CN109509901A - A kind of Alkaline Zinc iron liquid galvanic battery - Google Patents

A kind of Alkaline Zinc iron liquid galvanic battery Download PDF

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CN109509901A
CN109509901A CN201710830958.7A CN201710830958A CN109509901A CN 109509901 A CN109509901 A CN 109509901A CN 201710830958 A CN201710830958 A CN 201710830958A CN 109509901 A CN109509901 A CN 109509901A
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electrolyte
zinc
ferrocyanide
positive
iron liquid
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CN109509901B (en
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李先锋
袁治章
张华民
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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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    • 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
    • H01M8/083—Alkaline fuel cells
    • 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
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04791—Concentration; Density
    • H01M8/0482—Concentration; Density of the electrolyte
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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 relates to a kind of Alkaline Zinc iron liquid galvanic battery, battery module made of You Yijie monocell or the above monocell series/parallel of two sections, electrolyte fluid reservoir, circulating pump, circulation line composition；Positive and negative electrode uses identical electrolyte, and for highly basic as supporting electrolyte, carbon felt or carbon paper as electrode, graphite plate forms symmetric form flow battery as collector plate；Positive and negative electrode electrolyte is the oxide of ferrocyanide, zinc salt or/and zinc and the mixed aqueous solution of highly basic.This positive and negative electrode is had and traditional comparable battery performance of Alkaline Zinc iron liquid galvanic battery using the symmetric form Alkaline Zinc iron liquid galvanic battery of identical electrolyte, simultaneously because positive and negative electrode uses identical electrolyte, the osmotic pressure of positive and negative electrode electrolyte is consistent, avoid traditional Alkaline Zinc iron liquid galvanic battery because positive and negative electrode electrolyte permeability pressure it is inconsistent caused by electrolyte migrate the problem of, significantly reduce the maintenance cost of system in actual application.

Description

A kind of Alkaline Zinc iron liquid galvanic battery
Technical field
The present invention relates to flow battery field, in particular to a kind of Alkaline Zinc iron liquid galvanic battery technical field.
Background technique
Flow battery is a kind of electrochemical energy storage new technology, compared with other energy storage technologies, has system flexible design, stores Capacitance is big, addressing is free, energy conversion efficiency is high, can advantages, the Ke Yiguang such as deep discharge, safety and environmental protection, maintenance cost be low It is general to be filled out applied to renewable energy power generations energy storage, emergency power system, stand-by station and electric system peak clippings such as wind energy, solar energy Paddy etc..All-vanadium flow battery is since highly-safe, stability is good, the high-efficient, service life grows (service life > 15 year), at low cost etc. Advantage is considered to have good application prospect, but the electrolyte price of VFB is more expensive, and it is big that this limits it to a certain extent Sizable application.Therefore exploitation is had excellent performance, and low-cost electrochemical energy storage cell is very heavy to renewable energy popularization and application It wants.
Other than all-vanadium flow battery, develop at present more mature flow battery mainly there are also zinc-bromine flow battery, Sodium polysulfide bromine and zinc-nickel cell system.Wherein zinc-bromine flow battery and sodium polysulfide Zn-Br battery are being filled due to side of the positive electrode electrolyte Bromine simple substance can be generated when electric and causes environmental pollution, constrain its large-scale application；And the electrolyte of zinc-nickel cell system needs to use The highly basic of 10~14mol/L is as supporting electrolyte, the aqueous slkali severe corrosion to equipment of this high concentration.
Alkaline Zinc iron liquid galvanic battery has preferable due to the advantage at low cost with electrolyte in extensive flow battery Application prospect.Existing Alkaline Zinc iron liquid galvanic battery anode electrolyte uses the alkaline solution of ferrocyanide, electrolyte Liquid dissolved solution in highly basic using the oxide of zinc salt or zinc, the battery of this electrolyte system in the process of running by It is inconsistent in positive and negative electrode electrolyte permeability pressure, cause electrolyte migration serious, so as to cause the decline of cell voltage efficiency, thus Cause energy content of battery efficiency to decay, considerably increases the maintenance cost of battery.Alkaline Zinc iron liquid galvanic battery cathode is surveyed in electricity simultaneously The extremely upper deposition dissolution that zinc occurs, can generate serious zinc dendrite or class dendritic crystalline deposition when running under high current densities Object causes battery short circuit.
