WO2018103517A1 - 一种碱性锌铁液流电池 - Google Patents

一种碱性锌铁液流电池 Download PDF

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WO2018103517A1
WO2018103517A1 PCT/CN2017/111224 CN2017111224W WO2018103517A1 WO 2018103517 A1 WO2018103517 A1 WO 2018103517A1 CN 2017111224 W CN2017111224 W CN 2017111224W WO 2018103517 A1 WO2018103517 A1 WO 2018103517A1
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zinc
battery
negative
positive
electrolyte
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French (fr)
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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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    • 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
    • H01M8/08—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
    • 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

Definitions

  • the invention relates to the field of flow batteries, and in particular to the technical field of zinc iron flow batteries.
  • the flow battery is a new electrochemical energy storage technology. Compared with other energy storage technologies, it has flexible system design, large storage capacity, free site selection, high energy conversion efficiency, deep discharge, safety and environmental protection, and low maintenance cost. Other advantages, can be widely used in wind energy, solar energy and other renewable energy power generation, emergency power systems, backup power stations and power system peaking and valley filling.
  • Vanadium flow battery (VFB) is considered to have good application prospects due to its high safety, good stability, high efficiency, long life (lifetime >15 years), and low cost.
  • the solution is more expensive, which limits its large-scale application to a certain extent. Therefore, the development of electrochemical storage cells with excellent performance and low cost is very important for the popularization of renewable energy.
  • the more mature flow batteries are mainly zinc-bromine flow batteries, sodium polysulfide bromine and zinc-nickel battery systems.
  • the zinc bromine flow battery and the sodium sulfide bromine battery cause environmental pollution due to the formation of bromine element during charging of the positive electrode side electrolyte, which restricts its large-scale application; and the electrolyte of the zinc-nickel battery system needs 10 to 14 mol/
  • the strong base of L acts as a supporting electrolyte, and this high concentration of alkali solution is severely corroded to the equipment.
  • Patent 201180016873.6 discloses a class of alkaline zinc-iron liquid flow batteries comprising conductive mesh and non-conductive mesh; screen; belt; foam structure; array of cones, cylinders or pyramids; and wires or tubes Other arrangements are made, the electrode is a porous mesh metal electrode, although it shows better performance, its structure is more complicated, the electrochemical performance is lower, and the membrane material is selected from a perfluorosulfonic acid membrane (Nafion), and the cost is high. Poor stability.
  • the invention develops an alkaline zinc-iron liquid flow battery, and the specific technical solutions are as follows:
  • the battery includes a single battery or a battery module in which two or more single cells are connected in series/parallel, a liquid storage tank equipped with positive and negative electrolytes, a circulation pump and a circulation line, and the single battery includes a positive current collecting plate,
  • the negative current collecting plate, the electrode, the ion conductive membrane, and the ion conductive membrane are prepared from an aromatic polymer containing a nitrogen heterocycle, preferably a dense membrane, the electrode is carbon felt or carbon paper;
  • the positive electrolyte is ferrocyanide and strong a mixed aqueous solution of a base,
  • the negative electrode electrolyte is a mixed aqueous solution of a zinc salt or/and a zinc oxide and a strong alkali, and the concentration of the strong base in the positive and negative electrolytes in the aqueous solution is 0.001 to 10 mol/L, in the positive electrode electrolyte
  • the active material is one or two of ferricyanide (Fe(CN) 6 3- ) or
  • the polybenzimidazole dense film is preferred, and its ultra-high mechanical strength (elastic modulus > 2.9 GPa) and extremely low swelling effect (swelling rate: 4.348%) can effectively solve the zinc deposition caused by uneven deposition of zinc during battery charging.
  • the dendrite pierces the diaphragm causing a problem with the battery being shorted.
  • the ion-conducting membrane is used for blocking the positive and negative electrolytes, preventing the positive and negative electrodes from short-circuiting and transmitting ions to form an internal circuit; and the circulating pump is for circulating the electrolyte through the electrochemical of the positive and negative half-cells. Reaction zone.
