CN108461784A - 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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Publication number
CN108461784A
CN108461784A CN201611133465.XA CN201611133465A CN108461784A CN 108461784 A CN108461784 A CN 108461784A CN 201611133465 A CN201611133465 A CN 201611133465A CN 108461784 A CN108461784 A CN 108461784A
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electrolyte
battery
zinc
positive
concentration
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李先锋
张华民
袁治章
段寅琦
谢聪鑫
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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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Priority to PCT/CN2017/111224 priority patent/WO2018103517A1/en
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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, ion-conductive membranes are prepared by nitrogenous heterocyclic aroma type polymer, and electrode is carbon felt or carbon paper；Anode electrolyte is the mixed aqueous solution of ferrocyanide work and highly basic, electrolyte liquid is zinc salt or/and the oxide of zinc and the mixed aqueous solution of highly basic, a concentration of 0.001~the 10mol/L of highly basic in aqueous solution in positive and negative electrolyte, a concentration of 0.001~3mol/L of active material in positive and negative electrode electrolyte.A kind of high-energy density, high power density, the Alkaline Zinc iron liquid galvanic battery of long-life are invented, the battery performance shown and the current ripe battery performance of all-vanadium flow battery are suitable even more excellent, show good application prospect.

Description

A kind of Alkaline Zinc iron liquid galvanic battery
Technical field
The present invention relates to flow battery fields, more particularly to a kind of zinc-iron flow battery technology field.
Background technology
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 (Vanadium flow battery, VFB) due to safe, stability is good, it is efficient, Long lifespan (the service life>15 years), it is at low cost the advantages that, be considered to have good application prospect, but the electrolyte solution price of VFB More expensive, this limits its large-scale application to a certain extent.Therefore exploitation is had excellent performance, low-cost electrochemical energy storage electricity Pond is extremely important to regenerative resource popularization and application.
Other than all-vanadium flow battery, develop at present more mature flow battery mainly also have 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.
Zinc-iron flow battery in extensive flow battery due to electrolyte advantage at low cost, having and preferably answering Use foreground.It is by conductive mesh and non-conductive net that patent 201180016873.6, which discloses a kind of Alkaline Zinc iron liquid galvanic battery group, Hole；Sieve；Band；Foaming structure；The array of cone, cylinder or pyramid；It is made with other of line or pipe arrangement, electrode For porous web mesoporous metal electrode, although showing preferable performance, structure is complex, and chemical property is relatively low, in addition Membrane material selects perfluoro sulfonic acid membrane (Nafion), and cost is higher, and stability is poor.
Invention content
In order to solve the above technical problems, a kind of inexpensive, simple in structure, electrochemical performance zinc-iron liquid stream electricity of exploitation Pond is particularly important, in order to achieve the above objectives,
The present invention develops a kind of Alkaline Zinc iron liquid galvanic battery, and specific technical solution is as follows：
Battery includes battery module made of a section monocell or the two above monocell series/parallels of section, 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, ion-conductive membranes are prepared by nitrogenous heterocyclic aroma type polymer, and electrode is carbon felt or carbon paper；Anode electrolyte is The mixed aqueous solution of ferrocyanide and highly basic, electrolyte liquid are that the mixing of the oxide and highly basic of zinc salt or/and zinc is water-soluble Liquid, a concentration of 0.001~10mol/L of highly basic in aqueous solution in positive and negative electrolyte, active material is in anode electrolyte The iron cyanide (Fe (CN)6 3-) or ferrocyanide (Fe (CN)6 4-One or both of), active material is in electrolyte liquid Zn(OH)4 2-；A concentration of 0.001~3mol/L of active material in positive and negative electrode electrolyte；The wherein aromatic series containing azacyclo- Polymer is polybenzimidazoles, polyvinyl imidazole, polypyridine, polyvinyl pyridine, poly- pyrazoles, poly- pyrimidine, polythiazole, polyphenyl and thiophene It is one or more in azoles, Ju oxazoles, polybenzoxazole, polyoxadiazoles, poly quinoline, polyquinoxaline, polythiadiazoles, poly- four purine Polymer.