Summary of the invention
In order to solve the above technical problems, developing, a kind of low cost, structure be simple, zinc-iron liquid stream storage of electrochemical performance Energy battery is particularly important, and in order to achieve the above objectives, the present invention proposes a kind of Alkaline Zinc iron liquid galvanic battery electrolyte, particular technique Scheme is as follows:
Battery includes battery module made of a section monocell or the above monocell series/parallel of two sections, equipped with positive and negative electrode electricity Fluid reservoir, circulating pump and the circulation line of liquid are solved, the monocell includes anode collection plate, negative pole currect collecting plate, electrode, ion biography Guided membrane.Electrode is carbon felt or carbon paper；Positive and negative electrode uses identical electrolyte: being by ferrocyanide, zinc salt or/and zinc The mixed aqueous solution of oxide and highly basic composition.
The Alkaline Zinc iron liquid galvanic battery anode electrolyte is the oxide of ferrocyanide, zinc salt or/and zinc and strong The mixed aqueous solution of alkali；Electrolyte liquid be ferrocyanide identical with anode electrolyte, zinc salt or/and zinc oxide with The mixed aqueous solution of highly basic.
Wherein the ferrocyanide include potassium ferrocyanide, sodium ferrocyanide, ferrocyanide lithium, ferrocyanide magnesium or One of calcium ferrocyanide or more than one；The preferred potassium ferrocyanide of ferrocyanide or sodium ferrocyanide；The zinc salt Or/and the oxide of zinc include: zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate, zinc oxide, one of Or more than one, preferred zinc chloride, more preferable zinc oxide；Highly basic includes one in sodium hydroxide, lithium hydroxide or potassium hydroxide Kind or more than one.
The Alkaline Zinc iron fluid cell electrolyte is prepared according to the following procedure:
By one of ferrocyanide or more than one be dissolved in deionized water or strong base solution, temperature be 20~ It is sufficiently stirred at 100 DEG C 0.5~10 hour and homogeneous solution is made；
By one of oxide of zinc salt or/and zinc or more than one one of with highly basic or after more than one mix Deionized water stirring is slowly added to be made after homogeneous solution and above-mentioned ferrocyanide solution mixing system is standby obtains Alkaline Zinc iron liquid The electrolyte of galvanic battery；
The electrolyte can also by one of ferrocyanide or more than one, in the oxide of zinc salt or/and zinc One or more and one of highly basic or more than one mix after addition deionized water in the case where temperature is 20~100 DEG C It is sufficiently stirred 0.5~10 hour and is prepared.
Wherein, in electrolyte ferrocyanide concentration be 0.0001~1mol/L, preferably 0.05~0.8mol/L, it is more excellent Select 0.4-0.8mol/L；The Zn (OH) that the oxide of zinc salt or zinc generates after dissolving in highly basic4 2-Concentration be 0.0001~ 2mol/L, preferably 0.05~0.8mol/L, more preferable 0.1-0.5mol/L；The concentration of highly basic be 0.0001~5mol/L, preferably 1 ~8mol/L, more preferable 2-4mol/L.
It can be also added in electrolyte in the soluble-salt of potassium chloride, sodium sulphate, sodium chloride, ammonium chloride, ammonium acetate, potassium sulfate One or more as assisted electrolysis matter, to improve the conductivity of supporting electrolyte；The assisted electrolysis matter it is dense Degree is 0.001~5mol/L, preferably 0.5~3mol/L.
The zinc salt of negative side or/and the oxide of zinc generate Zn (OH) after dissolving in highly basic4 2-It is heavy to occur on the electrode afterwards The electrochemical reaction of product dissolution, reaction equation are as follows:
The reaction of appraising at the current rate of iron occurs on the electrode for the ferrocyanide or/and the iron cyanide of side of the positive electrode, and reaction equation is such as Under:
In charging process, negative side, the oxide of zinc salt or zinc generates Zn (OH) after dissolving in highly basic4 2-Afterwards in carbon felt Or two electronics are obtained in carbon paper electrode and are reduced into zinc simple substance；It is corresponding in side of the positive electrode, Fe (CN)6 4-In carbon felt or carbon paper electricity Electronics is lost on extremely is oxidized to Fe (CN)6 3-。
Wherein, the ferrocyanide in negative side electrolyte is not involved in electrochemical reaction, the zinc simple substance that negative side generates Chemical side reactions do not occur with ferrocyanide；Zn (OH) in side of the positive electrode electrolyte4 2-It is not involved in electrochemical reaction, side of the positive electrode The iron cyanide of generation also not with Zn (OH)4 2-Chemical side reactions occur.