  • the ferrocyanide or/and ferricyanide on the positive electrode side undergoes a valence reaction of iron on the electrode, and the reaction equation is as follows:
  • the active material in the positive electrode electrolyte is one or two of ferricyanide (Fe(CN) 6 3- ) or ferrocyanide (Fe(CN) 6 4- );
  • the oxide of zinc in the negative electrode electrolyte is zinc oxide (ZnO), and the zinc salt is one of zinc chloride (ZnCl 2 ) and zinc sulfate (ZnSO 4 ).
  • the strong base is one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH) or lithium hydroxide (LiOH) as a supporting electrolyte.
  • the concentration of the strong base is from 0.001 mol/L to 10 mol/L, preferably from 2 to 5 mol/L; a certain amount of auxiliary electrolyte may also be added to the above electrolyte solution (the concentration of the auxiliary electrolyte is 0.1 to 6 mol/L, preferably 2 to 4 mol).
  • Soluble salts such as potassium chloride (KCl), sodium sulfate (Na 2 SO 4 ), sodium chloride (NaCl), potassium sulfate (K 2 SO 4 ) to increase the conductivity of the supporting electrolyte.
  • the positive and negative electrolyte storage tanks are connected to the positive and negative inlets and outlets of the pipeline unit or the stack via the liquid transfer pump.
  • the concentration of the active material in the negative electrode electrolyte is 1/2 of the concentration of the active material in the positive electrode electrolyte to a saturated concentration in the corresponding strong alkali solution.
  • the electrolyte solution must be disposed at different temperatures depending on the concentration, and the temperature range is between 5 and 90 °C.
  • the electrolyte When charging a single cell or a stack, the electrolyte is transported from the positive and negative liquid storage tanks to the positive and negative electrodes via a pump, and the active material Fe(CN) 6 4- in the positive electrode storage tank undergoes electrochemical oxidation to form Fe (CN). 6 3- , Zn(OH) 4 2- ion is deposited directly on the carbon felt or carbon paper anode as a simple substance of zinc; when discharged, the anode zinc element is oxidized to Zn(OH) 4 2- ion in an alkaline solution environment.
  • the pump returns to the negative liquid storage tank, and the active material Fe(CN) 6 3- in the positive electrode electrolyte reacts electrochemically to form Fe(CN) 6 4 - and returns to the positive liquid storage tank via the pump.
  • the ion-conducting membrane may or may not be activated in a concentration of 0 mol/L ⁇ alkali aqueous solution ⁇ 10 mol/L.
  • An appropriate amount of quaternary ammonium salt, thiourea, polyvinyl alcohol, Bi 3+ , Ti + , Pd 2+ , Pb 2+ dendrite formation inhibitor may be added to the negative electrode electrolyte to control the deposition morphology of zinc.
  • the dendrite formation inhibitor concentration ranges from 0 to 0.02 mol/L.
  • the electrochemical oxidation-reduction potential of the negative electrode varies with the alkali concentration in the electrolyte solution, and its electrochemical redox potential ranges from -0.74 V vs. Hg/HgO to -1.44 V vs. Hg/HgO.
  • the alkaline zinc-iron flow battery has an operating current density of between 1 mA cm -2 and 200 mA cm -2 .
  • the charge and discharge time can be controlled according to the concentration of the electrolyte and the volume of the electrolyte.
  • the transport mechanism of the ion-conducting membrane containing a nitrogen-containing heterocycle in an alkaline zinc-iron battery is as shown in FIG. 10: conduction through a free aqueous solution adsorbed in the region or alternately dissociative adsorption between the ion exchange group and the aqueous solution. Conduction.
  • the assembled alkaline zinc-iron flow battery can be continuously and stably operated between the working current densities of 1 mA cm -2 to 200 mA cm -2 , showing the total vanadium solution
  • the flow battery is quite or even better battery performance.