The wherein described ion-conductive membranes prevent positive and negative anodes short circuit and transmission ion from being formed interior for obstructing positive and negative anodes electrolyte Portion circuit；The electrochemical reaction region that the circulating pump is used to that electrolyte to be made to cycle through the positive and negative half-cell.
The zinc salt of negative side or/and the oxide of zinc generate Zn (OH) after being dissolved in highly basic4 2-It is heavy to occur on the electrode afterwards The electrochemical reaction of product dissolving, reaction equation are as follows：
The change covalent reaction 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 being dissolved 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-。
Active material in anode electrolyte is the iron cyanide (Fe (CN)6 3-) or ferrocyanide (Fe (CN)6 4-) in It is one or two kinds of；
The oxide of zinc is zinc oxide (ZnO) in electrolyte liquid, and zinc salt is zinc chloride (ZnCl2), zinc sulfate (ZnSO4) In one kind.
Highly basic is sodium hydroxide (NaOH), one or more of potassium hydroxide (KOH) or lithium hydroxide (LiOH) As supporting electrolyte.
A concentration of 0.001mol/L~10mol/L of highly basic, preferably 2-5mol/L；Also can add into above-mentioned electrolyte solution Enter a certain amount of assisted electrolysis matter (0~30wt% of a concentration of alkali concentration of assisted electrolysis matter) such as potassium chloride (KCl), sodium sulphate (Na2SO4), sodium chloride (NaCl), potassium sulfate (K2SO4) etc. soluble-salts, to improve the conductivity of supporting electrolyte.
Positive and negative electrode electrolyte fluid reservoir by the positive and negative electrode entrance of pipeline monocell or pile and goes out through liquid delivery pump Mouth is connected.
It is preferred that in electrolyte liquid in a concentration of anode electrolyte of active material active material concentration 1/2~pair Saturated concentration in the strong base solution answered.
The electrolyte solution must configure at different temperatures according to the difference of concentration, the temperature range 5~ Between 90 DEG C.
When monocell or pile charge, electrolyte is delivered to positive and negative electrode, anode storage respectively via pump from positive and negative anodes fluid reservoir 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 It is directly deposited with zinc simple substance form 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 ion-conductive membranes can (or not needing) in 0mol/L<The concentration of the aqueous solution of alkali<It is living in 10mol/L Change.
Suitable quaternary ammonium salt, thiocarbamide, polyvinyl alcohol, Bi can be added in electrolyte liquid3+、Ti+、Pd2+、Pb2+Branch Crystalline substance forms inhibitor to regulate and control the deposition morphology of zinc, and the dendrite being added forms inhibitor concentration ranging from 0~0.02mol/L.
The electrochemical redox current potential that cathode occurs is different with the difference of alkali concentration in electrolyte solution, electrification Redox potential range is learned 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.
Wherein, transporting mechanism of the nitrogenous heterocyclic ion-conductive membranes in alkaline zinc iron cell is illustrated in fig. 10 shown below：Pass through In region adsorb free aqueous solution carry out conduction or by between ion-exchange group and aqueous solution replace Dissociative into Row conduction.
By screening electrode and ion-conductive membranes, optimization electrolyte composition, the Alkaline Zinc iron liquid galvanic battery assembled can be with In 1mA cm-2~200mA cm-2Working current density between continuous and steady operation, show suitable with all-vanadium flow battery Even more preferably battery performance.
