CN105702976B - Electrode, flow battery and liquid stream battery stack - Google Patents
Electrode, flow battery and liquid stream battery stack Download PDFInfo
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- CN105702976B CN105702976B CN201610173301.3A CN201610173301A CN105702976B CN 105702976 B CN105702976 B CN 105702976B CN 201610173301 A CN201610173301 A CN 201610173301A CN 105702976 B CN105702976 B CN 105702976B
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- 230000009257 reactivity Effects 0.000 claims abstract description 93
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
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- 230000005611 electricity Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
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- 238000000034 method Methods 0.000 description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 3
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- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 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
- 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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- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
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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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- Life Sciences & Earth Sciences (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
The present invention provides a kind of electrode, flow battery and liquid stream battery stacks.Wherein, the electrode includes first electrode layer, first electrode layer has opposite first surface and second surface, electrode further includes the second electrode lay being set on first surface and/or the third electrode layer being set on second surface, the reactivity number of sites mesh of the second electrode lay is greater than the reactivity number of sites mesh of first electrode layer, and the reactivity number of sites mesh of third electrode layer is greater than the reactivity number of sites mesh of first electrode layer.By the application of electrode after flow battery, region in electrode layer group close to amberplex and/or bipolar plates can have bigger reactivity number of sites mesh compared to remaining area, to which the reactivity number of sites mesh in electrode can not only be made to meet the needs of flow battery on the basis of not increasing thickness of electrode, it can also be effectively reduced the amplification of the internal resistance of cell by adjusting the thickness of electrode, improve the voltage efficiency of flow battery.
Description
Technical field
The present invention relates to flow battery technology fields, in particular to a kind of electrode, flow battery and flow battery
Heap.
Background technique
Flow battery has safety since the electrolyte of storage energy is mutually separated with the battery pile that energy conversion occurs
High, power and Capacity design is flexible, the service life is long and the advantages such as maintenance cost is low, is answered in various energy storage fields extensively
With.
For existing liquid stream battery stack, on the one hand, in order to improve the voltage efficiency of battery, need to reduce the interior of battery
Resistance, and then need to reduce the thickness of electrode or increase the reactivity number of sites mesh of electrode；On the other hand, in order to improve battery
Power density needs to increase raising current density, in order to allow battery to be able to bear bigger current density, then needs to increase electrode
Reactivity number of sites mesh.
For each electrode, a uniform carbon felt is generallyd use in the prior art as pile, in unit bodies carbon deposit felt
Reactivity number of sites mesh determine in the case where, in order to keep response area constant, can only by increase charcoal felt thickness come
Increase reactivity site.However, the thickness for increasing charcoal felt will increase the internal resistance of battery, so as to cause voltage efficiency decline again.
Summary of the invention
The main purpose of the present invention is to provide a kind of electrode, flow battery and liquid stream battery stacks, to solve the prior art
In flow battery the lower problem of voltage efficiency.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of electrode, including first electrode layer,
First electrode layer has opposite first surface and second surface, and electrode further includes the second electrode lay being set on first surface
And/or it is set to the third electrode layer on second surface, the reactivity number of sites mesh of the second electrode lay is greater than first electrode layer
Reactivity number of sites mesh, the reactivity number of sites mesh of third electrode layer is greater than the reactivity number of sites of first electrode layer
Mesh.
Further, the ratio between the second electrode lay and the reactivity number of sites mesh of first electrode layer are greater than 1.05；Third electricity
The ratio between pole layer and the reactivity number of sites mesh of first electrode layer are greater than 1.05.
Further, the unit volume specific surface area of the second electrode lay is greater than the unit volume specific surface of first electrode layer
Product；The unit volume specific surface area of third electrode layer is greater than the unit volume specific surface area of first electrode layer.
Further, the ratio between unit volume specific surface area of the second electrode lay and first electrode layer is greater than 1.05；Third electricity
The ratio between pole layer and the unit volume specific surface area of first electrode layer are greater than 1.05.
Further, first electrode layer includes the multiple sons being sequentially laminated along the direction that first surface is directed toward second surface
Electrode layer.
Further, when electrode includes the second electrode lay, each son electricity along the direction that first surface is directed toward second surface
The reactivity number of sites mesh of pole layer successively reduces.
