CN108550884A - A kind of flow battery - Google Patents
A kind of flow battery Download PDFInfo
- Publication number
- CN108550884A CN108550884A CN201810507307.9A CN201810507307A CN108550884A CN 108550884 A CN108550884 A CN 108550884A CN 201810507307 A CN201810507307 A CN 201810507307A CN 108550884 A CN108550884 A CN 108550884A
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- China
- Prior art keywords
- flow battery
- electrolyte
- dihydroxy
- active material
- anode
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Classifications
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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
-
- 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
The present invention provides a kind of flow battery, including plus plate current-collecting body, anode, diaphragm, cathode, negative current collector, for store be dissolved with active material electrolyte fluid reservoir and drive electrolyte flow through anode and cathode occur redox reaction power source, the solvable electricity of anode is to the sulfonation benzoquinone compound of sulfonation diphenol compounds and oxidation state for reduction-state in flow battery of the present invention, and the solvable electricity of cathode is to the Pb for oxidation state2+With the Pb of reduction-state.It is cheap that the active material that battery system of the present invention uses compares the mineral elements such as vanadium used by traditional flow battery, while reducing flow battery system cost, ensure that the advantages such as flow battery high-energy density, long-life, width running temperature section；Also, by using Pb2+, sulfonation benzenediol mixed type positive and negative anodes electrolyte, be further able to overcome the problems, such as positive and negative electrode active material cross contamination.
Description
Technical field
The invention belongs to technical field of chemical power, more particularly to a kind of flow battery.
Background technology
The energy is the important substance basis of the national economic development and people's lives.With economic development and energy supply contradiction
Become increasingly conspicuous, imbalance between power supply and demand, which has become, restricts the bottleneck that economic development and living standards of the people improve.In order to guarantee I
State's national economy sustainable development and living standards of the people steadily improve, and fully developing and utilizing regenerative resource, there is strategy to anticipate
Justice.Have many advantages, such as that cleaning, zero carbon emission, distribution are wide as the regenerative resource of representative using wind energy, solar energy, but these can be again
Often there is discontinuous, unstable defect in the raw energy.Energy storage technology can improve regenerative resource Stability and dependability, be
Develop the key technology of clean energy resource.In order to ensure that stablizing for regenerative resource exports, there is an urgent need to matched energy storage to set
It is standby.
Since the concept of flow battery proposes, the pass of numerous scientific researchers has been caused by its unique technical advantage
Note.Flow battery have many advantages, such as pollution-free, long-life, energy-efficient and safeguard it is simple, in solar energy, wind energy storage and simultaneously
Net and peak load regulation network, remote districts power supply, uninterruptible power supply lamp field show huge application prospect.With it is existing other
Battery system is compared, and the difference of flow battery is that：The positive and negative electrode active material of flow battery is primarily present in electrolysis
In liquid, and positive-negative polarity active electrolyte is separately stored in two fluid reservoirs, the positive and negative electrode electrolyte in battery usually by from
Proton exchange separates, and during charging, discharging electric batteries, electrolyte is pumped to reaction tank and redox reaction occurs by the road, leads to
The variation that valence state occurs in electrode surface for active material is crossed, to realize the storage or release of electric energy.However, study at this stage compared with
More all-vanadium flow battery systems is due to the higher price of active material vanadium, and V5+Oxidisability is strong, generally requires the complete of costliness
Fluosulfonic acid amberplex can effectively reduce self-discharge of battery to improve energy content of battery efficiency, this allows for energy-storage system
Cost is excessively high, simultaneously because V5+Problem is precipitated in high temperature, causes the running temperature section of battery relatively narrow (5~40 DEG C), this is just limited
The large-scale application of all-vanadium flow battery so that flow battery functionization is under pressure.
Invention content
In view of described above, the purpose of the present invention is to provide it is a kind of it is of low cost, running temperature section is wide, it is excellent to have
The flow battery of energy efficiency.
Pile made of a kind of flow battery, including monocell or multiple cells in series, the monocell include just
Pole collector, negative current collector, the diaphragm between plus plate current-collecting body and negative pole currect collecting, be located at plus plate current-collecting body and diaphragm it
Between anode, the cathode between negative current collector and diaphragm, the fluid reservoir for storing the electrolyte containing active material and
Drive the power source of electrolyte flow direction anode and cathode；In anode and cathode redox reaction occurs for active material in electrolyte
It is respectively formed positive reaction zone and negative reaction area, the active material includes positive active material and negative electrode active material,
It is characterized in that：The reduction-state of the positive active material of the flow battery is sulfonation diphenol compounds, the flow battery
Positive active material oxidation state be sulfonation benzoquinone compound；The oxidation state of the negative electrode active material of the flow battery is
Pb2+, the reduction-state of the negative electrode active material of the flow battery is Pb.
