2When, voltage efficiency and energy efficiency are respectively 90.8% He
85.4%；Electric current density brings up to 160mA/cm2When, voltage efficiency and energy efficiency still remain in 83.3% and 79.1%.
Diffusion layer is compared together with Catalytic Layer simple superposition in comparative example, voltage efficiency and energy efficiency are all significantly improved.
Embodiment 2
It is 0.1gcm to choose 4mm thickness, body density-3Carbon fiber felt as diffusion layer, choose that 1mm is thick, body density is 0.2gcm-3
Carbon fiber felt as Catalytic Layer, then two-layer felt is superimposed, with needing machine by it is its acupuncture integral be obtained in the vertical
Gradient electrode with different densities, needling density are 200 pins/cm2.During assemble, the diffusion layer of the gradient electrode is close
Bipolar plates, Catalytic Layer is near film.All-vanadium flow monocell is assembled under the compression of end plate, rear electrode thickness is compressed and is about 4mm,
Electrode area is 48cm2.Anode electrolyte is 1.5M VO2+3M H2SO4Solution 60ml, electrolyte liquid are 1.5M V3+
3M H2SO4Solution 60ml.Using the monocell of gradient electrode of the present invention, electric current density is 80mA/cm2When, voltage effect
Rate and energy efficiency are respectively 90.2% and 85.2%；Electric current density brings up to 140mA/cm2When, voltage efficiency and energy efficiency
Still remain in 84.3% and 80.5%.
Comparative example
It is 0.08gcm to choose 2.5mm thickness, body density-3Graphite fibre felt as diffusion layer, choose that 2mm is thick, body density is
0.16gcm-3Carbon fiber felt as Catalytic Layer, then by the two-layer felt simple superposition electrode as all-vanadium flow battery together.
During assemble, near bipolar plates, Catalytic Layer is near film for the diffusion layer of the electrode.All-vanadium flow is assembled under the compression of end plate
Monocell, compresses rear electrode thickness and is about 3mm, and electrode area is 48cm2.Anode electrolyte is 1.5M VO2+3M H2SO4
Solution 60ml, electrolyte liquid are 1.5M V3+3M H2SO4Solution 60ml.Using the monocell of the electrode, electric current density
For 80mA/cm2When, voltage efficiency and energy efficiency are respectively 88.8% and 83.5%；Electric current density brings up to 160mA/cm2
When, voltage efficiency and energy efficiency are respectively 80.7% and 77.5%.
Claims (6)
1. a kind of flow battery gradient electrode, it is characterised in that：Gradient electrode is had the stone of different body density by least two-layer
Black fiber or carbon fiber felt are laminated composition from low to high by body density, and are made by the longitudinal acupuncture perpendicular to electrode surface
Integrally.
2. electrode according to claim 1, it is characterised in that：Gradient electrode is had the graphite fibre of different body density by two-layer
Or carbon fiber felt is laminated composition from low to high by body density, wherein, graphite fibre felt or carbon fiber felt are diffusion layer, thickness
Account for the 30～90% of thickness of electrode, preferably 40～75%；Carbon fiber felt is Catalytic Layer, and the body density of Catalytic Layer is closeer than the body of diffusion layer
Degree is high.
3. electrode according to claim 1 or claim 2, it is characterised in that：The diffusion layer is 0.05～0.17gcm of body density-3
Graphite fibre felt or carbon fiber felt, porosity 90-97%, preferably 92-96%.
4. electrode according to claim 1 or claim 2, it is characterised in that：The Catalytic Layer is 0.15～0.8gcm of body density-3's
Carbon fiber felt, preferably porosity 50-90%, 70-90%.
5. electrode according to claim 1, it is characterised in that：When flow battery is assembled into, diffusion layer and bipolar plates are contacted,
Catalytic Layer and film contact.
