CN105680082A - Long-lifetime zinc-bromine flow battery structure and electrolyte - Google Patents
Long-lifetime zinc-bromine flow battery structure and electrolyte Download PDFInfo
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- CN105680082A CN105680082A CN201410659524.1A CN201410659524A CN105680082A CN 105680082 A CN105680082 A CN 105680082A CN 201410659524 A CN201410659524 A CN 201410659524A CN 105680082 A CN105680082 A CN 105680082A
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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
- H01M8/02—Details
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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
- H01M8/08—Fuel cells with aqueous electrolytes
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides a long-lifetime zinc-bromine flow battery structure and an electrolyte. A positive electrode and a negative electrode of a battery adopt an activated carbon felt as an electrode material. In order to solve the problem of short cycle lifetime of the battery caused by zinc accumulation due to the carbon felt. Chloride ions are added to electrolytes of the positive electrode and the negative electrode, so that, on one hand, the open-circuit voltage and the energy density of the battery are improved; and on the other hand, due to addition of the chloride ions, the problems of zinc deposition shape and form and zinc accumulation are greatly solved and the problem of relatively poor cycling stability caused by the activated carbon felt is solved.
Description
Technical field
The present invention relates to a kind of long-life zinc-bromine flow battery structure and electrolyte composition.
Background technology
Owing to zinc-bromine flow battery needs the equipment needed for the electrolyte circulation system such as circulating pump, hopper, result in the energy density of zinc-bromine flow battery to reduce due to the impact of system loss, these batteries auxiliary equipment makes zinc-bromine flow battery system structure complicated on the other hand, is unfavorable for miniaturization.
The electrolyte circulation systems such as patent CN99245261.9 describes a kind of zinc bromine accumulator, which eliminates the circulating pump of zinc-bromine flow battery, hopper, make battery structure simple and compact, reduce system energy consumption. But, this system does not propose to be suitable for the electrode that zinc bromine accumulator uses but the carbon felt electrode directly adopting zinc bromine liquid flow energy storage battery to use, result in the energy efficiency of system relatively low, and owing to not considering the suppression problem of battery liberation of hydrogen, cause that system needs to arrange steam vent, system design complexity, is unfavorable for sealing.
Along with the development of human economy and society, the demand of the energy is got more and more so that fossil energy ensures that pressure is increasing; And fossil energy conversion process produces many environmental problems: such as, discharge nitrogen and sulfur oxide cause acid rain, and emission greenhouse gas accelerates the process of global warming. Therefore, Renewable Energy Development, expand its proportion in energy resource structure, improve efficiency of energy utilization, social sustainable development will be promoted.
Electric energy is as the secondary energy sources of clean and effective, closely related with the daily productive life of the mankind, and ever-increasing electrical energy demands and the requirement to power quality, needing frequently network system to be carried out dilatation and upgrading, greatly developing the renewable energy power generation such as solar energy, wind energy is the important channel solving this problem. But, solar energy, wind energy have significantly discontinuous, unstable characteristic, and the reliable and stable operation of electrical network is proposed huge challenge, become and hinder its bottleneck developed further. Developing high-efficiency energy-storage technology for this, in order to smooth and to stablize the output of renewable energy power generation and to solve the time difference contradiction of generating and electricity consumption, improve power quality and electric network reliability, tool is of great significance.
For ensureing the stable power-supplying of the renewable energy system such as solar energy, wind energy, be necessary for exploitation efficiently, cheap, pollute less with safe and reliable energy storage technology. Making a general survey of various types of chemical storage batteries, flow battery becomes one of accumulator of the extensive energy storage of optimum with the advantage of its uniqueness.The same with all electrochemical cells, liquid flow energy storage battery is also realize electric energy by active substance generation redox reaction and battery system that chemical energy converts mutually. Different from traditional secondary battery, the electrode of liquid flow energy storage battery is inert electrode, provides reacting environment for electrode reaction, simultaneously works as the effect of eelctro-catalyst. Usual liquid flow energy storage battery is in original state, and active substance is stored in the middle of electrolyte with ionic condition, and positive pole and electrolyte liquid are attached separately in two storage tanks, realize electrolyte circulation in pipe-line system by liquid-feeding pump. In running, some battery system redox reaction show as the change of ionic valence condition, the deposition showing as metal having and dissolution, generally the battery of the latter's form of expression are referred to as appositional pattern liquid flow energy storage battery. At present research thinks that zinc is as the highest metal of specific energy density in the metal of stable existence in aqueous, is best suited for and uses as appositional pattern liquid flow energy storage battery negative pole, as: the liquid flow energy storage batteries such as zinc bromine, zinc-nickel, zinc-manganese, zinc are empty.