The useful achievement of the present invention：
1. this patent for the first time uses nitrogen heterocyclic ring amberplex, carbon felt class electrode and high concentration high stability electrolyte In alkaline zinc iron cell, a kind of high-energy density, high power density, the Alkaline Zinc iron liquid galvanic battery of long-life have been invented.Institute The Alkaline Zinc iron liquid galvanic battery of it is proposed is used as electrode using conductive carbon felt or carbon paper, with the amberplex of nitrogen heterocyclic ring one kind with The porous ion conductive membranes of nitrogen heterocyclic ring one kind are as battery diaphragm, the battery performance and the all-vanadium flow ripe at present that show The battery performance of battery is quite even more excellent, and Alkaline Zinc iron liquid galvanic battery positive and negative anodes oxidation-reduction pair is respectively Fe (CN)6 3-/Fe(CN)6 4-With Zn (OH)4 2-/ Zn, zinc-iron rich reserves, cost are far below all-vanadium flow battery, and satisfaction is answered on a large scale Demand shows good application prospect.
2. carbon felt electrode can effectively improve its chemical property in alkaline electrolyte by in-situ activation, in addition, electrolysis The problem of additive can add up the short life brought due to zinc dendrite with effective solution with zinc is introduced in liquid.Such battery table Reveal with all-vanadium flow battery compare favourably even higher than full vanadium energy density and power density battery performance, but cost is much Less than all-vanadium flow battery, there is good application prospect in extensive energy storage field.
3. negative electricity is to Zn (OH)4 2-The current potential of/Zn can regulate and control according to the size of alkali concentration in electrolyte, in high ph-values Under, 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 tool assembled after pairing There is higher open-circuit voltage, thus there is higher power density.
4. this Alkaline Zinc iron liquid galvanic battery has, safe, stability is good, at low cost, structure and manufacturing process are simple The characteristics of.
5. the concentration of positive and negative anodes active material can be improved by regulating and controlling the concentration of supporting electrolyte highly basic, to improve The energy density of battery.
Description of the drawings
Fig. 1 Alkaline Zinc iron liquid galvanic battery structural schematic diagrams；
The electrochemical property test of Fig. 2 positive and negative anodes active materials.(a)0.1mol/L Zn(OH)4 2-+ 3mol/L NaOH are molten Liquid and 0.2mol/L Fe (CN)6 3-+0.2mol/L Fe(CN)6 4-The cyclic voltammetry of+3mol/L NaOH solutions；(b) 0.1mol/L Zn(OH)4 2-+ 3mol/L NaOH solutions are in 10~60mV s-1Sweep the cyclic voltammogram under speed；(c)0.2mol/L Fe(CN)6 3-+0.2mol/L Fe(CN)6 4-+ 3mol/L NaOH solutions are in 10~60mV s-1Sweep the cyclic voltammogram under speed；(d) Redox peak current ip corresponding with the figure c and half power (v for sweeping speed1/2) linear graph.
The structural schematic diagram of the ion-conductive membranes of several nitrogen heterocyclic ring classes for Alkaline Zinc iron liquid galvanic battery of Fig. 3；
Fig. 4 is that comparative example 1 uses the Alkaline Zinc iron liquid galvanic battery that 115 amberplexes of Nafion assemble in 80mA cm-2's Battery performance under current density condition.(a) charging and discharging curve of the 5th cycle；(b) cycle performance is tested.Anode electrolyte Composition：0.6mol/L Fe(CN)6 4-+5mol/L OH-Solution；Electrolyte liquid forms：0.3mol/L Zn(OH)4 2-+5mol/L OH-Solution；Each 60mL of positive and negative anodes electrolyte volume；Battery uses constant current charge-discharge pattern, in 80mA cm-2Current density Under the conditions of charge 10min, then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0V.