Further, sulfonation diphenol compounds include in the present invention：2,5- dihydroxy benzenes sulfonic acids, 2,4- dihydroxy benzenes
Sulfonic acid, 3,5- dihydroxy benzenes sulfonic acids, 2,6- dihydroxy benzenes sulfonic acids, 2,3- dihydroxy benzenes sulfonic acids, 3,4- dihydroxy benzenes sulfonic acids, 2,5-
Dihydroxy benzenes -1,3- disulfonic acid, 2,5- dihydroxy benzenes -1,6- disulfonic acid, 2,5- dihydroxy benzenes-Isosorbide-5-Nitrae-disulfonic acid, 1,2- dihydroxy
Base benzene -3,4- disulfonic acid, 1,2- dihydroxy -3,5- benzenedisulfonic acid, 1,2- dihydroxy -3,6- benzenedisulfonic acid, 1,2- dihydroxy -4,
5- benzenedisulfonic acids, 1,3- dihydroxy -2,4- benzenedisulfonic acid, 1,3- dihydroxy -2,5- benzenedisulfonic acid, 1,3- dihydroxy -4,5- benzene
It is one or more in disulfonic acid and 1,3- dihydroxy -4,6- benzenedisulfonic acids.
Further, a concentration of 0.2mol/L of sulfonation diphenol compounds is dense to its saturation in electrolyte of the present invention
Degree.
Further, solvable Pb in the present invention2+Salt includes Pb (CH3SO3)2, Pb (NH2SO3)2, Pb (CF3SO3)2In one
Kind is a variety of.
Further, Pb in electrolyte of the present invention2+A concentration of 0.2mol/L to its saturated concentration.
Further, anode and cathode respectively use different electrolyte；I.e. under off working state, in positive reaction zone
The electrolyte of reaction contains positive active material, does not contain negative electrode active material, i.e., has soluble sulfonation benzenediol in electrolyte
Class compound；Contain negative electrode active material in the electrolyte reacted in negative reaction area, does not contain positive active material, i.e., it is electric
There is soluble Pb in solution liquid2+Salt.
Further, positive in of the invention to overcome the problems, such as cross contamination caused by ion interpenetrating between anode, cathode
Same electrolyte is shared with cathode；Existing solubility sulfonation in the electrolyte reacted in positive reaction zone, negative reaction area
Diphenol compounds also have soluble Pb2+Salt.
Further, further include supporting electrolyte in electrolyte of the present invention, the supporting electrolyte includes pyrovinic acid
(CH3SO3H), sulfamic acid (NH2SO3H), trifluoromethanesulfonic acid (CF3SO3H one or more in).
Further, in the present invention in electrolyte supporting electrolyte a concentration of 0.1mol/L~6.0mol/L.
Further, anode and cathode use tabular or cellular carbon material in the present invention, including：Carbon plate, carbon paper, carbon
Cloth or carbon felt.
Further, septation of the present invention is amberplex or perforated membrane.
According to embodiments of the present invention, electrolyte flows through pipeline to positive reaction zone and cathode through circulating pump from fluid reservoir
Reaction zone.
The charge-discharge principle of flow battery of the present invention：In charging process, anode electrolyte and electrolyte liquid are respectively from storage
Flow container is pumped to anode and cathode, sulfonation diphenol compounds are oxidized to sulfonation benzoquinone compound, Pb in anode2+
It is reduced into metal Pb in cathode；In charging process, sulfonation benzoquinone compound is reduced into sulfonation benzenediol class in anode
Object is closed, metal Pb is oxidized to Pb in cathode2+。
Compared with prior art, the beneficial effects of the present invention are：
(1) present invention is used as positive oxidation-reduction pair, Pb using sulfonated phenol quinones2+With Pb as cathode oxygen
It is right to change reduction electricity, since active material has higher solubility, good electrochemical redox active and good steady
It is qualitative so that flow battery has the advantages such as energy density height, long lifespan, running temperature section be wide.
(2) sulfonated phenol quinones as a positive electrode active material, compares traditional liquid stream electricity in flow battery of the present invention
The mineral elements procurement cost such as vanadium, manganese used by pond is low, and the present invention proposes the active material cost of flow battery it is estimated that only
For 350 yuan per kilowatt hour, well below the active material cost of existing vanadium flow battery (800 yuan per kilowatt hour).