Positive and negative electrode electrolyte fluid reservoir passes through the positive and negative electrode entrance of pipeline monocell or pile through liquid delivery pump and goes out Mouth is connected.
When monocell or pile charge, electrolyte is delivered to positive and negative electrode, anode storage from positive and negative anodes fluid reservoir via pump respectively Active material Fe (CN) in flow container6 4-Electrochemical oxidation reactions occur and generate Fe (CN)6 3-, Zn (OH)4 2-Ion is in carbon felt or carbon Directly with zinc simple substance form deposition on paper cathode；When electric discharge, cathode zinc simple substance is oxidized to Zn (OH) under aqueous slkali environment4 2-From Son is via being pumped back in cathode fluid reservoir, active material Fe (CN) in corresponding anode electrolyte6 3-Electrochemical reduction occurs Reaction generates Fe (CN)6 4-, via being pumped back in positive fluid reservoir.
The electrochemical redox current potential that cathode occurs different, electrochemistry oxygen with the difference of alkali concentration in electrolyte Change reduction potential range between -0.74V vs.Hg/HgO~-1.44V vs.Hg/HgO.
Alkaline Zinc iron liquid galvanic battery, working current density is in 1mA cm-2~200mA cm-2Between.
Alkaline Zinc iron liquid galvanic battery, the charge and discharge time can according to the size of electrolyte concentration, electrolyte volume it is more It is few to control.
By optimization electrolyte composition, the Alkaline Zinc iron liquid galvanic battery assembled can be in 1mA cm-2~200mA cm-2 Working current density between continuous and steady operation, battery efficiency attenuation problem caused by being migrated as electrolyte effectively solved Certainly, system maintenance cost caused by while being migrated as electrolyte is greatly lowered, and shows good application prospect.
Beneficial achievement of the invention:
1. Alkaline Zinc iron fluid cell electrolyte migration problem: zinc-iron flow battery of the invention is effectively reduced, effectively Solve traditional Alkaline Zinc iron liquid galvanic battery causes to be electrolysed since positive and negative electrode electrolyte permeability pressure is inconsistent in the process of running Liquid migrates the efficiency attenuation problem to another pole and battery by a pole, simultaneously effective reduces caused by being migrated as electrolyte and is System maintenance cost, shows good application prospect.
2. being obviously improved Alkaline Zinc iron liquid galvanic battery zinc dendrite: by largely studying textual criticism discovery, under solution state, Due to introducing ferrocyanide in electrolyte liquid, negatively charged ferrous cyanide ion can hinder negatively charged zincic acid Radical ion deposits on high activity growing point, slows down the growth of protrusion dendrite, improves zinc depositional configuration, to inhibit zinc branch Brilliant growth；Ferrous cyanide ion negatively charged simultaneously can effectively inhibit corrosion of the zinc in alkaline electrolyte, make it Reduce in the current density of electrode surface, to play good corrosion inhibition.
3. any side reaction is not present in electrolyte: the ferrocyanide in negative side electrolyte of the invention is not involved in electricity Also with ferrocyanide chemical side reactions do not occur for chemical reaction, the zinc simple substance that negative side generates；Zn in side of the positive electrode electrolyte (OH)4 2-Be not involved in electrochemical reaction, the iron cyanide that side of the positive electrode generates also not with Zn (OH)4 2-Chemical side reactions occur.
4. energy density with higher and power density: negative electricity is to Zn (OH)4 2-The current potential of/Zn can be according to electrolyte The size of middle alkali concentration regulates and controls, and at a high ph, negative electricity is to Zn (OH)4 2-The current potential of/Zn is more negative, with positive Fe (CN)6 3-/ Fe(CN)6 4-The monocell assembled after pairing has higher open-circuit voltage, thus has higher power density.Pass through regulation The concentration of supporting electrolyte highly basic improves the concentration of positive and negative anodes active material, to improve the energy density of battery.Therefore originally The zinc-iron flow battery of invention shows higher energy density and power density, and battery is at low cost, in extensive energy storage field It has a good application prospect.
5. this Alkaline Zinc iron liquid galvanic battery is with high security, stability is good, at low cost, structure and manufacturing process are simple The characteristics of.
