CN102856573A - Zinc-vanadium redox flow energy storage battery - Google Patents
Zinc-vanadium redox flow energy storage battery Download PDFInfo
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- CN102856573A CN102856573A CN2011101823500A CN201110182350A CN102856573A CN 102856573 A CN102856573 A CN 102856573A CN 2011101823500 A CN2011101823500 A CN 2011101823500A CN 201110182350 A CN201110182350 A CN 201110182350A CN 102856573 A CN102856573 A CN 102856573A
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Abstract
The invention provides a zinc-vanadium redox flow energy storage battery, which comprises a battery module, an electrolyte storage tank, a liquid pump, and pipelines. The battery comprises a cathode, an anode, terminal plates for the cathode and the anode, and a diaphragm. The cathode comprises a cathode collector and a carbon felt. The anode is a deposited electrode. The cathode electrolyte is V<4+> containing sulfuric acid solution. The anode electrolyte is Zn<2+> containing acidic solution. The redox flow energy storage battery has the advantages of low cost, environment friendliness, high energy density, high temperature adaptability, and long cycle life.
Description
Technical field
The present invention relates to a kind of novel liquid flow energy storage battery, specially refer to a kind of almagrerite liquid flow energy storage battery.
Background technology
The liquid flow energy storage battery concept is Thaller in 1974 the earliest, a kind of electrochemical energy storage concept that L.H. (NASA LewisResearch Center, Cleveland, US) proposes.The core of flow battery is that the active material that carries out redox reaction, realization charge and discharge process is present in the electrolyte, and monocell or half-cell electrode are just as the place that reacts, rather than the place of active material storage.Because active material is stored in the electrolyte, flow battery has the advantages such as power separates with capacity, the life-span is long.So far oneself has more than 30 year history in the flow battery development, the various countries researcher is right by two oxidation/reduction electricity of conversion, obtained multiple available flow battery system, liquid phase energy storage chemical system has early stage CrlFe and TilFe system, and in recent years full vanadium, the development of zinc bromine flow battery system better.
All-vanadium liquid flow energy storage battery is phase late 1980s, the scholar university exploitation by the Xin Nanwei of Australia.All-vanadium liquid flow energy storage battery just/negative pole electrolyte is the vanadic sulfate of different valence state, supporting electrolyte is H
2SO
4Cell reaction is:
Negative reaction is: V
2+→ V
3++ e
Anodal reaction is: V
5++ e → V
4+
Two reactions are reversible at the carbon felt, need not catalyst-loaded, H
+Migration to keep the electric neutrality on both sides.This system is because active material is the same element that appraises at the current rate, and the cross-contamination issue of polarization response thing gets alleviation to a certain extent, and is convenient to the regeneration of the mutual miscible fluid of both positive and negative polarity.
But all-vanadium liquid flow energy storage battery has caused the high cost of battery because the price of vanadium is more expensive, and the negative pole V of all-vanadium flow battery
2+, V
3+, in the situation that the higher solubility of temperature reduces very easily precipitation, and battery inevitably can make system temperature raise in running, has caused the stable operating performance of battery to be subject to impact.Because the solubility of vanadium is lower, caused the actual energy density of all-vanadium flow battery to be only had about 15Wh/kg in addition.
Zinc bromine flow battery: zinc bromine flow battery is a kind of electro-chemical systems that stores energy in the solution.Positive and negative half-cell is separated by barrier film, and both sides electrolyte is ZnBr
2Solution.Under the effect of kinetic pump, electrolyte circulates in the closed-loop path of fluid reservoir and battery formation.Electrical potential difference between the redox reaction electrode pair is the power that reacts.The electrode reaction of zinc bromine flow battery is:
Negative reaction is: Zn
2++ 2e → Zn
Anodal reaction is: 3Br
-→ Br
3 -+ 2e
Zinc bromine flow battery is because negative pole zinc is the highest metal of specific energy density in the aqueous solution can the metal simple-substance of stable existence, so this battery has higher actual energy density: 65Wh/kg.But because the toxicity of this anode bromine is larger, restricted its further development.
Summary of the invention
The present invention seeks to for expensive, the low energy densities that solved all-vanadium liquid flow energy storage battery, negative pole hot operation poor-performing that the easy crystallization of high temperature negative pole electrolyte causes and the toxicity problem of zinc bromine flow battery bromine, in conjunction with the advantage of two kinds of batteries, a kind of almagrerite liquid flow energy storage battery is proposed simultaneously.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of almagrerite liquid flow energy storage battery, it is by battery module, and electrolyte storage tank, liquid pump and pipeline that positive and negative electrolyte is housed form, wherein battery module is made of positive pole, negative pole, battery diaphragm, and the electrolyte storage tank of positive and negative electrolyte is imported and exported with the both positive and negative polarity raw material of battery module by the road by liquid pump respectively and linked to each other; Anode electrolyte is the acid solution of tetravalence vanadium, and negative pole electrolyte is for containing Zn
2+Acid solution; The actual energy density of almagrerite flow battery is 35wh/kg.