Fig. 5 is the battery performance test for the Alkaline Zinc iron liquid galvanic battery that embodiment 4 is assembled with PBI amberplexes.(a) The charging and discharging curve of 5 cycles；(b) part charge and discharge cycles curve (voltage change with time relationship)；(c) long circulating performance Test；(d) during loop test discharge capacity and discharge energy with recurring number variation relation curve.Anode electrolyte group At：0.6mol/L Fe(CN)6 4-+5mol/L OH-Solution；Electrolyte liquid forms：0.3mol/L Zn(OH)4 2-+5mol/L OH-Solution；Each 60mL of positive and negative anodes electrolyte volume；Battery uses constant current charge-discharge pattern, in 60mA cm-2Current density Under the conditions of charge 12min, then voltage cut-off is condition, 60mA cm-2Current density condition under be discharged to 0V.
Fig. 6 is the battery performance test for the Alkaline Zinc iron liquid galvanic battery that embodiment 4 is assembled with PBI amberplexes.(a) not With the battery performance test under current density；(b) charging and discharging curve of the 5th cycle；(c) part charge and discharge cycles curve (electricity Press the relationship that changes with time)；(d) cycle performance is tested.Anode electrolyte forms：0.6mol/L Fe(CN)6 4-+5mol/L OH-Solution；Electrolyte liquid forms：0.3mol/L Zn(OH)4 2-+5mol/L OH-Solution；Positive and negative anodes electrolyte volume is each 60mL；Battery uses constant current charge-discharge pattern, in 60mA cm-2Current density condition under charge 12min, then voltage is cut It is only condition, 60mA cm-2Current density condition under be discharged to 0V；80mA cm-2Current density condition under charge 10min, Then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0V；100mA cm-2Current density condition Lower charging 8min, then voltage cut-off is condition, 100mA cm-2Current density condition under be discharged to 0V；120mA cm-2's Charge 8min under current density condition, and then voltage cut-off is condition, 120mA cm-2Current density condition under be discharged to 0V.
The battery performance test for the Alkaline Zinc iron liquid galvanic battery that Fig. 7 PBI amberplexes assemble.(a) the 5th cycle Charging and discharging curve；(b) part charge and discharge cycles curve (voltage change with time relationship)；(c) cycle performance is tested；(d) it follows During ring test discharge capacity and discharge energy with recurring number variation relation curve.Anode electrolyte forms：1mol/L Fe (CN)6 4-+3mol/L OH-Solution；Electrolyte liquid forms：0.5mol/L Zn(OH)4 2-+3mol/L OH-Solution；Positive and negative anodes electricity It solves liquid and accumulates each 60mL；Battery uses constant current charge-discharge pattern, in 60mA cm-2Current density condition under charge 30min, Then voltage cut-off is condition, 60mA cm-2Current density condition under be discharged to 0V.
Fig. 8 is the battery performance test for the Alkaline Zinc iron liquid galvanic battery that embodiment 4 is assembled with PBI amberplexes.(a) The charging and discharging curve of 5 cycles；(b) part charge and discharge cycles curve (voltage change with time relationship)；(c) cycle performance is surveyed Examination；(d) during loop test discharge capacity and discharge energy with recurring number variation relation curve.Anode electrolyte forms： 1mol/L Fe(CN)6 4-+3mol/L OH-Solution；Electrolyte liquid forms：0.5mol/L Zn(OH)4 2-+3mol/L OH-It is molten Liquid；Each 60mL of positive and negative anodes electrolyte volume；Battery uses constant current charge-discharge pattern, in 80mA cm-2Current density condition under Charge 20min, and then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0V.
