CN104716374A - Neutral zinc iron double fluid flow battery - Google Patents

Neutral zinc iron double fluid flow battery Download PDF

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Publication number
CN104716374A
CN104716374A CN201310694610.1A CN201310694610A CN104716374A CN 104716374 A CN104716374 A CN 104716374A CN 201310694610 A CN201310694610 A CN 201310694610A CN 104716374 A CN104716374 A CN 104716374A
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zinc
positive
neutral
flow battery
electrolyte
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CN104716374B (en
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张华民
程元徽
赖勤志
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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 discloses a neutral zinc iron double fluid flow battery, a single cell comprises positive and negative electrode end plates, a collector, a positive electrode, a film, a negative electrode, positive and negative electrode liquid storage tanks, a pipeline and a pump, wherein the positive electrode is a porous electrode, the negative electrode is a deposition type electrode, a positive electrode electrolyte solution is a neutral K4Fe (CN) 6 solution, and a negative electrolyte solution is a neutral zinc-ion-containing; when in charging, the electrolyte solutions respectively pass through the positive and negative electrode liquid storage tanks to be respectively sent to the positive electrode and the negative electrode, K3Fe (CN) 6 is produced by oxidation reaction of active material K4Fe (CN) 6 in the positive electrode storage tank, and zinc ions are directly deposited in the form of elemental zinc in the negative electrode; when in discharge, K4Fe (CN) 6 is produced by reduction reaction of active material K3Fe (CN) 6 in the positive electrode electrolyte solution, and the elemental zinc is oxidized into zinc ions to return through the pump back to the negative electrode liquid storage tank. The positive and negative electrode electrolyte solutions are neutral solutions, overcome the corrosion problems caused by a strong acid and a strong alkali as support electrolytes in the traditional liquid flow battery.