Zinc bromine liquid flow energy storage battery (Zinc-bromineredoxflowbattery, ZBB) it is a kind of low energy consumption, high efficiency, environmentally friendly liquid flow energy storage battery, have that energy density and current efficiency are high, device is simply steerable, long service life, the advantage such as with low cost, be mainly used in the fields such as renewable energy power generation, electric automobile such as peak load regulation network, wind energy and solar energy.
Zinc-bromine flow battery, when charge/discharge operation, drives electrolyte at battery internal circulation flow with circulating pump. When battery does not work, electrolyte is extracted out from cell cavity, is stored in hopper, makes to realize between inside battery both positive and negative polarity electrolyte open circuit, it is possible to prevents positive pole Charging state bromine to be diffused into negative pole and directly occurs chemical reaction to cause self discharge. When circular electrolyte is also prevented from charging simultaneously, zinc dendrite growth makes both positive and negative polarity short circuit through barrier film. Patent EPBIO167517, CN1087209A etc. are exactly this kind of circular electrolyte zinc-bromine bettery.
Current zinc-bromine flow battery all adopts conducting base and adheres to the method for catalysis material and prepare anode, and activity is poor on the one hand, adds operation on the other hand, is unfavorable for cost control. And carbon felt is widely used in all-vanadium flow battery as electrode, and carbon felt is just having good catalysis activity as zinc-bromine flow battery, but owing to the deposition that negative pole is zinc dissolves reaction, uses carbon felt can cause the accumulation of zinc, affect battery life.
The invention provides and a kind of carbon felt can be used as the solution of electrode material, while ensureing that battery performance improves, solve the accumulation of zinc and the problem that cycle life is relatively low.
Summary of the invention
The present invention provides a kind of long-life zinc-bromine flow battery structure and electrolyte composition.
For achieving the above object, the concrete technical scheme of the present invention is as follows:
Battery is made up of a joint or the two joint battery modules of above cells in series, electrolyte fluid reservoir, circulating pump and circulation line; Monocell includes positive pole, barrier film, negative pole, it is characterised in that both positive and negative polarity all adopts activated carbon-fiber felt as electrode material. Barrier film is perforated membrane or ion exchange membrane. The main salt of both positive and negative polarity electrolyte is bromide solutions, and zinc bromide concentration is 1.0mol/L 5.0mol/L. Both positive and negative polarity electrolyte all contains Chloride Solution, and chlorine ion concentration is 1.0mol/L 5.0mol/L.
Beneficial effects of the present invention:
1. this battery plus-negative plate all adopts carbon felt material, simplifies the preparation process of anode electrode.
2. this battery and electrolyte composition improve the energy density of battery.
3. this battery has good cyclical stability.
Accompanying drawing explanation
Fig. 1 is embodiment zinc bromine accumulator loop-around data figure;
Fig. 2 is comparative example zinc bromine accumulator loop-around data figure.
Detailed description of the invention
Embodiment 1
Electrode area 36cm2, charging and discharging currents density 20mA/cm2,
Electrolyte forms: the 2.0M bromide solutions+2.0M Klorvess Liquid of positive pole and each 40ml of negative pole;
Comparative example 1
Electrode area 36cm2, charging and discharging currents density 20mA/cm2,
Electrolyte forms: the 2.0M bromide solutions of each 40ml of both positive and negative polarity.
Battery plus-negative plate of the present invention all adopts activated carbon-fiber felt as electrode material, the zinc caused to solve negative pole employing carbon felt accumulates the problem that the battery cycle life caused is on the low side, both positive and negative polarity electrolyte adds chloride ion, improve open-circuit voltage and the energy density of battery on the one hand, on the other hand due to the addition of chloride ion, substantially improve zinc deposition morphology and zinc accumulation problem, solve a battery difficult problem owing to adopting the cyclical stability that brings of high activity carbon felt poor.
As seen from the figure: adding after chloride ion in electrolyte, the cycle performance of battery significantly improves. The conventional batteries not adding chloride ion circulates about 10 times, and namely performance decay substantially occurs.