The all-vanadium flow battery that Fig. 9 (a) is assembled with 115 films of Nafion is in 80mA cm-2Current density condition under electricity The Alkaline Zinc iron liquid galvanic battery that pond performance is assembled with use PBI amberplexes is in 80mA cm-2Current density condition under battery The comparison of performance；(b) use the all-vanadium flow battery that 115 films of Nafion assemble in 80mA cm-2Current density condition under put Capacitance, the Alkaline Zinc iron liquid galvanic battery that discharge energy is assembled with use PBI amberplexes is in 80mA cm-2Current density item Discharge capacity under part, the comparison of discharge energy.All-vanadium flow battery：Positive and negative anodes concentration of electrolyte each 1.5mol/L, H2SO4It is dense Spend 3mol/L, each 60mL of positive and negative anodes electrolyte volume；Battery uses constant current charge-discharge pattern, and charge and discharge blanking voltage is respectively 1.55V 1V；Alkaline Zinc iron liquid galvanic battery：Anode electrolyte forms：1mol/L Fe(CN)6 4-+3mol/L OH-Solution；Cathode Electrolyte forms：0.5mol/L Zn(OH)4 2-+4mol/L OH-Solution；Each 60mL of positive and negative anodes electrolyte volume；Battery is using permanent Current charge-discharge power mode, in 80mA cm-2Current density condition under charge 20min, then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0V.
Figure 10 is transporting mechanism of the nitrogenous heterocyclic ion-conductive membranes in alkaline zinc iron cell.
Specific implementation mode
The cyclic voltammetric (CV) of positive active material is tested：By 0.2mol/L Fe (CN)6 4-+0.2mol/L Fe(CN)6 3- It is dissolved in 3mol/L NaOH, respectively using graphite cake as working electrode (working electrode area：1cm2) and to electrode, Hg/HgO electricity Extremely reference electrode, in 10~60mV s-1Sweep the curve (Fig. 2 c) that electric current and current potential are measured under speed, it can be seen that anode electricity is to Fe (CN)6 3-/Fe(CN)6 4-Show excellent electro-chemical activity and electrochemical reversibility.By to peak current ip and sweep speed two / first power (v1/2) mapping (Fig. 2 d) discovery, Fe (CN)6 3-/Fe(CN)6 4-The electrochemical redox reaction of electricity pair belongs to expansion Dissipate control.
The cyclic voltammetric (CV) of negative electrode active material is tested：0.1mol/L ZnO are dissolved in 3.2mol/L NaOH, respectively Using graphite cake as working electrode (working electrode area：1cm2) and to electrode, Hg/HgO electrodes are reference electrode, in 10~60mV s-1Sweep the curve (Fig. 2 b) that electric current and current potential are measured under speed, it can be seen that negative electricity is to Zn (OH)4 2-/ Zn is influenced less by speed is swept.
Pass through Zn (OH)4 2-/ Zn electricity pair and Fe (CN)6 3-/Fe(CN)6 4-Electricity is in 40mV s-1Sweep the half wave potential point under speed Analysis is as can be seen that positive and negative anodes potential difference is 1.74V (Fig. 2 a), far above the open-circuit voltage (1.2V) of full vanadium.
Monocell assembles：Monocell assembles in the following order：Positive end plate, graphite collector, anode 6x8cm2Carbon felt, from (the porous ion conductive membranes of the amberplex and nitrogen heterocyclic ring one kind of nitrogen heterocyclic ring one kind, partial structural formula is such as sub- conductive membranes Fig. 3), cathode 6x8cm2Carbon felt, graphite collector, negative end plate.Single-cell structure is shown in Fig. 1.
Comparative example 1
It is amberplex with Nafion 115, anode electrolyte is 0.6mol/L Fe (CN)6 4-+5mol/L OH-It is molten Liquid；Electrolyte liquid is 0.3mol/L Zn (OH)4 2-+5mol/L OH-Solution；Each 60mL of positive and negative anodes electrolyte volume；Battery is adopted With constant current charge-discharge pattern, in 80mA cm-2Current density condition under charge 10min, then voltage cut-off is condition, 80mA cm-2Current density condition under be discharged to 0V.From the charging and discharging curve (Fig. 4 a) of battery as can be seen that the electric discharge of battery Voltage is close to 1.8V, and for the initial coulombic efficiency of battery (CE) close to 100%, energy efficiency (EE) and voltage efficiency (VE) are close 80%.After 100 cycles, the coulombic efficiency of battery is held essentially constant, and voltage efficiency and energy efficiency are down to 70% or so (Fig. 4 b).