Detailed description of the invention
Alkaline Zinc iron liquid galvanic battery structural schematic diagram Fig. 1 of the invention
The electrolyte of Fig. 2 traditional Alkaline Zinc iron liquid galvanic battery and 1 Alkaline Zinc iron liquid galvanic battery of embodiment, which migrates, to be tested
Traditional Alkaline Zinc iron liquid galvanic battery test condition: electrode effective area: 48cm2；Battery uses constant current charge and discharge Power mode, in 80mA cm-2Current density condition under charge 12min, then voltage cut-off is condition, 80mA cm-2Electric current 0.1V is discharged under density conditions；Anode electrolyte composition: 0.4mol L-1Fe(CN)6 4-+3mol L-1KOH；Electrolyte liquid Composition: 0.2mol L-1Zn(OH)4 2-+3mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is porous Carbon felt electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes.
1 Alkaline Zinc iron liquid galvanic battery test condition of embodiment: electrode effective area: 48cm2；Battery uses constant current charge and discharge Power mode, in 80mA cm-2Current density condition under charge 12min, then voltage cut-off is condition, 80mA cm-2Electric current 0.1V is discharged under density conditions；Anode electrolyte composition: 0.4mol L-1Fe(CN)6 4-+0.2mol L-1Zn(OH)4 2-+3mol L-1KOH；Electrolyte liquid composition: 0.4mol L-1Fe(CN)6 4-+0.2mol L-1Zn(OH)4 2-+3mol L-1KOH；Positive and negative anodes electricity Solve each 100mL of liquid product；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion-conductive membranes are polyphenyl And imidazol ion conductive membranes.
Fig. 3 traditional Alkaline Zinc iron liquid galvanic battery performance test, A battery efficiency；B battery capacity
The 1 Alkaline Zinc iron liquid galvanic battery performance test of Fig. 4 embodiment, A battery efficiency；B battery capacity
The power density (figure A) of Fig. 5 traditional Alkaline Zinc iron liquid galvanic battery and 1 Alkaline Zinc iron liquid galvanic battery of the present embodiment, Energy density (figure B) comparison diagram
Fig. 6 traditional Alkaline Zinc iron liquid galvanic battery (left figure) is with 1 Alkaline Zinc iron liquid galvanic battery (right figure) of embodiment same Under the conditions of at the end of the 182nd cycle charging the zinc of cathode deposition SEM figure
Specific embodiment
Monocell assembling: monocell assembles in the following order: positive end plate, graphite collector, anode 6x8cm2Carbon felt is gathered Benzimidazole ion-conductive membranes, cathode 6x8cm2Carbon felt, graphite collector, negative end plate.Battery structure such as Fig. 1.
Comparative example 1
It is comparison with traditional Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.4mol L-1 Potassium ferrocyanide+3mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.2mol L-1Zn(OH)4 2-+3mol L- 1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion Conductive membranes are polybenzimidazoles ion-conductive membranes；In 80mA cm-2Current density condition under charge 12min, then voltage cut-off For condition, 80mA cm-2Current density condition under be discharged to 0.1V.Electric discharge latter stage measures positive and negative anodes electrolyte volume, from Fig. 2 This traditional Alkaline Zinc iron liquid galvanic battery be can be seen that in less than 150 cyclic processes, due to positive and negative anodes electrolyte permeability The imbalance of pressure, electrolyte are migrated from cathode to anode；Corresponding battery shows preferable cell performance in first 140 circulations Can, but later period battery efficiency (Fig. 3 A) and battery capacity (Fig. 3 B) are greatly lowered.Battery caused by this migration because of electrolyte Efficiency decays in practical applications by the maintenance cost for the system that will increase, and is unfavorable for large-scale application.
Embodiment 1
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.4mol L-1 Potassium ferrocyanide+0.2mol L-1Zn(OH)4 2-+3mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.4mol L-1Potassium ferrocyanide+0.2mol L-1Zn(OH)4 2-+3mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode It is Porous carbon felt electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 80mA cm-2 Current density condition under charge 12min, then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0.1V.Electric discharge latter stage measures positive and negative anodes electrolyte volume, figure it is seen that the Alkaline Zinc iron liquid galvanic battery of this symmetric form Within 600 circulations, positive and negative anodes electrolyte volume is without significant change.Operation 1100 of corresponding battery continuous-stable follow Ring, for energy content of battery efficiency (Fig. 4 A) all-the-time stable 85% or more, discharge capacity of the cell is maintained at 6.5Ah/L (Fig. 4 B), equal nothing Obvious decaying, show excellent cyclical stability, and the traditional Alkaline Zinc iron liquid galvanic battery of effective solution is because of positive and negative anodes electricity The problem of migration of electrolyte caused by electrolyte solution osmotic pressure is inconsistent and battery efficiency decay, in practical applications, more answers Use prospect.
