CN106558704B - 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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- CN106558704B CN106558704B CN201510621446.0A CN201510621446A CN106558704B CN 106558704 B CN106558704 B CN 106558704B CN 201510621446 A CN201510621446 A CN 201510621446A CN 106558704 B CN106558704 B CN 106558704B
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- carbon fiber
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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
Abstract
A kind of flow battery gradient electrode gradient electrode be laminated from low to high by volume density and is formed by least two layers graphite fibre or carbon fiber felt with different volume densitys, and is pierced by longitudinal needle perpendicular to electrode surface and one is made.This electrode can effectively reduce electrode body resistance, and reduces the flow resistance of electrolyte and provide more reacting environment, final ohmic polarization, activation polarization and the concentration polarization for reducing flow battery.The present invention improves the energy efficiency and voltage efficiency of flow battery, so that its working current density is improved, so that the battery weight of identical output power, volume and cost substantially reduce.
Description
Technical field
The present invention relates to the flow battery fields in chemical energy storage technology, the in particular to electrode of all-vanadium flow battery.
Background technique
All-vanadium flow battery is because it is mutually indepedent with output power and capacity, system flexible design；Energy efficiency is high, the longevity
Life length, operation stability and high reliablity, self discharge are low；Addressing freedom degree is big, and simply, operation cost is low for pollution-free, maintenance, peace
The advantages that Quan Xinggao, has vast potential for future development in terms of scale energy storage, it is considered to be it is renewable to solve solar energy, wind energy etc.
The effective ways of energy electricity generation system randomness and intermittent unstable state feature are built in renewable energy power generation and smart grid
In have great demand.
Different from the function of general chemistry power electrode, the electrode of flow battery is chemical energy storage system charge and discharge reaction
Place, the electrode of this kind of battery itself is not involved in electrochemical reaction, and the active material in electrolyte solution connects in electrode surface
By or provide electronics and complete battery chemistries reaction, carry out the transformation between electric energy and chemical energy and realize the storage of energy or release
It puts.
Critical component one of of the electrode as flow battery, influence of the performance to flow battery are very big.Its conductance is blunt
Connect the ohmic internal resistance for affecting battery；Its porosity and pore structure influence whether active material in the transmission speed of electrode interface
Rate；Its electrochemical catalysis activity also will directly determine the intrinsic reaction rate of electrochemical reaction, in short, electrode material affects
Activation polarization, concentration polarization and the ohmic polarization of battery have been related to whole elements of battery electrochemical impedance.These
Element largely affects the working current density and energy efficiency of battery.
Currently, the working current density of flow battery operation is lower, cause battery module volume big, materials demand amount is big,
It is at high cost.And the power density of battery can be improved in the raising of working current density, reduces the cost of whole system, reduces energy storage
The mobility of its adaptive capacity to environment and system is improved in the occupied area of system and space, extends the application neck of flow battery
Domain.
The working current density for improving flow battery needs to reduce battery polarization, i.e. ohmic polarization, electrochemistry as much as possible
Polarization and concentration polarization reduce voltage loss.
Mainly have in current published patent document for the reduction polarized method of flow battery:
(1) metallization is carried out to electrode material such as graphite felt, carbon paper etc. or oxidation modification is handled, modified in carbon fiber surface
Upper metal 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 is
The activation polarization for reducing battery does not help the ohmic polarization for reducing battery.And the reduction of ohmic polarization is for improving
It is more important for the working current density of battery, because activation polarization is directly proportional to the logarithm of electric current, and ohmic voltage drop
It is then directly proportional with the size of electric current.Therefore, with the raising of working current density, the influence of battery ohmic internal resistance can increasingly
Greatly.
(2) the research and development electrode and integrated combination electrode of bipolar plates, i.e. integrated pole dual-pole board reduce electricity
Contact resistance between the bipolar plates of pole.As disclosed in CN 101009376A, bipolar plates and porous electrode are passed through into conductive bond material
Material is bonded together to form integrated pole dual-pole board.However, the ohmic internal resistance of all-vanadium flow battery mainly include electrode, it is bipolar
Contact resistance between plate, electrolyte and the bulk resistance and electrode and bipolar plates of diaphragm.It is double that this method only reduces electrode
Contact resistance between pole plate has no influence to the bulk resistance for accounting for the biggish electrode of internal resistance of cell specific gravity and electrolyte, therefore right
In the raising limitation of voltage efficiency and energy efficiency.
Summary of the invention
The present invention is intended to provide a kind of flow battery gradient electrode, density, surface area and hole with gradient distribution
Gap rate, it is ensured that the good mobility of electrolyte can reduce activation polarization and the concentration polarization of flow battery, improve battery
Working current density, with achieve the purpose that improve cell power density.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of gradient electrode used for all-vanadium redox flow battery, gradient electrode is by least two layers graphite fibre with different volume densitys
Or composition is laminated by volume density from low to high for carbon fiber felt, and is made one by longitudinal needle thorn perpendicular to electrode surface
Body.