Further, when electrode includes third electrode layer, each son electricity along the direction that first surface is directed toward second surface
The reactivity number of sites mesh of pole layer successively increases.
Further, when electrode includes the second electrode lay and third electrode layer, close to first surface sub-electrode layer and
It is greater than the reactivity number of sites mesh of remaining each sub-electrode layer close to the reactivity number of sites mesh of the sub-electrode layer of second surface.
Further, the material for forming first electrode layer is carbon felt；The material for forming the second electrode lay is selected from carbon paper, electrification
Learn modified charcoal felt and it is hydrophilically modified after charcoal felt it is any one or more of；The material for forming third electrode layer is selected from charcoal
Charcoal felt after paper, electrochemical modification and it is hydrophilically modified after charcoal felt it is any one or more of.
According to another aspect of the present invention, a kind of flow battery, including bipolar plates, liquid flow frame, electrode and ion are provided
Exchange membrane, electrode are above-mentioned electrode, wherein when electrode includes the second electrode lay, the second electrode lay is close to amberplex
Setting；When electrode includes third electrode layer, third electrode layer is arranged close to bipolar plates.
According to another aspect of the present invention, a kind of liquid stream battery stack, including multiple flow batteries, flow battery are additionally provided
For above-mentioned flow battery.
It applies the technical scheme of the present invention, providing a kind of further includes second electrode on the basis of including first electrode layer
The electrode of layer and/or third electrode layer, since the reactivity number of sites mesh of the second electrode lay is greater than the reaction of first electrode layer
Number of active sites, the reactivity number of sites mesh of third electrode layer are greater than the reactivity number of sites mesh of first electrode layer, from
And by the application of electrode after flow battery, the second electrode lay is close to the setting of the surface of amberplex and/or third electrode layer
It is arranged close to the surface of bipolar plates, makes in electrode layer group close to the region of amberplex and/or bipolar plates compared to remaining area
Domain can have bigger reactivity number of sites mesh, to can not only make in electrode on the basis of not increasing thickness of electrode
Reactivity number of sites mesh meet the needs of flow battery, additionally it is possible to be effectively reduced in battery by adjusting the thickness of electrode
The amplification of resistance improves the voltage efficiency of flow battery；Also, inhomogeneities is reacted as present in the electrode of flow battery,
Biggish kinetic current density is being needed close to amberplex and close to the region of bipolar plates, thus by improving above-mentioned electrode
In close to the region of amberplex and/or bipolar plates reactivity number of sites mesh, improve the kinetic current of desired zone
Density, and then improve the power density of flow battery.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to figure, the present invention is described in further detail.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the structural schematic diagram of electrode provided by the present invention；
Fig. 2 shows the stereo-resolution structural schematic diagrams of flow battery provided by the present invention；
Fig. 3 shows the structural schematic diagram of the flow battery provided by the present invention including the second electrode lay；
Fig. 4 shows the structural schematic diagram of the flow battery provided by the present invention including third electrode layer；And
Fig. 5 shows the structural representation of the flow battery provided by the present invention including the second electrode lay and third electrode layer
Figure.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein.In addition, term " includes " and " tool
Have " and their any deformation, it is intended that cover it is non-exclusive include, for example, containing a series of steps or units
Process, method, system, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include without clear
Other step or units listing to Chu or intrinsic for these process, methods, product or equipment.
As described in background technique, in the prior art in order to improve the power density of battery, need to increase electrode
Reactivity number of sites mesh can only increase reaction by increasing the thickness of charcoal felt however in order to keep response area constant
Active site, the thickness for increasing charcoal felt will increase the internal resistance of battery again, so as to cause voltage efficiency decline.The present inventor
It is studied regarding to the issue above, proposes a kind of electrode, as shown in Figure 1, the electrode includes first electrode layer 310, the first electricity
Pole layer 310 has opposite first surface and second surface, which further includes the second electrode lay being set on first surface
320 and/or the third electrode layer 330 that is set on second surface, and when electrode includes the second electrode lay 320, second electrode
The reactivity number of sites mesh of layer 320 is greater than the reactivity number of sites mesh of first electrode layer 310, when electrode includes third electrode
When layer 330, the reactivity number of sites mesh of third electrode layer 330 is greater than the reactivity number of sites mesh of first electrode layer 310.