(3) Pb further can be used in the present invention2+, sulfonation benzenediol mixed type positive and negative anodes electrolyte, and then can overcome just
The problem of negative electrode active material cross contamination.
(4) different bases are introduced by being designed to solvable phenol quinones structure in flow battery proposed by the present invention
Group can reach the purpose for adjusting its electrode potential height.
Description of the drawings
Fig. 1 is the single-cell structure schematic diagram of flow battery of the present invention, and in figure, 1 is positive, and 2 be diaphragm, and 3 be cathode, 4
It is negative pole currect collecting plate for anode collection plate, 5,6 be anode electrolyte fluid reservoir, and 7 be electrolyte liquid fluid reservoir, and 8 be circulating pump,
9 be circulation line.
Fig. 2 is the charging and discharging curve figure of the flow battery of the embodiment of the present invention 1.
Specific implementation mode
To facilitate the understanding of the present invention, with reference to the accompanying drawings of the specification and embodiment to technical solution of the present invention carry out more
Comprehensive description：
Embodiment 1：
The structural schematic diagram of monocell is as shown in Figure 1, monocell includes anode collection plate 1, (the present embodiment uses 2 to anode 2
×2cm2Carbon felt, thickness 2mm), diaphragm 3 (Nafion 117), 4 (2 × 2cm of cathode2Carbon felt, thickness 2mm), negative pole currect collecting plate 5,
Anode electrolyte fluid reservoir 6, electrolyte liquid fluid reservoir 7, circulating pump 8 and circulation line 9；Anode electrolyte and electrolyte liquid
It is 25 milliliters of aqueous solutions, before charging, the ingredient of the anode electrolyte and electrolyte liquid is consistent, and includes
0.2mol/L 2,5- dihydroxy benzenes sulfonic acid, 0.2mol/L Pb (CH3SO3)2, 2.0mol/L CH3SO3H。
Under the conditions of Fig. 2 is 25 DEG C monocell 40,60,80mA cm-2Constant current charge-discharge curve graph under current density, from Fig. 2
In can be seen that：It is tested by monocell constant current charge-discharge, in 40mA cm-2Under current density when constant current charge-discharge, coulombic efficiency reaches
To 90.5%, voltage efficiency reaches 75.7%.
Embodiment 2：
The structural schematic diagram of monocell is as shown in Figure 1, monocell includes anode collection plate 1, (the present embodiment uses 2 to anode 2
×2cm2Carbon felt, thickness 2mm), diaphragm 3 (Nafion 115), 4 (2 × 2cm of cathode2Carbon felt, thickness 2mm), negative pole currect collecting plate 5,
Anode electrolyte fluid reservoir 6, electrolyte liquid fluid reservoir 7, circulating pump 8 and circulation line 9；Anode electrolyte and electrolyte liquid
It is 25 milliliters of aqueous solutions, before charging, the ingredient of the anode electrolyte and electrolyte liquid is consistent, and includes
0.4mol L-12,5- dihydroxy benzenes sulfonic acids, 0.4mol L-1Pb(NH2SO3)2, 2.0mol L-1NH2SO3H。
Tested by monocell constant current charge-discharge, monocell 40,60,80mA cm-2Constant current under current density, in 60mA
cm-2Under current density when constant current charge-discharge, coulombic efficiency reaches 91.3%, and voltage efficiency reaches 76.4%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. pile made of a kind of flow battery, including monocell or multiple cells in series, the monocell includes anode
Collector (4), the diaphragm (2) between plus plate current-collecting body (4) and negative current collector (5), is located at just negative current collector (5)
Anode (1) between pole collector (4) and diaphragm (2), is used the cathode (3) between negative current collector (5) and diaphragm (2)
In storage electrolyte containing active material fluid reservoir and drive the power source of electrolyte flow direction positive (1) and cathode (2)；Electrolysis
Active material is respectively formed positive reaction zone and negative reaction area, the work in anode and cathode generation redox reaction in liquid
Property substance includes positive active material and negative electrode active material, it is characterised in that：The positive active material of the flow battery
Reduction-state is sulfonation diphenol compounds, and the oxidation state of the positive active material of the flow battery is sulfonation benzoquinones chemical combination
Object；The oxidation state of the negative electrode active material of the flow battery is solvable Pb2+Salt, the negative electrode active material of the flow battery
Reduction-state is Pb.