  • this patent uses a nitrogen-containing heterocyclic ion exchange membrane, a carbon felt electrode and a high concentration and high stability electrolyte in an alkaline zinc-iron battery to invent a class of high energy density, high power density and long life.
  • Alkaline zinc iron flow battery uses a conductive carbon felt or carbon paper as an electrode, an ion exchange membrane such as a nitrogen-containing heterocycle, and an ion-conducting membrane such as a nitrogen-containing heterocycle as a battery separator, and the battery is represented.
  • the performance is comparable to or better than that of the currently mature all-vanadium redox flow battery, and the positive and negative redox couples of alkaline zinc-iron flow battery are Fe(CN) 6 3- /Fe(CN) 6 4- And Zn(OH) 4 2- /Zn, zinc iron is rich in reserves, and the cost is much lower than that of the whole vanadium redox flow battery, which meets the demand of large-scale applications and shows a good application prospect.
  • An ion-conducting membrane such as a nitrogen-containing heterocycle exhibits excellent chemical stability and mechanical stability as a battery separator in an alkaline electrolyte system, and particularly a preferred polybenzimidazole-based ion-conducting membrane, which is extremely high
  • the mechanical stability (elastic modulus > 2.9GPa), combined with the porous carbon felt with 3D network structure, effectively alleviates the short circuit problem caused by zinc dendrite piercing the diaphragm during zinc deposition.
  • the deposition process of zinc along the film direction is resisted, and is deposited along the interior of the porous carbon felt to form a metal zinc/3D porous carbon felt composite electrode.
  • the metal zinc and the 3D porous carbon felt have excellent bonding ability.
  • the zinc gradually dissolves from the outside to the inside, and the internal metal zinc maintains good contact with the 3D porous carbon felt, effectively alleviating the battery. Accumulation of metallic zinc during discharge.
  • the carbon felt electrode can be activated in situ in the alkaline electrolyte to effectively improve its electrochemical performance.
  • the carbon felt electrode can effectively alleviate the damage caused by zinc dendrite and zinc accumulation, resulting in short battery life.
  • These batteries exhibit battery performance comparable to or higher than that of all vanadium redox flow batteries, but at a much lower cost than all vanadium redox flow batteries, which are excellent in large-scale energy storage. Application prospects.
  • the potential of the negative electrode to Zn(OH) 4 2- /Zn can be adjusted according to the alkali concentration in the electrolyte. At high pH, the potential of the negative electrode is more negative for Zn(OH) 4 2- /Zn.
  • the unit cells assembled after pairing with the positive Fe(CN) 6 3- /Fe(CN) 6 4- have a higher open circuit voltage and thus have higher power density.
  • This alkaline zinc-iron liquid flow battery has the characteristics of high safety, good stability, low cost, simple structure and manufacturing process.
  • the concentration of the positive and negative active materials can be increased by adjusting the concentration of the supporting strong alkali, thereby increasing the energy density of the battery.
  • Figure 1 is a schematic view showing the structure of an alkaline zinc-iron liquid flow battery
  • Figure 2 shows the electrochemical performance test of the positive and negative active materials.
  • Figure 3 is a schematic view showing the structure of an ion-conducting membrane containing nitrogen-containing heterocyclic rings for an alkaline zinc-iron flow battery;
  • Figure 4 is a graph showing the battery performance of a basic zinc-iron flow battery assembled with a Nafion 115 ion exchange membrane at a current density of 80 mA cm -2 in Comparative Example 1.
  • Positive electrolyte composition 0.6mol/L Fe(CN) 6 4- +5mol/L OH - solution; negative electrolyte composition: 0.3mol/L Zn(OH) 4 2- +5mol/L OH - solution; positive and negative
  • the volume of the electrolyte is 60 mL each; the battery is charged in a constant current charge and discharge mode, charged at a current density of 80 mA cm -2 for 10 min, then the voltage is cut off, and discharged to 0 V at a current density of 80 mA cm -2 .