Since the reactivity number of sites mesh of the second electrode lay 320 is greater than the reaction of first electrode layer 310 in above-mentioned electrode
Number of active sites, the reactivity number of sites mesh of third electrode layer 330 are greater than the reactivity number of sites of first electrode layer 310
Mesh, so that, when in electrode including the second electrode lay 320, the second electrode lay 320 is arranged by the application of electrode after flow battery
In on the surface of amberplex, when in electrode including third electrode layer 330, third electrode layer 330 is set to bipolar plates
On surface, enable to have more greatly close to the region of amberplex and/or bipolar plates compared to remaining area in electrode layer group
Reactivity number of sites mesh, so that the reactivity site in electrode can not only be made on the basis of not increasing thickness of electrode
Number meets the needs of flow battery, additionally it is possible to be effectively reduced the amplification of the internal resistance of cell by adjusting the thickness of electrode, improve
The voltage efficiency of flow battery；Also, inhomogeneities is reacted as present in the electrode of flow battery, close to ion exchange
The region of film and close bipolar plates needs biggish kinetic current density, thus by improving in above-mentioned electrode close to ion exchange
The reactivity number of sites mesh in the region of film and/or bipolar plates, improves the kinetic current density of desired zone, and then improve
The power density of flow battery.
The reactivity number of sites mesh of the application is identical as reactivity number of sites purpose concept in the prior art, each means
The number of the position of electrochemical reaction can occur in electrode.In a preferred embodiment, above-mentioned electrode includes being set to
The second electrode lay 320 of first surface, by the application of electrode after flow battery, which is set to ion friendship
It changes on the surface of film；In another preferred embodiment, above-mentioned electrode includes the third electrode layer for being set to second surface
330, by the application of electrode after flow battery, which is set on the surface of bipolar plates；Above-mentioned electrode may be used also
Simultaneously to include being set to the second electrode lay 320 of first surface and being set to the third electrode layer 330 of second surface, second is electric
Pole layer 320 is set on the surface of amberplex, and third electrode layer 330 is set on the surface of bipolar plates.
When above-mentioned electrode includes the second electrode lay 320, it is preferable that the second electrode lay 320 is anti-with first electrode layer 310
The ratio between number of active sites is answered to be greater than 1.05.The reactivity number of sites mesh of first electrode layer 310 and the second electrode lay 320 is limited
It is scheduled in above-mentioned preferred proportional region, can have biggish reactivity number of sites purpose guaranteeing the second electrode lay 320
Meanwhile making first electrode layer 310 that there is lesser reactivity number of sites mesh, to make electrode that can not only there is lesser thickness
Degree, additionally it is possible to there is lesser internal resistance, and then by the application of electrode after flow battery, flow battery can be further increased
Voltage efficiency；Also, by the application of electrode after flow battery, by having the second electrode lay 320 close to amberplex
There is biggish reactivity number of sites mesh, meets the need in electrode close to the region of amberplex to kinetic current density
It asks, to further improve the kinetic current density of desired zone, and then also further increases the power of flow battery
Density.
When above-mentioned electrode includes third electrode layer 330, it is preferable that third electrode layer 330 is anti-with first electrode layer 310
The ratio between number of active sites is answered to be greater than 1.05.The reactivity number of sites mesh of first electrode layer 310 and third electrode layer 330 is limited
It is scheduled in above-mentioned preferred proportional region, can have biggish reactivity number of sites purpose guaranteeing third electrode layer 330
Meanwhile making first electrode layer 310 that there is lesser reactivity number of sites mesh, to electrode equally can be made not only having and is smaller
Thickness, also have lesser internal resistance, and then by the application of electrode after flow battery, flow battery can be further increased
Voltage efficiency；Also, by the application of electrode after flow battery, by make close to bipolar plates third electrode layer 330 have compared with
Big reactivity number of sites mesh meets demand of the region in electrode close to bipolar plates to kinetic current density, thus into
One step improves the kinetic current density of desired zone, and then also further increases the power density of flow battery.