Description

A kind of neutral zinc-iron double flow battery
Technical field
The present invention relates to flow battery field, particularly a kind of zinc-iron flow battery.
Background technology
Electric energy is the energy that the mankind depend on for existence, and current electric energy is mainly derived from fossil energy, and the transition of fossil energy consumption not only causes energy shortage, and gives off a large amount of poisonous and hazardous gas, causes environmental pollution.Therefore people start the development and utilization paying close attention to the regenerative resource such as wind energy, solar energy, but because the regenerative resource such as solar energy, wind energy has discontinuity and unsteadiness, if be directly incorporated into electrical network, can impact electrical network, therefore to effectively utilize these regenerative resources, just must be equipped with efficient, cheap, safe and reliable energy storage device.Flow battery on the basis meeting above-mentioned condition, with its capacity and power can independent design, not by the restriction of territorial environment unique advantage and become one of equipment of the extensive energy storage of current optimum.
The comparatively ripe flow battery system of current development has: zinc bromine, sodium polysulfide bromine, Quan Fan and zinc-nickel system.The above two can overflow bromine simple substance and cause environmental pollution when Charging state due to side of the positive electrode electrolyte, constrain its large-scale application.Full vanadium system is lower due to the solubility of vanadium ion, needs the acid of high concentration as solvent, can cause the corrosion of electrode and pipeline.And the electrolyte of zinc-nickel system is overbasic zincate solution, needing by concentration is 6 ~ 14mol dm ?3alkali lye as solvent, not only waste resource, and the corrosivity of alkali is even more serious.
Summary of the invention
In order to solve the problem, reach the object reducing corrosion, concrete technical scheme of the present invention is as follows:
A kind of neutral zinc-iron double flow battery, battery one saves pile, anolyte liquid storage tank, the cathode electrolyte storage tank of monocell or the above cells in series of two joints; Anode electrolyte is K4Fe (CN) 6 aqueous solution, and electrolyte liquid is the neutral aqueous solution containing zinc ion.
Anolyte liquid storage tank is in-built is filled with anode electrolyte, and anolyte liquid storage tank is connected through the positive pole entrance and exit of liquid delivery pump by pipeline monocell or pile;
Be filled with electrolyte liquid in cathode electrolyte storage tank, cathode electrolyte storage tank is connected through the negative pole entrance and exit of liquid delivery pump by pipeline monocell or pile.
During charging, electrolyte is delivered to positive and negative electrode via pump respectively from both positive and negative polarity fluid reservoir, the active material K in positive pole storage tank 4fe (CN) 6there is oxidation reaction and generate K 3fe (CN) 6, zinc ion directly deposits with zinc simple substance form at negative pole; During electric discharge, in anode electrolyte active material K 3fe (CN) 6there is reduction reaction and generate K 4fe (CN) 6; Zinc simple substance is oxidized to zinc ion via being pumped back in negative pole fluid reservoir.
Monocell comprises both positive and negative polarity end plate, collector, film, positive pole and negative pole.
Active material in anode electrolyte is K 4fe (CN) 6, concentration range 0.1mol dm -3~ 1mol dm -3, also can add the conductivity that some additives improve electrolyte, as K 2sO 4, KNO 3with one or more in KCl.Electrolyte liquid is the neutral aqueous solution containing zinc ion, as ZnSO 4, Zn (NO 3) 2, and ZnCl 2deng, concentration range 0.1mol dm -3~ 3mol dm -3, neutral aqueous solution ph6-8, also can add some supporting electrolytes, as K 2sO 4, KNO 3with one or more in KCl.
Neutral aqueous solution concentration containing zinc ion is 1 ~ 3mol dm -3.
Positive and negative electrode is the porous carbon felt, foam metal, carbon cloth or the graphite cake that conduct electricity.
Beneficial effect of the present invention:
Right by screening positive and negative electrode reaction electricity, propose the concept of neutral zinc-iron flow battery, improving traditional flow battery needs strong acid and strong base to cause the problem of corrosion as supporting electrolyte, and neutral zinc-iron flow battery both positive and negative polarity reduction potential is respectively K 4fe (CN) 6/ K 3fe (CN) 6and Zn 2+/ Zn, solvent is water, non-corrosiveness, and zinc-iron rich reserves, with low cost, can meet the demand of large-scale application, be a kind of energy storage device having application prospect; There is fail safe high, stablize, cost is low, structure and the simple feature of manufacturing process; Neutral electrolyte can improve zinc load zinc ion solubility simultaneously, thus improves energy density.
Accompanying drawing explanation
Fig. 1 is zinc-iron double flow battery schematic diagram;
1 ?positive end plate; 2 ?collector; 3 ?positive pole; 4 ?film; 5 ?negative pole; 6 ?negative end plate; 7,8, pump; 9 ?anolyte liquid storage tanks; 10 ?cathode electrolyte storage tank;
Fig. 2 is cycle performance of battery figure prepared by embodiment 1.
Embodiment
Electrolyte configures:
Electrolyte: anode electrolyte is 40ml0.4mol dm -3k 4fe (CN) 6solution; Electrolyte liquid is 40mL0.4moldm -3znSO 4solution.
Battery is assembled:
Monocell is positive end plate, collector, positive pole 3x3cm successively 2carbon felt, film, negative pole 3x3cm 2graphite cake, negative end plate.Single-cell structure and system are shown in Fig. 1.
Battery testing:
Electrolyte flow rate: 5ml/min; Charging and discharging currents density 20mA/cm 2; Charging capacity 180mAh, discharge cut-off voltage is 0.8V.Battery performance is shown in Fig. 2, known at 20mA/cm by charging and discharging currents density map 2 2; Under charging capacity 180mAh condition, the energy efficiency of battery reaches about 74%, and 30 times cycle performance has no obvious decay.

Claims (9)