Embodiment 1
Nitrogen heterocyclic ring class polyoxadiazoles (POD) dense film, anode electrolyte are 0.6mol/L Fe (CN)6 4-+3mol/L OH-Solution；Electrolyte liquid is 0.3mol/L Zn (OH)4 2-+3mol/L OH-Solution；Each 60mL of positive and negative anodes electrolyte volume；Electricity Pond uses constant current charge-discharge pattern, in 80mA cm-2Current density condition under charge 10min, then voltage cut-off is item Part, 80mA cm-2Current density condition under be discharged to 0V.By the charging and discharging curve of battery it is found that the discharge voltage of battery exists 1.76V or so, CE, EE and the VE of battery are respectively 99%, 81% and 82% or so.Within being recycled at 70, the charge and discharge of battery Capacitance and charge-discharge energy keep stable, and battery performance has no apparent decaying.
Embodiment 2
The crosslinked chloromethyl polysulphone porous ion conductive membranes (CMPSF-Im) of imidazoles of branch nitrogen heterocyclic ring class, battery are surveyed Strip part and the battery testing assembled with POD films are consistent.By the charging and discharging curve of battery it is found that battery polarization is less than use The monocell of POD films assembling, thus other than with high ion selectivity (CE~99%), ionic conductivity also compared with Height, VE are 82% or so.This may be because the pore structure in perforated membrane is conducive to the liquid holdup in film, thus is conducive to ion Conduction.Within more than 100 cycle, the charge/discharge capacity and charge-discharge energy of battery keep stable, show preferable Stability and battery performance.
Embodiment 3
The crosslinked chloromethyl polysulphone amberplex (CMPSF-Biy) of 4,4'-Bipyridine of branch nitrogen heterocyclic ring class, electricity Pond test condition and the battery testing assembled with POD films are consistent.By the charging and discharging curve of battery it is found that battery polarization is high In the monocell assembled with POD films, it is 99% or so that the VE with the monocell of its assembling, which is 78% or so, CE,.Although this kind of film VE in alkaline zinc iron cell is relatively low, but preferable with the circulating battery stability of its assembling, after more than 100 cycle, The charge/discharge capacity and charge-discharge energy of battery keep stable.
Embodiment 4
Porous ion conductive membranes are the polybenzimidazoles amberplex (PBI) of nitrogen heterocyclic ring class, and anode electrolyte is 0.6mol/L Fe(CN)6 4-+5mol/L OH-Solution；Electrolyte liquid is 0.3mol/L Zn (OH)4 2-+5mol/L OH-Solution； Each 60mL of positive and negative anodes electrolyte volume；Battery uses constant current charge-discharge pattern, in 60mA cm-2Current density condition under fill Electric 12min, then voltage cut-off is condition, 60mA cm-2Current density condition under be discharged to 0V.Since current density is 60mA cm-2, thus the charging time 12min is extended to by initial 10min, the ohmic polarization of inside battery is can be seen that from Fig. 5 a Relatively low, the voltage efficiency and energy efficiency of battery show excellent battery performance close to 90%.Randomly select portion voltage Versus time curve (Fig. 5 b) can be seen that in long circulating operational process (battery operation 90h or so), in cyclic process Voltage curve without significant change, show excellent stability.After more than 500 cycle, the CE of battery, VE, EE (figures 5c), discharge capacity and discharge energy (Fig. 5 d) have no apparent decaying, show excellent stability.