2. a kind of flow battery as described in claim 1, it is characterised in that：The sulfonation diphenol compounds include：2,
5- dihydroxy benzenes sulfonic acids, 2,4- dihydroxy benzenes sulfonic acids, 3,5- dihydroxy benzenes sulfonic acids, 2,6- dihydroxy benzenes sulfonic acids, 2,3- dihydroxy
Benzene sulfonic acid, 3,4- dihydroxy benzenes sulfonic acids, 2,5- dihydroxy benzenes -1,3- disulfonic acid, 2,5- dihydroxy benzenes -1,6- disulfonic acid, 2,5-
Dihydroxy benzenes-Isosorbide-5-Nitrae-disulfonic acid, 1,2- dihydroxy benzenes -3,4- disulfonic acid, 1,2- dihydroxy -3,5- benzenedisulfonic acid, 1,2- dihydroxy
Base -3,6- benzenedisulfonic acid, 1,2- dihydroxy -4,5- benzenedisulfonic acid, 1,3- dihydroxy -2,4- benzenedisulfonic acid, 1,3- dihydroxy -2,
5- benzenedisulfonic acids, 1,3- dihydroxy -4,5- benzenedisulfonic acid and 1 are one or more in 3- dihydroxy -4,6- benzenedisulfonic acids.
3. a kind of flow battery as described in claim 1, it is characterised in that：Sulfonation diphenol compounds in the electrolyte
A concentration of 0.2mol/L to its saturated concentration.
4. a kind of flow battery as described in claim 1, it is characterised in that：The solvable Pb2+Salt includes Pb (CH3SO3)2, Pb
(NH2SO3)2, Pb (CF3SO3)2In it is one or more.
5. a kind of flow battery as described in claim 1, it is characterised in that：Pb in the electrolyte2+A concentration of 0.2mol/
L is to its saturated concentration.
6. a kind of flow battery as described in claim 1, it is characterised in that：The anode (1) and the cathode (2) respectively make
With different electrolyte.
7. a kind of flow battery as described in claim 1, it is characterised in that：The anode (1) and the cathode (2) share same
One electrolyte.
8. a kind of flow battery as described in claim 1, it is characterised in that：Further include supporting electrolyte in the electrolyte,
The supporting electrolyte includes one or more in pyrovinic acid, sulfamic acid, trifluoromethanesulfonic acid, and electrolysis is supported in electrolyte
A concentration of 0.1mol/L~6.0mol/L of matter.
9. a kind of flow battery as described in claim 1, it is characterised in that：The anode (1) and the cathode (2) are using flat
Plate or cellular carbon material, including：Carbon plate, carbon paper, carbon cloth or carbon felt.
10. a kind of flow battery as described in claim 1, it is characterised in that：The diaphragm (3) is amberplex or porous
Film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810507307.9A CN108550884A (en) | 2018-05-24 | 2018-05-24 | A kind of flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810507307.9A CN108550884A (en) | 2018-05-24 | 2018-05-24 | A kind of flow battery |
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| Publication Number | Publication Date |
|---|---|
| CN108550884A true CN108550884A (en) | 2018-09-18 |
Family
ID=63495550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810507307.9A Pending CN108550884A (en) | 2018-05-24 | 2018-05-24 | A kind of flow battery |
Country Status (1)
| Country | Link |
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| CN (1) | CN108550884A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697240A (en) * | 2020-07-31 | 2020-09-22 | 济南大学 | Preparation method of flow battery positive electrode material |
| CN112993355A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Organic flow battery |
| CN113363544A (en) * | 2021-06-24 | 2021-09-07 | 常州大学 | Cathode deep eutectic electrolyte of zinc-organic mixed flow battery and flow battery thereof |
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| CN103500841A (en) * | 2013-10-18 | 2014-01-08 | 中国科学院宁波材料技术与工程研究所 | Composite bipolar plate of flow battery and method for manufacturing composite bipolar plate |
| CN106549179A (en) * | 2015-09-21 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of organic system lithium quinone flow battery |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7645856B2 (en) * | 2004-11-19 | 2010-01-12 | National Research Council Of Canada | Ether nitrile co-polymers containing sulfonic acid groups for PEM application |
| CN102035007A (en) * | 2009-09-25 | 2011-04-27 | 中国人民解放军63971部队 | Water-soluble organic couple redox flow battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993355A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Organic flow battery |
| CN112993355B (en) * | 2019-12-12 | 2022-05-31 | 中国科学院大连化学物理研究所 | Organic flow battery |
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| CN113363544A (en) * | 2021-06-24 | 2021-09-07 | 常州大学 | Cathode deep eutectic electrolyte of zinc-organic mixed flow battery and flow battery thereof |
| CN113363544B (en) * | 2021-06-24 | 2024-02-13 | 常州大学 | Cathode deep eutectic electrolyte of zinc organic mixed flow battery and flow battery thereof |
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