Electrode reaction is as follows:
Negative reaction is: Zn
2++ 2e → Zn
Anodal reaction is: V
5++ e → V
4+
Anode electrolyte V
4+Concentration is 0.5-2.0mol/L; Negative pole electrolyte Zn
2+Concentration is 1.0-5.0mol/L.
The positive pole of battery is comprised of plus plate current-collecting body and carbon felt; Negative pole is the deposition type electrode of material with carbon element, metal forming, metallic plate or foam metal.Battery diaphragm adopts anion-exchange membrane.
In charge and discharge process, electrolyte constantly flows between electrolyte storage tank and pile by pipeline under liquid pump promotes.Zinc deposits to negative current collector during charging from electrolyte becomes negative electrode active material, V
4+Be oxidized to V
5+Be positive active material, zinc is dissolved into the electrolyte from negative current collector during discharge.V
5+Be reduced to V
4+Because the active material of battery is cation, and anionic membrane has the less characteristics of cation percent of pass, so solved the problem that the both positive and negative polarity active material mixes mutually.
Beneficial effect of the present invention:
1. the actual energy density of almagrerite liquid flow energy storage battery is 35wh/kg, far above the actual energy density of all-vanadium liquid flow energy storage battery 15wh/kg;
2. the thermal adaptability of almagrerite liquid flow energy storage battery is strong, all can work at-10 ℃ to 50 ℃;
3. the active material owing to battery is cation, and anionic membrane has the less characteristics of cation percent of pass, so solved the problem that the both positive and negative polarity active material mixes mutually;
4. almagrerite liquid flow energy storage battery environmental pollution is less, the paint having no volatile substances overflow problem;
5. battery has advantages of that cost is low, cycle life is higher.
Description of drawings
Fig. 1 is almagrerite structure of liquid-flow energy storage cell schematic diagram of the present invention;
The 1-battery module; The 2-negative end plate; The 3-positive end plate; The 4-negative pole; 5-is anodal; The 6-battery diaphragm; 7-negative pole storage tank; The anodal storage tank of 8-; The 9-pump;
Fig. 2 is the charging and discharging curve figure of embodiment 1 assembled battery;
Fig. 3 is the charging and discharging curve figure of embodiment 2 assembled batteries.
Embodiment
A kind of almagrerite liquid flow energy storage battery, it is by battery module, and electrolyte storage tank, liquid pump and pipeline that positive and negative electrolyte is housed form, wherein battery module is made of positive pole, negative pole, battery diaphragm, and the electrolyte storage tank of positive and negative electrolyte is imported and exported with the both positive and negative polarity raw material of battery module by the road by liquid pump respectively and linked to each other; In charge and discharge process, electrolyte constantly flows between electrolyte storage tank and pile by pipeline under liquid pump promotes.
Add 40ml in anode electrolyte storage tank, the vanadic sulfate of 1.5mol/L is dissolved in the sulfuric acid solution of 3mol/L as anode electrolyte, adds 40ml in the anolyte storage tank, and the 2.0mol/L solution of zinc sulfate is as negative pole electrolyte.Anodal carbon felt by collector graphite cake and 9cm2 forms, and the negative pole currect collecting plate is 9cm
2Graphite cake, battery diaphragm is the imidazole type anion-exchange membrane, at 50 ℃ battery is carried out 20mA/cm
2Charge-discharge test.As can be seen from Figure 2, the battery coulombic efficiency 97% that obtains, energy efficiency 69%.
Embodiment 2
Add 40ml in anode electrolyte storage tank, the vanadic sulfate solution of 1.0mol/L and the sulfuric acid solution of 3mol/L add 40ml as anode electrolyte in the anolyte storage tank, and the 3.0mol/L solution of zinc sulfate is as negative pole electrolyte.Anodal by collector graphite cake and 9cm
2The carbon felt form, the negative pole currect collecting plate is 9cm
2Foam zinc, battery diaphragm is the imidazole type anion-exchange membrane, at-10 ℃ battery is carried out 20mA/cm
2Charge-discharge test.As can be seen from Figure 3, the battery coulombic efficiency 96% that obtains, energy efficiency 70%.