It is calculated from the charging and discharging curve of battery, in 80mA cm-2Current density condition under, traditional Alkaline Zinc The power density of iron liquid galvanic battery is 0.0854W cm-2(Fig. 5 A), discharge energy density are 28.756Wh L-1(Fig. 5 B)；Battery At the end of 182 cycle chargings, by battery roll, it can be seen that apparent zinc dendrite (Fig. 6 left figure) in cathode carbon felt, for a long time In operational process, this dendrite will wear out diaphragm, so that short circuit occurs for battery；And the Alkaline Zinc iron liquid stream that this patent is implemented Under the same conditions, the power density of battery is 0.132W cm to battery-2(Fig. 5 A), discharge energy density are 35.0756Wh L-1 (Fig. 5 B) is regulated and controled the deposition morphology of zinc by dendritic crystalline due to the presence of ferrous cyanide ion negatively charged in negative electrode For compact little crystal grain shape (Fig. 6 right figure), the nonuniform deposition of zinc is efficiently solved the problems, such as, in actual application, more Application prospect.
Comparative example 2
It is comparison with traditional Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.2mol L-1 Potassium ferrocyanide+1mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.2mol L-1Zn(OH)4 2-+1mol L- 1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion Conductive membranes are polybenzimidazoles ion-conductive membranes；In 100mA cm-2Current density condition under charge 10min, then voltage is cut It is only condition, 100mA cm-2Current density condition under be discharged to 0.1V.Electrolyte liquid product is after 82 circulations 46mL, anode electrolyte volume are 154mL, and electrolyte migration problem under high running current density conditions is even more serious.
Embodiment 2
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.2mol L-1 Potassium ferrocyanide+0.1mol L-1Zn(OH)4 2-+1mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.4mol L-1Potassium ferrocyanide+0.1mol L-1Zn(OH)4 2-+1mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode It is Porous carbon felt electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 100mA cm-2Current density condition under charge 10min, then voltage cut-off is condition, 100mA cm-2Current density condition decentralization Electricity is to 0.1V.Electric discharge latter stage measures positive and negative anodes electrolyte volume, and after 481 circulations, electrolyte liquid product is 95mL, Anode electrolyte volume is 104mL, and electrolyte is investigated without obvious migration, more than 600 charge and discharge cycles of process, energy content of battery efficiency For all-the-time stable 80% or so, discharge capacity of the cell is maintained at 5Ah/L, and battery efficiency shows this symmetric form without obvious decaying Alkaline Zinc iron liquid galvanic battery be also applied for running under high current densities.
Comparative example 3
It is comparison with traditional Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.6mol L-1 Potassium ferrocyanide+3mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.3mol L-1Zn(OH)4 2-+3mol L- 1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion Conductive membranes are polybenzimidazoles ion-conductive membranes；In 80mA cm-2Current density condition under charge 15min, then voltage cut-off For condition, 80mA cm-2Current density condition under be discharged to 0.1V.It is 53mL that 118, which recycle electrolyte liquid product later, Anode electrolyte volume is 147mL, and apparent migration occurs for positive and negative anodes electrolyte.
Embodiment 3
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.6mol L-1 Potassium ferrocyanide+0.3mol L-1Zn(OH)4 2-+3mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.6mol L-1Potassium ferrocyanide+0.3mol L-1Zn(OH)4 2-+3mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode It is Porous carbon felt electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 80mA cm-2 Current density condition under charge 15min, then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0.1V.Electric discharge latter stage measures positive and negative anodes electrolyte volume, and after 527 circulations, electrolyte liquid product is 92mL, positive Electrolyte volume is 108mL, and electrolyte is investigated without obvious migration, more than 721 charge and discharge cycles of process, and battery coulombic efficiency is always Stablize 95% or more, voltage efficiency is stablized 85% or so, and discharge capacity of the cell is maintained at 10Ah/L, and battery efficiency is without obvious Decaying.