  • Figure 5 is a graph showing the battery performance test of an alkaline zinc-iron flow battery assembled in a PBI ion exchange membrane of Example 4.
  • Positive electrolyte composition 0.6mol/L Fe(CN) 6 4- +5mol/L OH - solution; negative electrolyte composition: 0.3mol/L Zn(OH) 4 2- +5mol/L OH - solution; positive and negative
  • the volume of the electrolyte is 60 mL each; the battery is charged in a constant current charge and discharge mode, charged at a current density of 60 mA cm -2 for 12 min, then the voltage is cut off, and discharged to 0 V at a current density of 60 mA cm -2 .
  • Figure 6 is a graph showing the battery performance test of an alkaline zinc-iron flow battery assembled in a PBI ion exchange membrane of Example 4.
  • Positive electrolyte composition 0.6mol/L Fe(CN) 6 4- +5mol/L OH - solution; negative electrolyte composition: 0.3mol/L Zn(OH) 4 2- +5mol/L OH - solution; positive and negative
  • the volume of the electrolyte is 60 mL each; the battery is charged in a constant current charge and discharge mode, charged at a current density of 60 mA cm -2 for 12 min, then the voltage is cut off, and discharged to 0 V at a current density of 60 mA cm -2 ; 80 mA cm - Charge at a current density of 2 for 10 min, then the voltage is cut off, and discharge to 0 V at a current density of 80 mA cm -2 ; charge at a current density of 100 mA cm -2 for 8 min, then the voltage is cut off, 100 mA cm -2 The current density was discharged to 0 V; the current density of 120 mA cm -2 was charged for 8 min, and then the voltage was cut off,
  • FIG. 7 Battery performance test of an alkaline zinc-iron flow battery assembled with a PBI ion exchange membrane. (a) charge and discharge curve of the 5th cycle; (b) partial charge and discharge cycle curve (variation of voltage with time); (c) cycle performance test; (d) discharge capacity and discharge energy with cycle during cycle test The change curve of the number.
  • Positive electrolyte composition 1mol / L Fe (CN) 6 4- +3mol / L OH - solution; negative electrolyte composition: 0.5mol / L Zn (OH) 4 2- +3mol / L OH - solution; positive and negative
  • the volume of the electrolyte was 60 mL each; the battery was charged in a constant current charge and discharge mode, charged at a current density of 60 mA cm -2 for 30 min, then the voltage was cut off, and discharged to 0 V at a current density of 60 mA cm -2 .
  • Figure 8 is a graph showing the battery performance test of an alkaline zinc-iron flow battery assembled in a PBI ion exchange membrane of Example 4.
  • Positive electrolyte composition 1mol / L Fe (CN) 6 4- +3mol / L OH - solution; negative electrolyte composition: 0.5mol / L Zn (OH) 4 2- +3mol / L OH - solution; positive and negative
  • the volume of the electrolyte was 60 mL each; the battery was charged in a constant current charge and discharge mode, charged at a current density of 80 mA cm -2 for 20 min, then the voltage was cut off, and discharged to 0 V at a current density of 80 mA cm -2 .
  • Figure 9 Battery performance of a vanadium redox flow cell assembled with a Nafion 115 membrane at a current density of 80 mA cm -2 and an alkaline zinc-iron flow battery assembled with a PBI ion exchange membrane at 80 mA cm -2 Comparison of battery performance under current density conditions; (b) discharge capacity of a vanadium redox flow battery assembled with Nafion 115 membrane at a current density of 80 mA cm -2 , discharge energy and basicity assembled with PBI ion exchange membrane The discharge capacity and discharge energy of a zinc-iron flow battery at a current density of 80 mA cm -2 .