Pass through varying current density (60~120mA cm-2) test as can be seen that the Alkaline Zinc assembled with PBI amberplexes Iron liquid galvanic battery is in 120mA cm-2Current density condition under (Fig. 6 a), the CE of battery is maintained at 99% or more, EE and is maintained at 82% or more, VE are maintained at 83% or more, show excellent high rate performance.And in 80mA cm-2Charging and discharging currents density item Under part, 1.8V or more (Fig. 6 b), the variation tendency of charging/discharging voltage can be reached with the initial discharge voltage of the battery of PBI assemblings It is consistent (Fig. 6 c) with the variation of time, shows that the polarization of inside battery in cell operation is kept not substantially Become, is conducive to obtain and stablizes excellent battery performance.With the Alkaline Zinc iron liquid galvanic battery of PBI assemblings in 80mA cm-2Electric current it is close Obviously decaying (Fig. 6 d) do not occur in battery performance and battery capacity after more than 100 cycles of continuous-stable operation under the conditions of degree, into One step shows excellent cyclical stability.
Further to confirm the practicability of Alkaline Zinc iron liquid galvanic battery, reach and be currently in the all-vanadium flow of demonstration phase The battery performance (capacity and power density) that battery compares favourably, 1mol/L Fe are increased to by the concentration of positive active material (CN)6 4-, the concentration of alkali is reduced to 3mol/L OH-, corresponding electrolyte liquid is 0.5mol/L Zn (OH)4 2-+ 3mol/L OH-Solution.Each 60mL of positive and negative anodes electrolyte volume；It is assembled into monocell by amberplex of PBI, using permanent electricity Charge and discharge mode is flowed, in 60mA cm-2Current density condition under charge 30min, then voltage cut-off is condition, 60mA cm-2 Current density condition under be discharged to 0V.The ohmic polarization that can be seen that battery from Fig. 7 a further decreases, and the initial of battery is put Piezoelectric voltage is investigated, the initial discharge voltage of battery is remained at close to 1.9V by the charge and discharge cycles of more than 135 hours 1.9V or so (Fig. 7 b) shows that under the conditions of the active material of high concentration, the ohmic polarization of inside battery will not occur obviously Variation.After more than 150 cycle, the CE of battery remains at 99% or more, VE and EE remains at 91% or more (Fig. 7 c) shows excellent battery performance and cyclical stability.Due to the increase of active material in electrolyte, the electric discharge of battery Specific capacity is discharged than energy close to 25Ah/L close to 40Wh/L (Fig. 7 d), and is held essentially constant within being recycled at 150, Show good application prospect.
Further by working current density from 60mA cm-2It improves to 80mA cm-2, due to the raising of current density, battery Internal ohmic polarization increases, and the initial discharge voltage of battery is reduced to 1.8V or so (Fig. 8 a) by 1.9V, small by more than 90 When charge and discharge cycles investigate, the initial discharge voltage of battery remains at 1.8V or so (Fig. 8 b), shows in high concentration Under active material and high current densities, significant change will not occur for the ohmic polarization of inside battery.It is followed by more than 200 After ring, the CE of battery remains at 99% or more, VE and EE and remains at 88% or more (Fig. 8 c), shows excellent Battery performance and cyclical stability.Due to the increase of active material in electrolyte, the specific discharge capacity of battery recycled at 200 with 21Ah/L or more is inside remained at, and discharges and remains at 35Wh/L (Fig. 8 d) than energy.
With all-vanadium flow battery (positive and negative anodes the active material concentration each 1.5mol/L, H assembled with 115 films of Nafion2SO4 Concentration 3mol/L, each 60mL of positive and negative anodes electrolyte volume；Battery uses constant current charge-discharge pattern, the charging and discharging currents of battery close Degree is 80mA cm-2, charge and discharge blanking voltage is respectively 1.55V, 1V) and it compares, the Alkaline Zinc iron liquid galvanic battery assembled with PBI In 80mA cm-2Current density condition under, the CE of battery is 99.61%, EE 89.90%, and EE is 90.24% (Fig. 9 a), property Battery performance (CE 96.62%, EE 83.55%, VE of the all-vanadium flow battery assembled with Nafion115 films can be much better than For 86.47%).And after being recycled at 200 with the all-vanadium flow battery that 115 films of Nafion assemble, the specific discharge capacity of battery By initial 26.5Ah/L pad value 8.7Ah/L (Fig. 9 b), and the specific discharge capacity of the Alkaline Zinc iron liquid galvanic battery with PBI assemblings Remain at 21Ah/L or more (Fig. 9 b)；On the other hand, begun than energy with the electric discharge of the Alkaline Zinc iron liquid galvanic battery of PBI assemblings It is maintained at 35Wh/L or so (Fig. 9 b) eventually, after the all-vanadium flow battery assembled with 115 films of Nafion is recycled at 200, battery Electric discharge than energy by initial 33.4Wh/L pad value 10.8Wh/L (Fig. 9 b), performance is much better than all-vanadium flow battery, performance Go out good application prospect.