1. a neutral zinc-iron double flow battery, is characterized in that: battery one saves pile, anolyte liquid storage tank, the cathode electrolyte storage tank of monocell or the above cells in series of two joints; Anode electrolyte is K 4fe (CN) 6the aqueous solution, electrolyte liquid is the neutral aqueous solution containing zinc ion.
2. neutral zinc-iron double flow battery according to claim 1, is characterized in that:
Anolyte liquid storage tank is in-built is filled with anode electrolyte, and anolyte liquid storage tank is connected through the positive pole entrance and exit of liquid delivery pump by pipeline monocell or pile;
Be filled with electrolyte liquid in cathode electrolyte storage tank, cathode electrolyte storage tank is connected through the negative pole entrance and exit of liquid delivery pump by pipeline monocell or pile.
3. neutral zinc-iron double flow battery according to claim 1, is characterized in that: monocell comprises both positive and negative polarity end plate, collector, film, positive pole and negative pole.
4. neutral zinc-iron double flow battery according to claim 1, is characterized in that: the active material in anode electrolyte is K 4fe (CN) 6, concentration is 0.1 ~ 1mol dm -3.
5. neutral zinc-iron double flow battery according to claim 1, is characterized in that, the neutral aqueous solution containing zinc ion is ZnSO 4, Zn (NO 3) 2, ZnCl 2in the aqueous solution of one or two or more kinds, zinc ion concentration is 0.1 ~ 3mol dm -3, solution ph 6-8.
6. neutral zinc-iron double flow battery according to claim 5, is characterized in that: the neutral aqueous solution concentration containing zinc ion is 1 ~ 3mol dm -3.
7. the neutral zinc-iron double flow battery according to claim 1,3 or 4, is characterized in that: anode electrolyte is or/and containing additive K in electrolyte liquid 2sO 4, KNO 3, one or two or more kinds in KCl, additive concentration is 0.1 ~ 3moldm -3.
8. neutral zinc-iron double flow battery according to claim 1, it is characterized in that: during charging, electrolyte is delivered to positive and negative electrode via pump respectively from both positive and negative polarity fluid reservoir, the active material K in positive pole storage tank 4fe (CN) 6there is oxidation reaction and generate K 3fe (CN) 6, zinc ion directly deposits with zinc simple substance form at negative pole; During electric discharge, in anode electrolyte active material K 3fe (CN) 6there is reduction reaction and generate K 4fe (CN) 6; Zinc simple substance is oxidized to zinc ion via being pumped back in negative pole fluid reservoir.
9. neutral zinc-iron double flow battery according to claim 3, is characterized in that: positive and negative electrode is the porous carbon felt, foam metal, carbon cloth or the graphite cake that conduct electricity.
CN201310694610.1A 2013-12-15 2013-12-15 Neutral zinc iron double fluid flow battery Active CN104716374B (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105826587A (en) * 2016-03-26 2016-08-03 江西理工大学 Iron-based ionic liquid electrolyte for flow cell positive electrode and preparation method thereof
CN106558712A (en) * 2015-09-21 2017-04-05 中国科学院大连化学物理研究所 A kind of application of composite membrane in neutral system zinc-iron flow battery
CN107887629A (en) * 2017-11-10 2018-04-06 四川川润液压润滑设备有限公司 Double-liquid-flow energy storage battery
CN108123174A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery anode electrolyte and application
WO2018103518A1 (en) * 2016-12-10 2018-06-14 中国科学院大连化学物理研究所 Neutral zinc-iron flow battery
WO2018103517A1 (en) * 2016-12-10 2018-06-14 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery
CN108431999A (en) * 2015-11-18 2018-08-21 耶拿弗里德里希·席勒大学 Mixing flow battery group for storing electric energy and its application
CN108615921A (en) * 2016-12-10 2018-10-02 中国科学院大连化学物理研究所 A kind of neutrality zinc-iron flow battery electrolyte
CN109509901A (en) * 2017-09-15 2019-03-22 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery
CN109755620A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 A kind of zinc iodine solution galvanic battery
CN109755560A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 A kind of zinc-nickel double flow battery
CN109873190A (en) * 2017-12-01 2019-06-11 中国科学院大连化学物理研究所 A kind of neutrality Zinc-iron single flow battery
CN111180774A (en) * 2018-11-12 2020-05-19 湖南国昶能源科技有限公司 Preparation method of neutral iron-sulfur double-flow battery
CN112103545A (en) * 2020-09-01 2020-12-18 山东奥德储能科技有限公司 Preparation method of long-life neutral zinc-iron flow battery
CN113067025A (en) * 2020-01-02 2021-07-02 中国科学院大连化学物理研究所 Online recovery method for electrolyte of alkaline zinc-iron flow battery
CN115020756A (en) * 2022-06-13 2022-09-06 燕山大学 Zinc-bromine/iodine double flow battery