  • All vanadium redox flow battery positive and negative electrolyte concentration 1.5mol / L, H 2 SO 4 concentration 3mol / L, positive and negative electrolyte volume 60mL each; battery using constant current charge and discharge mode, charge and discharge cutoff voltage are 1.55V, 1V; alkaline zinc-iron flow battery: positive electrolyte composition: 1mol / L Fe (CN) 6 4- +3mol / L OH - solution; negative electrolyte composition: 0.5mol / L Zn (OH) 4 2- +4mol/L OH - solution; positive and negative electrolyte volume 60mL each; battery used in constant current charge and discharge mode, charged at 80mA cm -2 current density for 20min, then voltage cutoff condition, 80mA cm -2 Discharge to 0V under current density conditions.
  • Figure 10 is a diagram showing the transport mechanism of an ion-conducting membrane containing a nitrogen-containing heterocycle in an alkaline zinc-iron battery.
  • Fe(CN) 6 3- /Fe(CN) 6 4- exhibits excellent electrochemical activity and electrochemical reversibility. Electrochemical oxidation of Fe(CN) 6 3- /Fe(CN) 6 4- electrode was found by plotting the peak current ip and the sweep rate (v 1/2 ) (Fig. 2d). The reduction reaction is diffusion control.
  • Cyclic voltammetry (CV) test of negative active material 0.1 mol/L ZnO was dissolved in 3.2 mol/L NaOH, with graphite plate as working electrode (working electrode area: 1 cm 2 ) and counter electrode, Hg/HgO electrode
  • the current and potential curves were measured at a sweep speed of 10 to 60 mV s -1 (Fig. 2b). It can be seen that the negative electrode has little effect on the sweep rate of Zn(OH) 4 2- /Zn.
  • Single cell assembly Single cells are assembled in the following order: positive end plate, graphite current collector, positive 6x8 cm 2 carbon felt, ion conductive membrane (ion exchange membrane containing nitrogen heterocycle and porous ion conduction such as nitrogen heterocycle) The film is partially structured as shown in Fig. 3), the negative electrode is 6x8 cm 2 carbon felt, the graphite current collector, and the negative electrode end plate. The structure of the single cell is shown in Figure 1.
  • Nafion 115 is used as ion exchange membrane, both positive and negative electrodes are carbon felt, positive electrode electrolyte is 0.6mol/L Fe(CN) 6 4- +5mol/L OH - solution; negative electrolyte is 0.3mol/L Zn(OH 4 2- +5mol/L OH - solution; the volume of the positive and negative electrolytes is 60mL each; the battery is charged in a constant current charge and discharge mode, charged at a current density of 80mA cm -2 for 10min, then the voltage is cut off, 80mA cm Discharge to 0V at a current density of -2 . It can be seen from the charge-discharge curve of the battery (Fig.
  • POD polyoxadiazole
  • the discharge voltage of the battery is about 1.76V
  • the CE, EE and VE of the battery are 99%, 81% and 82%, respectively.
  • the charge and discharge capacity and charge and discharge energy of the battery were kept stable, and the battery performance was not significantly attenuated.
  • a branched nitrogen-containing heterocyclic imidazole cross-linked chloromethylated polysulfone porous ion-conducting membrane (CMPSF-Im), and battery test conditions are consistent with battery test conditions assembled with a POD film.
  • the battery polarization is lower than that of the single cell assembled with the POD film, so that in addition to having high ion selectivity (CE to 99%), the ionic conductivity is also high, and the VE is about 82%. .
  • CE high ion selectivity
  • the ionic conductivity is also high, and the VE is about 82%.
  • the pore structure in the porous membrane contributes to the liquid retention rate in the membrane and thus facilitates the conduction of ions.
  • the charge and discharge capacity and charge and discharge energy of the battery are stable, showing good stability and battery performance.
  • CPSF-Biy 4,4'-bipyridine crosslinked chloromethylated polysulfone ion exchange membrane having a branched nitrogen-containing heterocyclic ring was used, and the battery test conditions were the same as those of the battery assembled with the POD film.