In the above-mentioned electrode of the present invention, when the reactivity number of sites mesh of above-mentioned the second electrode lay 320 is greater than first electrode
When the reactivity number of sites mesh of layer 310, it is preferable that the unit volume specific surface area of the second electrode lay 320 is greater than first electrode
The unit volume specific surface area of layer 310.Unit volume specific surface area refers to total surface possessed by the porous media of unit volume,
Therefore, make the second electrode lay 320 that there is bigger unit volume specific surface area compared to first electrode layer 310, can not increase
On the basis of the volume for adding first electrode layer 310, by forming thickness equal first electrode layer 310 and the second electrode lay 320,
There is the second electrode lay 320 compared to the smaller volume of first electrode layer 310, it will be able to make the second electrode lay 320
Reactivity number of sites mesh is greater than the reactivity number of sites mesh of first electrode layer 310, to efficiently control the whole of electrode
Body thickness.
In above-mentioned preferred embodiment, it is further preferable that the unit of the second electrode lay 320 and first electrode layer 310
The ratio between volumetric surface area is greater than 1.05.The unit volume specific surface area of the second electrode lay 320 and first electrode layer 310 is set
In above-mentioned preferred range, there can be the basis compared to the smaller volume of first electrode layer 310 in the second electrode lay 320
On, so that the reactivity number of sites mesh of the second electrode lay 320 is greater than the reactivity number of sites mesh of first electrode layer 310, thus
Further reduce the integral thickness of electrode.
In the above-mentioned electrode of the present invention, when the reactivity number of sites mesh of above-mentioned third electrode layer 330 is greater than first electrode
When the reactivity number of sites mesh of layer 310, it is preferable that the unit volume specific surface area of third electrode layer 330 is greater than first electrode
The unit volume specific surface area of layer 310.Similarly, make third electrode layer 330 that there is bigger list compared to first electrode layer 310
Position volumetric surface area, can on the basis of not increasing the volume of first electrode layer 310, by formed thickness it is equal first
Electrode layer 310 and third electrode layer 330, or even there is third electrode layer 330 compared to the smaller body of first electrode layer 310
Product, it will be able to the reactivity number of sites mesh of third electrode layer 330 be made to be greater than the reactivity number of sites of first electrode layer 310
Mesh, to efficiently control the integral thickness of electrode.
In above-mentioned preferred embodiment, it is further preferable that the unit of third electrode layer 330 and first electrode layer 310
The ratio between volumetric surface area is greater than 1.05.The unit volume specific surface area of third electrode layer 330 and first electrode layer 310 is set
In above-mentioned preferred range, also there can be the base compared to the smaller volume of first electrode layer 310 in third electrode layer 330
On plinth, the reactivity number of sites mesh of third electrode layer 330 is made to be greater than the reactivity number of sites mesh of first electrode layer 310, from
And further reduce the integral thickness of electrode.
In the above-mentioned electrode of the present invention, it is preferable that first electrode layer 310 includes being directed toward the side of second surface along first surface
Multiple sub-electrode layers of upstream sequence stacking.Since above-mentioned first electrode layer 310 includes multiple sub-electrode layers, thus by the electrode
After flow battery, it can realize by adjusting the reactivity number of sites mesh of each sub-electrode layer to positions different in electrode
Place's reactivity number of sites purpose adjustment is set, and then more effectively controls the thickness of electrode, reduces the increasing of the internal resistance of cell
Width improves the voltage efficiency of flow battery；Also, it can also be by adjusting each sub-electrode layer, the second electrode lay 320 and third
The reactivity number of sites mesh of electrode layer 330 is gradually increased reactivity number of sites mesh of the electrode from centre to two sides, into one
Step is met in the demand close to amberplex and close to the region of bipolar plates to kinetic current density, thus by improving institute
The kinetic current density for needing region, improves the power density of flow battery.
In the above-mentioned electrode including multiple sub-electrode layers, it is preferable that when electrode includes the second electrode lay 320, along
The reactivity number of sites mesh that each sub-electrode layer on the direction of second surface is directed toward on one surface successively reduces.Due to flow battery
Inhomogeneities is reacted present in electrode, needs biggish kinetic current density in the region close to amberplex, and react
Current density gradually decreases on the direction that amberplex is directed toward bipolar plates, thus by above-mentioned application of electrode in flow battery
Afterwards, it by making that there is biggish reactivity number of sites mesh close to the side of amberplex in electrode, and is handed over closer to ion
It changes in the region of film that reactivity number of sites mesh is bigger, further increases the kinetic current density of desired zone, Jin Erti
The high power density of flow battery.