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CN102332596A (en) * 2011-08-16 2012-01-25 上海交通大学 All-iron redox energy storage cell, electrolyte of battery and preparation method of electrolyte
CN102823046A (en) * 2010-03-30 2012-12-12 应用材料公司 High performance flow battery
CN102856573A (en) * 2011-06-30 2013-01-02 中国科学院大连化学物理研究所 Zinc-vanadium redox flow energy storage battery

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102823046A (en) * 2010-03-30 2012-12-12 应用材料公司 High performance flow battery
CN102856573A (en) * 2011-06-30 2013-01-02 中国科学院大连化学物理研究所 Zinc-vanadium redox flow energy storage battery
CN102332596A (en) * 2011-08-16 2012-01-25 上海交通大学 All-iron redox energy storage cell, electrolyte of battery and preparation method of electrolyte

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106558712A (en) * 2015-09-21 2017-04-05 中国科学院大连化学物理研究所 A kind of application of composite membrane in neutral system zinc-iron flow battery
CN108431999A (en) * 2015-11-18 2018-08-21 耶拿弗里德里希·席勒大学 Mixing flow battery group for storing electric energy and its application
CN105826587A (en) * 2016-03-26 2016-08-03 江西理工大学 Iron-based ionic liquid electrolyte for flow cell positive electrode and preparation method thereof
CN105826587B (en) * 2016-03-26 2018-04-10 江西理工大学 A kind of flow battery positive pole iron-based ionic liquid electrolyte and preparation method thereof
CN108123174A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery anode electrolyte and application
WO2018103518A1 (en) * 2016-12-10 2018-06-14 中国科学院大连化学物理研究所 Neutral zinc-iron flow battery
WO2018103517A1 (en) * 2016-12-10 2018-06-14 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery
CN108232265A (en) * 2016-12-10 2018-06-29 中国科学院大连化学物理研究所 A kind of neutrality zinc-iron flow battery
CN108461784A (en) * 2016-12-10 2018-08-28 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery
CN108615921A (en) * 2016-12-10 2018-10-02 中国科学院大连化学物理研究所 A kind of neutrality zinc-iron flow battery electrolyte
CN109509901B (en) * 2017-09-15 2021-08-31 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery
CN109509901A (en) * 2017-09-15 2019-03-22 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery
CN109755620A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 A kind of zinc iodine solution galvanic battery
CN109755560A (en) * 2017-11-08 2019-05-14 中国科学院大连化学物理研究所 A kind of zinc-nickel double flow battery
CN107887629B (en) * 2017-11-10 2020-11-20 四川川润液压润滑设备有限公司 Double-liquid-flow energy storage battery
CN107887629A (en) * 2017-11-10 2018-04-06 四川川润液压润滑设备有限公司 Double-liquid-flow energy storage battery
CN109873190A (en) * 2017-12-01 2019-06-11 中国科学院大连化学物理研究所 A kind of neutrality Zinc-iron single flow battery
CN111180774A (en) * 2018-11-12 2020-05-19 湖南国昶能源科技有限公司 Preparation method of neutral iron-sulfur double-flow battery
CN111180774B (en) * 2018-11-12 2021-05-18 湖南国昶能源科技有限公司 Preparation method of neutral iron-sulfur double-flow battery
CN113067025A (en) * 2020-01-02 2021-07-02 中国科学院大连化学物理研究所 Online recovery method for electrolyte of alkaline zinc-iron flow battery
CN113067025B (en) * 2020-01-02 2022-04-29 中国科学院大连化学物理研究所 Online recovery method for electrolyte of alkaline zinc-iron flow battery
CN112103545A (en) * 2020-09-01 2020-12-18 山东奥德储能科技有限公司 Preparation method of long-life neutral zinc-iron flow battery
CN115020756A (en) * 2022-06-13 2022-09-06 燕山大学 Zinc-bromine/iodine double flow battery
CN115020756B (en) * 2022-06-13 2023-07-25 燕山大学 Zinc-bromine/iodine double flow battery

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