Claims (7)
1. almagrerite liquid flow energy storage battery is characterized in that:
The negative electrode reaction of battery system is: Zn
2++ 2e → Zn; The anode electrode reaction is: V
5++ e → V
4+
2. almagrerite liquid flow energy storage battery according to claim 1 is characterized in that:
Described battery system is by battery module, and electrolyte storage tank, liquid pump and pipeline that positive and negative electrolyte is housed form, wherein battery module comprises positive end plate, negative end plate, positive pole, negative pole, battery diaphragm, anode electrolyte is the acid solution of tetravalence vanadium, negative pole electrolyte is the acid solution of zinc ion, and the electrolyte storage tank of positive and negative electrolyte is imported and exported with the both positive and negative polarity raw material of battery module by the road by liquid pump respectively and linked to each other.
3. almagrerite liquid flow energy storage battery according to claim 2, it is characterized in that: the positive pole of battery is comprised of plus plate current-collecting body and carbon felt; Negative pole is the deposition type electrode of material with carbon element, metal forming, metallic plate or foam metal.
4. almagrerite liquid flow energy storage battery according to claim 2 is characterized in that: anode electrolyte V
4+Concentration is 0.5-2.0mol/L.
5. almagrerite liquid flow energy storage battery according to claim 2 is characterized in that: negative pole electrolyte Zn
2+Concentration is 1.0-5.0mol/L.
6. almagrerite liquid flow energy storage battery according to claim 2, it is characterized in that: battery diaphragm is anion-exchange membrane.
7. almagrerite liquid flow energy storage battery according to claim 2 is characterized in that: described battery is in charge and discharge process, and electrolyte constantly flows between electrolyte storage tank and battery by pipeline under liquid pump promotes; Zinc ion deposits to negative pole during charging from electrolyte becomes negative electrode active material, V
4+Be oxidized to V
5+Be positive active material, zinc is dissolved into the electrolyte from negative pole during discharge, V
5+Be reduced to V
4+
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| CN2011101823500A CN102856573A (en) | 2011-06-30 | 2011-06-30 | Zinc-vanadium redox flow energy storage battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716374A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| CN105789670A (en) * | 2016-03-26 | 2016-07-20 | 江西理工大学 | Vanadium-based ionic liquid electrolyte for cathode of flow battery and preparation method for vanadium-based ionic liquid electrolyte |
| CN105810986A (en) * | 2016-03-26 | 2016-07-27 | 江西理工大学 | Zinc-iron based ionic liquid redox flow battery |
| CN114784331A (en) * | 2022-05-18 | 2022-07-22 | 西安交通大学 | Acid-base regulation system of zinc-bromine flow battery and working method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2751982A1 (en) * | 2009-02-18 | 2010-08-26 | Jens Noack | Method for storing electrical energy in ionic liquids |
| CN101997129A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Liquid flow battery |
| CN102244285A (en) * | 2011-05-24 | 2011-11-16 | 周成壁 | High-concentration zinc-vanadium redox battery |
-
2011
- 2011-06-30 CN CN2011101823500A patent/CN102856573A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2751982A1 (en) * | 2009-02-18 | 2010-08-26 | Jens Noack | Method for storing electrical energy in ionic liquids |
| CN101997129A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Liquid flow battery |
| CN102244285A (en) * | 2011-05-24 | 2011-11-16 | 周成壁 | High-concentration zinc-vanadium redox battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716374A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| CN104716374B (en) * | 2013-12-15 | 2017-04-12 | 中国科学院大连化学物理研究所 | Neutral zinc iron double fluid flow battery |
| CN105789670A (en) * | 2016-03-26 | 2016-07-20 | 江西理工大学 | Vanadium-based ionic liquid electrolyte for cathode of flow battery and preparation method for vanadium-based ionic liquid electrolyte |
| CN105810986A (en) * | 2016-03-26 | 2016-07-27 | 江西理工大学 | Zinc-iron based ionic liquid redox flow battery |
| CN105789670B (en) * | 2016-03-26 | 2018-03-27 | 江西理工大学 | A kind of flow battery positive pole vanadium base il electrolyte and preparation method thereof |
| CN105810986B (en) * | 2016-03-26 | 2018-03-27 | 江西理工大学 | Zinc iron-based ionic liquid flow battery |
| CN114784331A (en) * | 2022-05-18 | 2022-07-22 | 西安交通大学 | Acid-base regulation system of zinc-bromine flow battery and working method thereof |
| CN114784331B (en) * | 2022-05-18 | 2023-09-22 | 西安交通大学 | Acid-base regulation and control system of zinc-bromine flow battery and working method thereof |
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Application publication date: 20130102 |