6. the application of the arbitrary electrode of a kind of claim 1-5, it is characterised in that：The electrode may apply to all-vanadium flow
In the electrode of battery.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155389A (en) * | 2017-11-29 | 2018-06-12 | 辽宁科技大学 | It is a kind of from the flow channel type flow battery preparation method of graphite felt electrode material |
| CN110718708A (en) * | 2019-09-11 | 2020-01-21 | 浙江大学 | Variable porosity electrode structure flow battery capable of improving battery efficiency |
| CN111082069A (en) * | 2019-12-20 | 2020-04-28 | 大连博融新材料有限公司 | Implanted gradient composite electrode, production method and application thereof |
| CN111584895A (en) * | 2020-05-25 | 2020-08-25 | 广州市香港科大霍英东研究院 | Oriented ordered electrode and preparation method and application thereof |
| CN112002910A (en) * | 2020-09-11 | 2020-11-27 | 杭州德海艾科能源科技有限公司 | Vanadium battery composite electrode and preparation method thereof |
| CN112768705A (en) * | 2021-01-19 | 2021-05-07 | 江苏大学 | Sectional type electrode for liquid-liquid type eutectic solvent electrolyte flow battery |
| CN112928321A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Flow battery structure |
| WO2021203932A1 (en) * | 2020-04-10 | 2021-10-14 | 国家能源投资集团有限责任公司 | Composite electrode for flow cell, flow cell, and pile |
| CN114256467A (en) * | 2020-09-23 | 2022-03-29 | 中国科学院金属研究所 | Preparation method of double-gradient-distribution carbon fiber electrode and application of carbon fiber electrode in flow battery |
| CN114583184A (en) * | 2022-03-11 | 2022-06-03 | 上海朗雄能源科技有限公司 | Flow battery stack or single battery, electrode-diaphragm composite assembly and composite electrode structure thereof |
| CN115074769A (en) * | 2022-05-06 | 2022-09-20 | 同济大学 | Large-area electrode support body structure of alkaline water electrolytic cell |
| CN117059828A (en) * | 2023-10-12 | 2023-11-14 | 寰泰储能科技股份有限公司 | Integrated gradient porosity electrode material, preparation method thereof and all-vanadium redox flow battery |
| CN118472287A (en) * | 2024-07-10 | 2024-08-09 | 杭州幄肯新材料科技有限公司 | Gradient stiffness carbon fiber felt electrode and preparation method thereof |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155389B (en) * | 2017-11-29 | 2020-05-12 | 辽宁科技大学 | Preparation method of graphite felt electrode material for self-flow-channel flow battery |
| CN108155389A (en) * | 2017-11-29 | 2018-06-12 | 辽宁科技大学 | It is a kind of from the flow channel type flow battery preparation method of graphite felt electrode material |
| CN110718708A (en) * | 2019-09-11 | 2020-01-21 | 浙江大学 | Variable porosity electrode structure flow battery capable of improving battery efficiency |
| CN112928321B (en) * | 2019-12-06 | 2022-06-28 | 中国科学院大连化学物理研究所 | Flow battery structure |
| CN112928321A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Flow battery structure |
| CN111082069A (en) * | 2019-12-20 | 2020-04-28 | 大连博融新材料有限公司 | Implanted gradient composite electrode, production method and application thereof |
| CN111082069B (en) * | 2019-12-20 | 2022-07-29 | 大连博融新材料有限公司 | Implanted gradient composite electrode, production method and application thereof |
| WO2021203932A1 (en) * | 2020-04-10 | 2021-10-14 | 国家能源投资集团有限责任公司 | Composite electrode for flow cell, flow cell, and pile |
| CN113517451A (en) * | 2020-04-10 | 2021-10-19 | 国家能源投资集团有限责任公司 | Composite electrode for flow battery, flow battery and electric pile |
| CN111584895A (en) * | 2020-05-25 | 2020-08-25 | 广州市香港科大霍英东研究院 | Oriented ordered electrode and preparation method and application thereof |
| CN111584895B (en) * | 2020-05-25 | 2022-02-11 | 广州市香港科大霍英东研究院 | Oriented ordered electrode and preparation method and application thereof |
| CN112002910A (en) * | 2020-09-11 | 2020-11-27 | 杭州德海艾科能源科技有限公司 | Vanadium battery composite electrode and preparation method thereof |
| CN114256467A (en) * | 2020-09-23 | 2022-03-29 | 中国科学院金属研究所 | Preparation method of double-gradient-distribution carbon fiber electrode and application of carbon fiber electrode in flow battery |
| CN114256467B (en) * | 2020-09-23 | 2023-10-10 | 中国科学院金属研究所 | Preparation method of carbon fiber electrode with double gradient distribution and application of carbon fiber electrode in flow battery |
| CN112768705A (en) * | 2021-01-19 | 2021-05-07 | 江苏大学 | Sectional type electrode for liquid-liquid type eutectic solvent electrolyte flow battery |
| CN114583184A (en) * | 2022-03-11 | 2022-06-03 | 上海朗雄能源科技有限公司 | Flow battery stack or single battery, electrode-diaphragm composite assembly and composite electrode structure thereof |
| CN114583184B (en) * | 2022-03-11 | 2024-08-16 | 上海朗雄能源科技有限公司 | Flow battery stack or single cell, electrode-diaphragm composite assembly and composite electrode structure thereof |
| CN115074769A (en) * | 2022-05-06 | 2022-09-20 | 同济大学 | Large-area electrode support body structure of alkaline water electrolytic cell |
| WO2023213054A1 (en) * | 2022-05-06 | 2023-11-09 | 同济大学 | Large-area electrode support body structure of alkaline water electrolytic cell |
| CN117059828A (en) * | 2023-10-12 | 2023-11-14 | 寰泰储能科技股份有限公司 | Integrated gradient porosity electrode material, preparation method thereof and all-vanadium redox flow battery |
| CN117059828B (en) * | 2023-10-12 | 2023-12-08 | 寰泰储能科技股份有限公司 | Integrated gradient porosity electrode material, preparation method thereof and all-vanadium redox flow battery |
| CN118472287A (en) * | 2024-07-10 | 2024-08-09 | 杭州幄肯新材料科技有限公司 | Gradient stiffness carbon fiber felt electrode and preparation method thereof |
| CN118472287B (en) * | 2024-07-10 | 2024-10-18 | 杭州幄肯新材料科技有限公司 | Gradient stiffness carbon fiber felt electrode and preparation method thereof |
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