Claims (6)

1. a kind of Alkaline Zinc iron liquid galvanic battery, battery includes electricity made of a section monocell or the two above monocell series/parallels of section Pond module, the fluid reservoir equipped with positive and negative electrode electrolyte, circulating pump and circulation line, the monocell include anode collection plate, bear Pole collector plate, anode, cathode, ion-conductive membranes, it is characterised in that：Ion-conductive membranes are by nitrogenous heterocyclic aroma type polymer system Standby to form, anode, cathode are respectively carbon felt or carbon paper；Anode electrolyte is the mixed aqueous solution of ferrocyanide and highly basic, is born Pole electrolyte is zinc salt or/and the oxide of zinc and the mixed aqueous solution of highly basic, and the highly basic in positive and negative electrolyte is in aqueous solution A concentration of 0.001~10mol/L, active material is the iron cyanide (Fe (CN) in anode electrolyte6 3-) or ferrocyanide (Fe(CN)6 4-One or both of), active material is Zn (OH) in electrolyte liquid4 2-；Active matter in positive and negative electrode electrolyte A concentration of 0.001~3mol/L of matter；Wherein the aromatic polymer containing azacyclo- is the aromatic series that main chain contains azacyclo- Polymer or branch contain the one or two or more kinds in the aromatic polymer of azacyclo-.
2. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that：Main chain contains the fragrant adoption of azacyclo- Conjunction object is polybenzimidazoles, polypyridine, poly- pyrazoles, poly- pyrimidine, polythiazole, polybenzothiozole, Ju oxazoles, polybenzoxazole, gathers One or two or more kinds of polymer in oxadiazole, poly quinoline, polyquinoxaline, polythiadiazoles, poly- four purine；Branch contains azepine The aromatic polymer of ring is polyvinyl imidazole, the crosslinked chloromethylation of imidazoles of polyvinyl pyridine, branch nitrogen heterocyclic ring class is poly- Sulfone, branch nitrogen heterocyclic ring class the crosslinked chloromethyl polysulphone of 4,4 '-bipyridyls in one or two or more kinds.
3. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that：Active material is dense in electrolyte liquid Degree is 1/2~saturated concentration in corresponding strong base solution of active material concentration in anode electrolyte.
4. negative half-cell according to claim 1, it is characterised in that：The oxide of zinc is zinc oxide, and zinc salt is chlorination One or both of zinc, zinc sulfate, highly basic are one or more of sodium hydroxide, potassium hydroxide or lithium hydroxide.
5. Alkaline Zinc iron liquid galvanic battery according to claim 1 or 3, it is characterised in that：Just and/or in electrolyte liquid go back One or more of soluble-salt of potassium chloride, sodium sulphate, sodium chloride, potassium sulfate can be added and be used as assisted electrolysis matter, To improve the conductivity of supporting electrolyte；0~30wt% of a concentration of strong base concentrations of the assisted electrolysis matter.
6. Alkaline Zinc iron liquid galvanic battery according to claim 1, it is characterised in that：The positive and negative electrode collector plate is stone Black plate or copper coin.
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