Comparative example 4
It is comparison with traditional Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.8mol L-1 Potassium ferrocyanide+4mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.5mol L-1Zn(OH)4 2-+4mol L- 1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion Conductive membranes are polybenzimidazoles ion-conductive membranes；In 120mA cm-2Current density condition under charge 10min, then voltage is cut It is only condition, 120mA cm-2Current density condition under be discharged to 0.1V.Electrolyte liquid product is after 92 circulations 31mL, anode electrolyte volume are 169mL, and apparent migration occurs for positive and negative anodes electrolyte.
Embodiment 4
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.8mol L-1 Potassium ferrocyanide+0.5mol L-1Zn(OH)4 2-+4mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.8mol L-1Potassium ferrocyanide+0.5mol L-1Zn(OH)4 2-+4mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode It is Porous carbon felt electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 120mA cm-2Current density condition under charge 10min, then voltage cut-off is condition, 120mA cm-2Current density condition decentralization Electricity is to 0.1V.Electric discharge latter stage measures positive and negative anodes electrolyte volume, and after 381 circulations, electrolyte liquid product is 89mL, Anode electrolyte volume is 111mL, and a small amount of negative side electrolyte is migrated to side of the positive electrode, and more than 437 charge and discharge cycles of process are examined It examines, battery coulombic efficiency all-the-time stable is 99% or more, and voltage efficiency is stablized in 86-88% or so, and discharge capacity of the cell is kept In 20Ah/L, battery efficiency is without obvious decaying.
Comparative example 5
It is comparison with traditional Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.8mol L- 1Fe(CN)6 4-+4mol L-1KOH+1mol L-1KCl；Electrolyte liquid (aqueous solution) solute group becomes 0..05mol L-1Zn (OH)4 2-+4mol L-1KOH+1mol L-1KCl；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is porous carbon felt Electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 80mA cm-2Current density item Charge 15min under part, and then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0.1V.103 circulations Later electrolyte liquid product is 43mL, and anode electrolyte volume is 157mL, and apparent migration occurs for positive and negative anodes electrolyte.
Embodiment 5
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.8mol L- 1Fe(CN)6 4-+0.5mol L-1Zn(OH)4 2-+4mol L-1KOH+1mol L-1KCl；Electrolyte liquid (aqueous solution) solute composition For 0.8mol L-1Fe(CN)6 4-+0.5mol L-1Zn(OH)4 2-+4mol L-1KOH+1mol L-1KCl；Positive and negative anodes electrolyte volume Each 100mL；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion-conductive membranes be polybenzimidazoles from Sub- conductive membranes；In 80mA cm-2Current density condition under charge 15min, then voltage cut-off is condition, 80mA cm-2Electricity 0.1V is discharged under the conditions of current density.Electric discharge latter stage measures positive and negative anodes electrolyte volume, after 571 circulations, negative electricity Solving liquid product is 93mL, and anode electrolyte volume is 107mL, and battery coulombic efficiency all-the-time stable is 99% or more, voltage efficiency Stablize 90% or so, discharge capacity of the cell is maintained at 20Ah/L, and positive and negative anodes electrolyte is filled without obvious migration, process more than 824 times Discharge cycles are investigated, and battery efficiency is without obvious decaying.
Comparative example 6
It is comparison with Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.05mol L-1Fe (CN)6 4-+0..05mol L-1Zn(OH)4 2-+0.01mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.05mol L-1Zn(OH)4 2-+0.01mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is Porous carbon felt electrode, Graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 120mA cm-2Current density condition under Charge 10min, and then voltage cut-off is condition, 120mA cm-2Current density condition under be discharged to 0.1V.204 circulation with Electrolyte liquid product is 72mL afterwards, and anode electrolyte volume is 128mL, and more apparent migration occurs for positive and negative anodes electrolyte.
Embodiment 6
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.05mol L- 1Fe(CN)6 4-+0.05mol L-1Zn(OH)4 2-+0.01mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.05mol L-1Fe(CN)6 4-+0.05mol L-1Zn(OH)4 2-+0.01mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume； Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes； In 120mA cm-2Current density condition under charge 10min, then voltage cut-off is condition, 120mA cm-2Current density Under the conditions of be discharged to 0.1V.Electric discharge latter stage measures positive and negative anodes electrolyte volume, after 381 circulations, electrolyte liquid Product is 89mL, and anode electrolyte volume is 111mL, and a small amount of negative side electrolyte is migrated to side of the positive electrode, more than 437 charge and discharges of process Electricity circulation is investigated, and battery coulombic efficiency all-the-time stable is 80% or more, and voltage efficiency is stablized 75% or so, discharge capacity of the cell It is maintained at 4Ah/L, battery efficiency is without obvious decaying.