In the above-mentioned electrode including multiple sub-electrode layers, it is preferable that when electrode includes third electrode layer 330, along
The reactivity number of sites mesh that each sub-electrode layer on the direction of second surface is directed toward on one surface successively increases.Due to flow battery
Inhomogeneities is reacted present in electrode, needs biggish kinetic current density, and kinetic current in the region close to bipolar plates
Density gradually decreases on the direction that bipolar plates are directed toward amberplex, to lead to by above-mentioned application of electrode after flow battery
Crossing makes have biggish reactivity number of sites mesh close to the side of bipolar plates in electrode, and anti-in the region of bipolar plates
It answers number of active sites bigger, further increases the kinetic current density of desired zone, and then improve flow battery
Power density.
In the above-mentioned electrode including multiple sub-electrode layers, it is preferable that when electrode includes the second electrode lay 320 and third electricity
When pole layer 330, the reactivity number of sites mesh close to the sub-electrode layer of the sub-electrode layer and second surface of first surface is greater than it
The reactivity number of sites mesh of remaining each sub-electrode layer；It is further preferable that make in electrode from centre to be directed toward first surface and second
The reactivity number of sites mesh on surface is gradually increased, preferably to meet distribution of the flow battery to kinetic current density in electrode
Demand to effectively improve the kinetic current density of desired zone, and then improves the power density of flow battery.
In the above-mentioned electrode of the present invention, it is preferable that the material for forming first electrode layer 310 is charcoal felt；Form second electrode
The material of layer 320 be independently selected from the charcoal felt after carbon paper, electrochemical modification and it is hydrophilically modified after any one of charcoal felt or more
Kind；Formed third electrode layer 330 charcoal felt of the material after carbon paper, electrochemical modification and it is hydrophilically modified after charcoal felt in
It is any one or more.Charcoal felt after above-mentioned electrochemical modification refers to the quantity for increasing effective functional group of material, modification
Method can be to be placed in 400 degrees Celsius lower 8 hours or longer for charcoal felt, or charcoal felt is placed in aqueous hydrogen peroxide solution 80
4 hours are handled under degree Celsius with first-class.The second electrode lay 320 and third can be guaranteed using above-mentioned carbon paper or modified material
The reactivity number of sites mesh of electrode layer 330 is greater than the reactivity number of sites mesh of first electrode layer 310, thus by above-mentioned electrode
After flow battery, the voltage efficiency and power density of flow battery are improved.
According to another aspect of the present invention, a kind of flow battery is provided, as shown in Fig. 2 to 5, including bipolar plates 10, liquid
Flow frame 20, amberplex 40 and above-mentioned electrode 30, wherein electrode 30 includes first electrode layer 310, and when electrode 30 also wraps
When including the second electrode lay 320, the second electrode lay 320 is arranged close to amberplex 40；When electrode further includes third electrode layer 330
When, third electrode layer 330 is arranged close to bipolar plates 10.
It is set on the surface of amberplex 40 in above-mentioned flow battery due to the second electrode lay 320, third electrode layer
330 are set on the surface of bipolar plates 10, to make the region in electrode layer group close to amberplex 40 and/or bipolar plates 10
There can be bigger reactivity number of sites mesh compared to remaining area, and then can have by the thickness of coordination electrode 30
The amplification for reducing to effect the internal resistance of cell, improves the voltage efficiency of flow battery；Also, due in the electrode of flow battery 30
Existing reaction inhomogeneities is needing biggish kinetic current close close to amberplex 40 and close to the region of bipolar plates 10
Degree, thus by improving in above-mentioned electrode 30 close to the reactivity site in amberplex 40 and/or the region of bipolar plates 10
Number, improves the kinetic current density of desired zone, and then improves the power density of flow battery.
In the above-mentioned flow battery of the present invention, bipolar plates 10 play a part of to collect discharge and recharge reaction charge, compression electrodes 30.