Claims (5)
1. a long-life zinc-bromine flow battery structure, it is characterized in that: include a joint monocell or by two battery modules saving above cells in series, monocell includes positive pole, barrier film, negative pole, it is characterised in that: the positive pole of monocell and negative pole all adopt activated carbon-fiber felt as electrode material.
2. battery structure according to claim 1, it is characterised in that: battery is saved monocell by one or the two joint battery modules of above cells in series, electrolyte fluid reservoir, circulating pump and circulation line form.
3. battery structure according to claim 1 and 2, it is characterised in that: barrier film is perforated membrane or ion exchange membrane.
4. battery structure according to claim 1 and 2, it is characterised in that: the positive pole of described zinc-bromine flow battery and electrolyte liquid are bromide solutions, and zinc bromide concentration is 1.0mol/L 5.0mol/L.
5. battery structure according to claim 4, it is characterised in that: positive pole and electrolyte liquid all contain Chloride Solution, and chlorine ion concentration is 1.0mol/L 5.0mol/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410659524.1A CN105680082A (en) | 2014-11-17 | 2014-11-17 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
| PCT/CN2015/092058 WO2016078491A1 (en) | 2014-11-17 | 2015-10-16 | Zinc-bromine flow battery having extended service life |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410659524.1A CN105680082A (en) | 2014-11-17 | 2014-11-17 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
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| CN105680082A true CN105680082A (en) | 2016-06-15 |
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| CN201410659524.1A Pending CN105680082A (en) | 2014-11-17 | 2014-11-17 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
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| WO (1) | WO2016078491A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134141A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of no diaphragm static state zinc-bromine bettery |
| CN109786799A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of Zn-Ni liquid battery |
| CN109860658A (en) * | 2017-11-28 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of restoration methods of zinc bromine single flow battery performance |
| CN111106373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院大连化学物理研究所 | Zinc-bromine storage battery |
| CN113036156A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Gel electrolyte and zinc-bromine or zinc-iodine single flow battery |
| CN114628715A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for improving surface capacity and circulation stability of zinc-bromine flow battery |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109841852B (en) * | 2017-11-28 | 2021-07-06 | 中国科学院大连化学物理研究所 | Positive electrode active material for zinc-bromine single flow battery, and preparation and application thereof |
| CN111180778B (en) * | 2018-11-13 | 2023-01-24 | 陕西华银科技股份有限公司 | Zinc-nickel single flow battery negative electrode electrolyte and application thereof |
| CN111244561B (en) * | 2020-03-08 | 2023-01-13 | 南开大学 | Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte |
| CN114614038A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Zinc-bromine flow battery electrolyte and application thereof in zinc-bromine flow battery |
| CN114628719B (en) * | 2020-12-11 | 2023-12-22 | 中国科学院大连化学物理研究所 | High-capacity zinc-bromine single flow battery |
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| KR20090046087A (en) * | 2007-11-05 | 2009-05-11 | 한국에너지기술연구원 | A separator structure and redox flow battery containing the separator membrane |
| CN102479968A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Zinc / polyhalide energy storage cell |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134141A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of no diaphragm static state zinc-bromine bettery |
| CN108134141B (en) * | 2016-12-01 | 2020-05-05 | 中国科学院大连化学物理研究所 | Static zinc-bromine battery without diaphragm |
| CN109786799A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of Zn-Ni liquid battery |
| CN109786799B (en) * | 2017-11-10 | 2021-09-14 | 中国科学院大连化学物理研究所 | Zinc-nickel flow battery |
| CN109860658A (en) * | 2017-11-28 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of restoration methods of zinc bromine single flow battery performance |
| CN109860658B (en) * | 2017-11-28 | 2022-02-22 | 中国科学院大连化学物理研究所 | Method for recovering performance of zinc-bromine single flow battery |
| CN111106373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院大连化学物理研究所 | Zinc-bromine storage battery |
| CN111106373B (en) * | 2018-10-25 | 2021-05-25 | 中国科学院大连化学物理研究所 | Zinc-bromine storage battery |
| CN113036156A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Gel electrolyte and zinc-bromine or zinc-iodine single flow battery |
| CN114628715A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for improving surface capacity and circulation stability of zinc-bromine flow battery |
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| WO2016078491A1 (en) | 2016-05-26 |
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Application publication date: 20160615 |