Comparative example 7
It is comparison with Alkaline Zinc iron liquid galvanic battery, anode electrolyte (aqueous solution) solute group becomes 0.001mol L-1Fe (CN)6 4-+0.001mol L-1Zn(OH)4 2-+0.001mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.001mol L-1Zn(OH)4 2-+0.001mol L-1KOH；Each 100mL of positive and negative anodes electrolyte volume；Positive and negative anodes electrode is more Hole carbon felt electrode, graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion-conductive membranes；In 120mA cm-2Electricity Charge 10min under the conditions of current density, and then voltage cut-off is condition, 120mA cm-2Current density condition under be discharged to 0.1V. It is 135mL that 216, which recycle electrolyte liquid product later, and anode electrolyte volume is 65mL, and positive and negative anodes electrolyte occurs more Apparent migration.
Embodiment 7
And for the Alkaline Zinc iron liquid galvanic battery of symmetric form, anode electrolyte (aqueous solution) solute group becomes 0.001mol L-1Fe(CN)6 4-+0.001mol L-1Zn(OH)4 2-+0.001mol L-1KOH；Electrolyte liquid (aqueous solution) solute group becomes 0.001mol L-1Fe(CN)6 4-+0.001mol L-1Zn(OH)4 2-+0.001molL-1KOH；Positive and negative anodes electrolyte volume is each 100mL；Positive and negative anodes electrode is Porous carbon felt electrode, and graphite plate is as collector plate；Ion-conductive membranes are polybenzimidazoles ion Conductive membranes；In 120mA cm-2Current density condition under charge 10min, then voltage cut-off is condition, 120mA cm-2Electricity 0.1V is discharged under the conditions of current density.Electric discharge latter stage measures positive and negative anodes electrolyte volume, after 381 circulations, negative electricity Solving liquid product is 89mL, and anode electrolyte volume is 111mL, and a small amount of negative side electrolyte is migrated to side of the positive electrode, process more than 437 Secondary charge and discharge cycles are investigated, and battery coulombic efficiency all-the-time stable is 60% or more, and voltage efficiency is stablized 50% or so, and battery is put Capacitance is maintained at 2Ah/L battery efficiency without obvious decaying.

Claims (9)

1. a kind of Alkaline Zinc iron liquid galvanic battery, battery includes a section monocell or the above monocell circuit string of two sections and/or parallel connection Made of battery module, the fluid reservoir equipped with anode electrolyte, the fluid reservoir equipped with electrolyte liquid, electrolyte circulating pump and follow Endless tube road, it is characterised in that: the anode electrolyte in the fluid reservoir of anode electrolyte and bearing in the fluid reservoir of electrolyte liquid Electrolyte composition in pole is identical, and electrolyte is the strong alkali aqueous solution of ferrocyanide and zinc compound.
2. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that: the electrolyte be include ferrocyanide Object, zinc compound, highly basic three mix the aqueous solution that solute forms；
The molar concentration of middle ferrocyanide is 0.0001~1mol/L in electrolyte, and zinc compound generates after dissolving in highly basic Zn (OH)4 2-Molar concentration be 0.0001~2mol/L, the molar concentration of highly basic is 0.0001~5mol/L.
3. Alkaline Zinc iron liquid galvanic battery electrolyte according to claim 1 or 2, it is characterised in that: the ferrous cyanogen Compound includes one or both of potassium ferrocyanide, sodium ferrocyanide, ferrocyanide lithium, ferrocyanide magnesium or calcium ferrocyanide More than；The zinc compound be one or more of zinc salt and/or zinc oxide, zinc salt include zinc chloride, zinc bromide, One or more of zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate；Zinc oxide is zinc oxide；Highly basic includes hydroxide One or more of sodium, lithium hydroxide, potassium hydroxide.
4. Alkaline Zinc iron liquid galvanic battery according to claim 1 or 2, it is characterised in that: ferrocyanide is ferrocyanide Potassium or/and sodium ferrocyanide；Highly basic is potassium hydroxide or/and sodium hydroxide.