Preferably, bipolar plates 10 are made of metal material or conductive polymer material or carbon/polymer composite or carbon material
's.Metal material or conductive polymer material or carbon/polymer composite or carbon material are big with hardness, are easily achieved
The characteristics of high-accuracy mechanical is processed.Amberplex 40 in the present invention is generally perfluoro sulfonic acid membrane, half fluosulfonic acid film or non-fluorine
Sulfonate film.By the way that two electrodes 30 and amberplex 40 of plane are placed between two bipolar plates 10, then make two
Electrode 30 and amberplex 40 are drawn close under the assembly force of liquid stream battery stack and squeezed to a bipolar plates 10, makes electrode 30, ion
Exchange membrane 40 and bipolar plates 10 are fitted closely and are exactly matched each other, to complete the assembly of flow battery.
In a preferred embodiment, above-mentioned electrode 30 includes the second electrode lay 320 for being set to first surface, this
When, which is set on the surface of amberplex 40, and the flow battery of composition is as shown in Figure 3；In another kind
In preferred embodiment, above-mentioned electrode 30 includes the third electrode layer 330 for being set to second surface, at this point, the third electrode
Layer 330 is set on the surface of bipolar plates 10, and the flow battery of composition is as shown in Figure 4；Above-mentioned electrode 30 can also include simultaneously
It is set to the second electrode lay 320 of first surface and is set to the third electrode layer 330 of second surface, the second electrode lay 320 is set
It is placed on the surface of amberplex 40, third electrode layer 330 is set on the surface of bipolar plates 10, and the flow battery of composition is such as
Shown in Fig. 5.
In accordance with a further aspect of the present invention, a kind of liquid stream battery stack including multiple flow batteries, each liquid stream electricity are provided
Pond has above-mentioned electrode, and when electrode includes the second electrode lay, and the second electrode lay is arranged close to amberplex, works as electrode
When including third electrode layer, third electrode layer is arranged close to bipolar plates.Above-mentioned liquid stream battery stack is using above-mentioned flow battery as base
Our unit, more piece, which successively stacks, to be compressed and is connected in series, and by improving the voltage efficiency and power density of flow battery, is improved
The voltage efficiency and power density of liquid stream battery stack.
Electrode and flow battery provided by the present application are further illustrated below in conjunction with embodiment and comparative example.
Embodiment 1
Flow battery provided in this embodiment as shown in figure 3, include bipolar plates, liquid flow frame, electrode and amberplex,
In, electrode includes first electrode layer and the second electrode lay that is set on the first surface of first electrode layer, and the second electrode lay leans on
Nearly amberplex setting, the ratio between the second electrode lay and reactivity number of sites mesh of first electrode layer are 1.05:1, and second
The ratio between unit volume specific surface area of electrode layer and first electrode layer is 1.05:1；
Wherein, the material for forming above-mentioned bipolar plates is graphite plate, and above-mentioned amberplex is perfluoro sulfonic acid membrane, is formed above-mentioned
The material of first electrode layer is unmodified charcoal felt, and the material for forming above-mentioned the second electrode lay is carbon paper.
Embodiment 2
Flow battery provided in this embodiment as shown in figure 4, include bipolar plates, liquid flow frame, electrode and amberplex,
In, electrode includes first electrode layer and the third electrode layer that is set on the second surface of first electrode layer, and third electrode layer leans on
Nearly bipolar plates setting, the ratio between third electrode layer and reactivity number of sites mesh of first electrode layer are 1.05:1, and third electrode
The ratio between layer and the unit volume specific surface area of first electrode layer are 1.05:1；
Wherein, the material for forming above-mentioned bipolar plates is graphite plate, and above-mentioned amberplex is perfluoro sulfonic acid membrane, is formed above-mentioned
The material of first electrode layer is unmodified charcoal felt, and the material for forming above-mentioned third electrode layer is carbon paper.