Gradient electrode presses volume density from low to high by two layers graphite fibre or carbon fiber felt with different volume densitys
Stacking composition, 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 volume density of Catalytic Layer is higher than the volume density of diffusion layer.
The diffusion layer is 0.05~0.17gcm of volume density-3Graphite fibre felt or carbon fiber felt, porosity 90-97%,
Preferably 92-96%.
The Catalytic Layer is 0.15~0.8gcm of volume density-3Carbon fiber felt, porosity 50-90%, preferably 70-
90%.
When being assembled into flow battery, diffusion layer and bipolar plates contact, Catalytic Layer and film are contacted.
As shown in Figure 1, gradient electrode provided by the invention has at least two of different volume densitys to be chopped by least two layers
Carbon fiber felt composition, and one is made by longitudinal needle thorn, wherein diffusion layer E1 is graphite fibre felt or carbon fiber felt, thickness
Account for the 30~90% of thickness of electrode, preferably 40~75%；Catalytic Layer E2 is carbon fiber felt.When being assembled into battery, diffusion layer E1 and
Bipolar plates contact, since diffusion layer E1 has high porosity, it is ensured that the good mobility of electrolyte ensures active goods and materials
Supply, reduce the concentration polarization of battery；Catalytic Layer E2 and film contact, due to its low porosity, will lead to higher density
I.e. bigger surface area provides more reacting environment for electrochemical reaction, can reduce the activation polarization of battery.
The present invention has the advantage that
(1) gradient electrode of the invention is used, since the diffusion layer in electrode has high porosity, it is ensured that electrolysis
The good mobility of liquid, has ensured the supply of active goods and materials, reduces the concentration polarization of battery.Needle pierces integral gradient electrode
Compared to the advantage that the electrode of simple superposition has longitudinal electrical resistance small, the ohmic polarization of battery can be reduced.
(2) gradient electrode of the invention is used, since the Catalytic Layer in electrode has low porosity and high volume density,
It will lead to bigger surface area, provide more reacting environment for electrochemical reaction, the activation polarization of battery can be reduced.
(3) using the flow battery of gradient electrode of the present invention, under the premise of energy efficiency is maintained at 80% or more, work
140mA/cm can be improved in current density2More than, so that the battery weight of identical output power, volume and cost are significantly
It reduces.
(4) gradient electrode of the invention is easy to prepare in batches, and used material is carbon materials cheap and easy to get, tool
There is commercialization application value.
Detailed description of the invention
Fig. 1 is the gradient electrode structural schematic diagram of flow battery of the present invention
Wherein: E1 diffusion layer；E2 Catalytic Layer
Fig. 2 is to use the all-vanadium flow monocell of gradient electrode of the present invention in different current densities in the embodiment of the present invention 1
Under charging and discharging curve figure.
Specific embodiment
The present invention is described in detail below by specific embodiment.
Embodiment 1
Choose 2.5mm thickness, volume density 0.08gcm-3Graphite fibre felt as diffusion layer, choose that 2mm is thick, volume density is
0.16gcm-3Carbon fiber felt as Catalytic Layer, then two layers of felt is superimposed, its needle is pierced into integral system with needing machine
Gradient electrode in the longitudinal direction with different densities is obtained, needling density is 100 needles/cm2.When assembling battery, the gradient electrode
Diffusion layer is close to bipolar plates, and Catalytic Layer is close to film.All-vanadium flow monocell is assembled under the compression of end plate, electrode is thick after compression
Degree is about 3mm, electrode area 48cm2.Anode electrolyte is 1.5M VO2+3M H2SO4Solution 60ml, electrolyte liquid are
1.5M V3+3M H2SO4Solution 60ml.Charging and discharging curve of the battery under different current densities is as shown in Figure 2.Using this hair
The monocell of bright gradient electrode, current density 80mA/cm2When, voltage efficiency and energy efficiency are respectively 90.8% He
85.4%；Current density is increased to 160mA/cm2When, voltage efficiency and energy efficiency still remain in 83.3% and 79.1%.
It is compared together in comparative example by diffusion layer and Catalytic Layer simple superposition, voltage efficiency and energy efficiency all significantly improve.
Embodiment 2
Choose 4mm thickness, volume density 0.1gcm-3Carbon fiber felt as diffusion layer, choose that 1mm is thick, volume density is
0.2gcm-3Carbon fiber felt as Catalytic Layer, then two layers of felt is superimposed, is made with needing machine by its needle thorn is integral
In the longitudinal direction with the gradient electrode of different densities, needling density is 200 needles/cm2.When assembling battery, the expansion of the gradient electrode
Layer is dissipated close to bipolar plates, and Catalytic Layer is close to film.All-vanadium flow monocell, thickness of electrode after compression are assembled under the compression of end plate
About 4mm, electrode area 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, current density 80mA/cm2When, voltage
Efficiency and energy efficiency are respectively 90.2% and 85.2%；Current density is increased to 140mA/cm2When, voltage efficiency and can dose-effect
Rate stills remain in 84.3% and 80.5%.