5. Alkaline Zinc iron liquid galvanic battery according to claim 1 or 2, it is characterised in that: the electrolyte presses following mistake Journey is prepared:
It is dissolved in the water after ferrocyanide, zinc compound, highly basic three are mixed, is sufficiently stirred at being 20~100 DEG C in temperature It mixes 0.5~10 hour and electrolyte is made；
Or, ferrocyanide is dissolved in deionized water or strong base solution, 0.5 is sufficiently stirred at being 20~100 DEG C in temperature Homogeneous solution is made within~10 hours；It is made in addition deionized water after zinc compound or zinc compound are mixed with highly basic uniformly molten After liquid, then with above-mentioned ferrocyanide solution mixing system is standby forms.
6. Alkaline Zinc iron liquid galvanic battery according to claim 2, it is characterised in that: the molar concentration of ferrocyanide is 0.1~0.8mol/L；The Zn (OH) that zinc compound generates after dissolving in highly basic4 2-Molar concentration be 0.05~0.8mol/L； The molar concentration of highly basic is 1~4mol/L.
7. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that: be additionally added in electrolyte potassium chloride, One or more of sodium sulphate, sodium chloride, ammonium chloride, ammonium acetate, soluble-salt of potassium sulfate are used as assisted electrolysis matter, To improve the conductivity of electrolyte；The molar concentration of assisted electrolysis matter described in electrolyte is 0.001~5mol/L, preferably 0.5~3mol/L.
8. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that: in charging process, negative side, electrolyte The Zn (OH) that middle zinc compound generates after dissolving in highly basic4 2-Two electronics are obtained on the electrode and are reduced into zinc simple substance, at this time Ferrocyanide is not involved in the electrochemical reaction of negative side, and it is secondary anti-that chemistry does not also occur with ferrocyanide for the zinc simple substance of generation It answers；The corresponding ferrocyanide in side of the positive electrode, electrolyte loses electronics on the electrode and is oxidized to the iron cyanide, zinc impregnation at this time Close the Zn (OH) generated after object dissolves in highly basic4 2-Be not involved in the electrochemical reaction of side of the positive electrode, the iron cyanide of generation also not with Zn(OH)4 2-Chemical side reactions occur.
9. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that: the monocell includes stacking gradually Anode collection plate, anode, ion-conductive membranes, cathode, negative pole currect collecting plate.
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CN110265694A (en) * 2019-05-29 2019-09-20 西安交通大学 One kind is talked endlessly pyridine class water system organic oxidation reducing solution galvanic battery
CN110534682A (en) * 2019-08-05 2019-12-03 长沙理工大学 A kind of preparation method of alkaline oxygenated reduction flow battery amberplex
CN111446508A (en) * 2020-05-01 2020-07-24 浙江大学 High-concentration solution and application and preparation method thereof
CN113013461A (en) * 2019-12-19 2021-06-22 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery adopting tetraborate as additive anode electrolyte
CN113013460A (en) * 2019-12-19 2021-06-22 中国科学院大连化学物理研究所 Negative electrolyte for alkaline zinc-iron flow battery and 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
WO2023082842A1 (en) * 2021-11-11 2023-05-19 中国科学院大连化学物理研究所 Alkaline negative electrode electrolyte and alkaline zinc-iron flow battery assembled by same

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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
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US4180623A (en) * 1977-12-19 1979-12-25 Lockheed Missiles & Space Company, Inc. Electrically rechargeable battery
CN103069632A (en) * 2010-08-25 2013-04-24 应用材料公司 Flow battery systems
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
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110265694A (en) * 2019-05-29 2019-09-20 西安交通大学 One kind is talked endlessly pyridine class water system organic oxidation reducing solution galvanic battery
CN110534682A (en) * 2019-08-05 2019-12-03 长沙理工大学 A kind of preparation method of alkaline oxygenated reduction flow battery amberplex
CN113013461A (en) * 2019-12-19 2021-06-22 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery adopting tetraborate as additive anode electrolyte
CN113013460A (en) * 2019-12-19 2021-06-22 中国科学院大连化学物理研究所 Negative electrolyte for alkaline zinc-iron flow battery and zinc-iron flow battery
CN113013460B (en) * 2019-12-19 2022-06-14 中国科学院大连化学物理研究所 Negative electrolyte for alkaline zinc-iron flow battery and 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
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
CN111446508A (en) * 2020-05-01 2020-07-24 浙江大学 High-concentration solution and application and preparation method thereof
WO2023082842A1 (en) * 2021-11-11 2023-05-19 中国科学院大连化学物理研究所 Alkaline negative electrode electrolyte and alkaline zinc-iron flow battery assembled by same

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