Embodiment 3
Flow battery provided in this embodiment as shown in figure 5, include bipolar plates, liquid flow frame, electrode and amberplex,
In, electrode includes first electrode layer and the second electrode lay being respectively arranged on first surface and is set on second surface
Third electrode layer, the second electrode lay are arranged close to amberplex, and third electrode layer is arranged close to bipolar plates, third electrode layer,
The ratio between the second electrode lay and the reactivity number of sites mesh of first electrode layer be 1.05:1.05:1, and third electrode layer, second electricity
The ratio between pole layer and the unit volume specific surface area of first electrode layer are 1.05:1.05:1；
Wherein, the material for forming above-mentioned bipolar plates is graphite plate, and above-mentioned amberplex is perfluoro sulfonic acid membrane, is formed above-mentioned
The material of first electrode layer is unmodified charcoal felt, and the material for forming above-mentioned the second electrode lay is carbon paper, and forms above-mentioned third
The material of electrode layer is carbon paper.
Embodiment 4
Flow battery provided in this embodiment the difference from embodiment 1 is that:
The ratio between the second electrode lay and the reactivity number of sites mesh of first electrode layer are 1.1:1, and the second electrode lay and the
The ratio between unit volume specific surface area of one electrode layer is 1.1:1, and the material for forming above-mentioned first electrode layer is unmodified charcoal
Felt, formed above-mentioned the second electrode lay material be it is hydrophilically modified after charcoal felt.
Embodiment 5
Flow battery provided in this embodiment the difference from example 2 is that:
The ratio between third electrode layer and the reactivity number of sites mesh of first electrode layer are 1.1:1, and third electrode layer and the
The ratio between unit volume specific surface area of one electrode layer is 1.1:1, and the material for forming above-mentioned first electrode layer is unmodified charcoal
Felt, formed above-mentioned third electrode layer material be it is hydrophilically modified after charcoal felt.
Embodiment 6
Flow battery provided in this embodiment and the difference of embodiment 3 are:
The ratio between reactivity number of sites mesh of third electrode layer, the second electrode lay and first electrode layer is 104: 103: 1, and
The ratio between unit volume specific surface area of third electrode layer, the second electrode lay and first electrode layer is 104: 103: 1, and formed above-mentioned
The material of first electrode layer be unmodified charcoal felt, formed above-mentioned the second electrode lay material be electrochemical modification after charcoal felt,
The material of above-mentioned third electrode layer is formed as the charcoal felt after electrochemical modification.
Comparative example 1
The flow battery that this comparative example provides includes bipolar plates, liquid flow frame, electrode layer and amberplex, wherein above-mentioned
Electrode layer is set between amberplex and bipolar plates using the first electrode layer in embodiment 1；
Wherein, the material for forming above-mentioned bipolar plates is graphite plate, and the material for forming above-mentioned amberplex is perfluorinated sulfonic acid
Film.
The voltage efficiency for the flow battery that above-described embodiment 1 to 6 and comparative example 1 provide is tested, test result is such as
Following table:
| Voltage efficiency | |
| Comparative example 1 | 88.0% |
| Embodiment 1 | 90.1% |
| Embodiment 2 | 90.1% |
| Embodiment 3 | 91.3% |
| Embodiment 4 | 91.6% |
| Embodiment 5 | 91.6% |
| Embodiment 6 | 92.2% |
The flow battery provided in the embodiment of the present application 1 to 6 be can be seen that from above-mentioned test result compared with comparative example 1
With higher voltage efficiency.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
1, enable to have more close to the region of amberplex and/or bipolar plates compared to remaining area in electrode layer group
Big reactivity number of sites mesh, so that the reaction active site in electrode can not only be made on the basis of not increasing thickness of electrode
Point number meets the needs of flow battery, additionally it is possible to be effectively reduced the amplification of the internal resistance of cell by adjusting the thickness of electrode, mention
The voltage efficiency of high liquid flow battery；
2, by improving in above-mentioned electrode close to the reactivity number of sites in amberplex and/or the region of bipolar plates
Mesh, improves the kinetic current density of desired zone, and then improves the power density of flow battery.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of electrode, including first electrode layer (310), the first electrode layer (310) has opposite first surface and the
Two surfaces, which is characterized in that the electrode further includes the second electrode lay (320) being set on the first surface and is set to
Third electrode layer (330) on the second surface, the reactivity number of sites mesh of the second electrode lay (320) are greater than described
The reactivity number of sites mesh of the reactivity number of sites mesh of first electrode layer (310), the third electrode layer (330) is greater than institute
State the reactivity number of sites mesh of first electrode layer (310).