Comparative example
Choose 2.5mm thickness, volume density 0.08gcm-3Graphite fibre felt as diffusion layer, choose that 2mm is thick, volume density is
0.16gcm-3Carbon fiber felt as Catalytic Layer, then two layers of felt simple superposition is used as to the electricity of all-vanadium flow battery together
Pole.When assembling battery, the diffusion layer of the electrode is close to bipolar plates, and Catalytic Layer is close to film.Vanadium is helped in assembly under the compression of end plate
Liquid stream monocell, thickness of electrode is about 3mm, electrode area 48cm after compression2.Anode electrolyte is 1.5M VO2+3M
H2SO4Solution 60ml, electrolyte liquid are 1.5M V3+3M H2SO4Solution 60ml.Using the monocell of the electrode, electric current is close
Degree is 80mA/cm2When, voltage efficiency and energy efficiency are respectively 88.8% and 83.5%；Current density is increased 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 by least two layers stone with different volume densitys
Composition is laminated by volume density from low to high for black fiber or carbon fiber felt, and pierces system by longitudinal needle perpendicular to electrode surface
Integrally；Gradient electrode presses volume density layer from low to high by two layers graphite fibre or carbon fiber felt with different volume densitys
It is stacked, wherein graphite fibre felt or carbon fiber felt are diffusion layer, and thickness accounts for the 30 ~ 90% of thickness of electrode；Carbon fiber felt is to urge
Change layer, the volume density of Catalytic Layer is higher than the volume density of diffusion layer；
The diffusion layer is 0.05 ~ 0.17 gcm of volume density-3Graphite fibre felt or carbon fiber felt, porosity 90-97%；
The Catalytic Layer is 0.15 ~ 0.8gcm of volume density-3Carbon fiber felt, porosity 50-90%.
2. the electrode according to claim 1, it is characterised in that: the thickness of diffusion layer accounts for the 40 ~ 75% of thickness of electrode.
3. the electrode according to claim 1, it is characterised in that: the diffusion layer porosity 92-96%.
4. the electrode according to claim 1, it is characterised in that: the catalysis layer porosity 70-90%.
5. the electrode according to claim 1, it is characterised in that: when being assembled into flow battery, diffusion layer and bipolar plates are connect
Touching, Catalytic Layer and film contact.
6. a kind of application of any electrode of claim 1-5, it is characterised in that: the application of electrode to all-vanadium flow electricity
In the electrode in pond.
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Families Citing this family (12)
| 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 |
| 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 |
| 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 |
| 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 |
| CN111584895B (en) * | 2020-05-25 | 2022-02-11 | 广州市香港科大***研究院 | Oriented ordered electrode and preparation method and application thereof |
| CN112002910B (en) * | 2020-09-11 | 2021-08-10 | 杭州德海艾科能源科技有限公司 | Vanadium battery composite electrode and preparation method thereof |
| 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 |
| CN115074769B (en) * | 2022-05-06 | 2023-07-04 | 同济大学 | Large-area electrode support body structure of alkaline water electrolysis tank |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102460790A (en) * | 2009-06-26 | 2012-05-16 | 日产自动车株式会社 | Gas diffusion electrode and production method for same, and membrane electrode assembly and production method for same |
| CN103477486A (en) * | 2011-02-18 | 2013-12-25 | 大日本印刷株式会社 | Membrane-electrode assembly for fuel cell, manufacturing method thereof, and solid polymer fuel cell using membrane-electrode assembly |
| CN103633330A (en) * | 2012-08-29 | 2014-03-12 | 中国科学院大连化学物理研究所 | Combined electrode for flow battery and flow energy storage battery |
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| US8808897B2 (en) * | 2011-07-19 | 2014-08-19 | Fu Jen Catholic University | Electrode structure of vanadium redox flow battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102460790A (en) * | 2009-06-26 | 2012-05-16 | 日产自动车株式会社 | Gas diffusion electrode and production method for same, and membrane electrode assembly and production method for same |
| CN103477486A (en) * | 2011-02-18 | 2013-12-25 | 大日本印刷株式会社 | Membrane-electrode assembly for fuel cell, manufacturing method thereof, and solid polymer fuel cell using membrane-electrode assembly |
| CN103633330A (en) * | 2012-08-29 | 2014-03-12 | 中国科学院大连化学物理研究所 | Combined electrode for flow battery and flow energy storage battery |
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