2. electrode according to claim 1, which is characterized in that
The ratio between reactivity number of sites mesh of the second electrode lay (320) and the first electrode layer (310) is greater than 1.05；
The ratio between reactivity number of sites mesh of the third electrode layer (330) and the first electrode layer (310) is greater than 1.05.
3. electrode according to claim 1, which is characterized in that
The unit volume specific surface area of the second electrode lay (320) is greater than the unit volume ratio of the first electrode layer (310)
Surface area；
The unit volume specific surface area of the third electrode layer (330) is greater than the unit volume ratio of the first electrode layer (310)
Surface area.
4. electrode according to claim 3, which is characterized in that
The ratio between unit volume specific surface area of the second electrode lay (320) and the first electrode layer (310) is greater than 1.05；
The ratio between unit volume specific surface area of the third electrode layer (330) and the first electrode layer (310) is greater than 1.05.
5. electrode according to claim 1, which is characterized in that the first electrode layer (310) includes along first table
It is directed toward the multiple sub-electrode layers being sequentially laminated on the direction of the second surface in face.
6. electrode according to claim 5, which is characterized in that when the electrode includes the second electrode lay (320),
The reactivity number of sites mesh of each sub-electrode layer successively drops along the direction that the first surface is directed toward the second surface
It is low.
7. electrode according to claim 5, which is characterized in that when the electrode includes third electrode layer (330),
The reactivity number of sites mesh of each sub-electrode layer successively increases along the direction that the first surface is directed toward the second surface
It is high.
8. electrode according to claim 5, which is characterized in that when the electrode include the second electrode lay (320) and
When third electrode layer (330), close to the sub-electrode layer of the first surface and close to the described of the second surface
The reactivity number of sites mesh of sub-electrode layer is greater than the reactivity number of sites mesh of remaining each sub-electrode layer.
9. electrode according to any one of claim 1 to 8, which is characterized in that
The material for forming the first electrode layer (310) is carbon felt；
Formed the second electrode lay (320) material be selected from carbon paper, the charcoal felt after electrochemical modification and it is hydrophilically modified after
Charcoal felt is any one or more of；
Formed the third electrode layer (330) material be selected from carbon paper, the charcoal felt after electrochemical modification and it is hydrophilically modified after
Charcoal felt is any one or more of.
10. a kind of flow battery, including bipolar plates (10), liquid flow frame (20), electrode (30) and amberplex (40), feature
It is, the electrode (30) electrode as claimed in any one of claims 1 to 9, wherein
When the electrode includes the second electrode lay (320), the second electrode lay (320) is close to the amberplex
(40) it is arranged；
When the electrode includes third electrode layer (330), the third electrode layer (330) is close to the bipolar plates (10)
Setting.
11. a kind of liquid stream battery stack, including multiple flow batteries, which is characterized in that the flow battery is claim 10 institute
The flow battery stated.
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| WO2018026005A1 (en) * | 2016-08-04 | 2018-02-08 | 昭和電工株式会社 | Redox flow cell |
| TWI703759B (en) * | 2019-09-05 | 2020-09-01 | 行政院原子能委員會核能研究所 | Storage module of distributed flow battery |
| 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 |
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| US20090092882A1 (en) * | 2007-10-09 | 2009-04-09 | University Of Victoria Innovation And Development Corporation | Fuel cell with flow-through porous electrodes |
| CN202917583U (en) * | 2011-10-04 | 2013-05-01 | 住友电气工业株式会社 | Cell unit framework, cell unit group and redox flow cell |
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| US20090092882A1 (en) * | 2007-10-09 | 2009-04-09 | University Of Victoria Innovation And Development Corporation | Fuel cell with flow-through porous electrodes |
| CN103636039A (en) * | 2011-04-11 | 2014-03-12 | 联合工艺公司 | Flow battery having electrodes with a plurality of different pore sizes and/or different layers |
| CN202917583U (en) * | 2011-10-04 | 2013-05-01 | 住友电气工业株式会社 | Cell unit framework, cell unit group and redox flow cell |
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