  • the battery polarization is higher than that of the single cell assembled with the POD film, and the VE assembled by the single cell has a VE of about 78% and a CE of about 99%.
  • the assembled batteries have better cycle stability. After more than 100 cycles, the charge and discharge capacity and charge and discharge energy of the batteries remain stable.
  • the ion conductive membrane is a polybenzimidazole ion exchange membrane (PBI) containing a nitrogen heterocyclic ring
  • the positive electrolyte is 0.6 mol/L Fe(CN) 6 4- +5 mol/L OH - solution
  • the negative electrolyte is 0.3 mol /L Zn(OH) 4 2- +5mol/L OH - solution
  • the volume of the positive and negative electrolytes is 60mL each; the battery is charged in a constant current charge and discharge mode, charged at a current density of 60mA cm -2 for 12min, then the voltage is cut off. Under the condition, the current density of 60 mA cm -2 was discharged to 0 V.
  • variable current density 60-120 mA cm -2
  • the alkaline zinc-iron flow battery assembled with PBI ion exchange membrane has a current density of 120 mA cm -2 (Fig. 6a)
  • the CE retention of the battery At 99% or more, EE is maintained at 82% or more, and VE is maintained at 83% or more, exhibiting excellent rate performance.
  • the initial discharge voltage of the battery assembled with PBI can reach 1.8 V or more (Fig. 6b), and the change trend of charge and discharge voltage is consistent with time (Fig. 6c).
  • the alkaline zinc-iron flow battery assembled with PBI has no significant attenuation of battery performance and battery capacity after continuous operation for more than 100 cycles under the current density of 80 mA cm -2 (Fig. 6d), further showing excellent circulation. stability.
  • the battery performance (capacity and power density) comparable to that of the all-vanadium flow battery currently in the demonstration stage is increased, and the concentration of the positive active material is increased to 1 mol/L Fe. (CN) 6 4- , the concentration of the base is reduced to 3 mol/L OH - , and the corresponding negative electrode electrolyte is 0.5 mol/L Zn(OH) 4 2- +3 mol/L OH - solution.
  • the positive and negative electrolyte volumes are each 60 mL; PBI is used as an ion exchange membrane to assemble a single cell, which is charged in a constant current charge and discharge mode, charged at a current density of 60 mA cm -2 for 30 min, and then the voltage is cut off, 60 mA cm -2 Discharge to 0V under current density conditions. It can be seen from Fig. 7a that the ohmic polarization of the battery is further reduced, and the initial discharge voltage of the battery is close to 1.9V. After more than 135 hours of charge and discharge cycles, the initial discharge voltage of the battery is always maintained at about 1.9V (Fig. 7b).
  • the CE of the battery is always above 99%, and VE and EE are always above 91% (Fig. 7c), showing excellent battery performance and cycle stability. Due to the increase of active substances in the electrolyte, the discharge specific capacity of the battery is close to 25Ah/L, and the discharge specific energy is close to 40Wh/L (Fig. 7d), and it remains basically unchanged within 150 cycles, showing a good application prospect. .
  • the ohmic polarization inside the battery increases due to the increase in current density, and the initial discharge voltage of the battery is reduced from 1.9 V to about 1.8 V (Fig. 8a).
  • the initial discharge voltage of the battery is always maintained at about 1.8V (Fig. 8b), indicating that the ohmic polarization inside the battery will not be under the condition of high concentration of active material and high current density.
  • Significant changes have occurred.
  • the CE of the battery is always above 99%, and VE and EE are always above 88% (Fig. 8c), showing excellent battery performance and cycle stability. Due to the increase in the active material in the electrolyte, the discharge specific capacity of the battery was maintained above 21 Ah/L for more than 200 cycles, and the discharge specific energy was always maintained at 35 Wh/L (Fig. 8d).
  • All vanadium redox flow battery assembled with Nafion 115 membrane (positive and negative active material concentration 1.5mol/L, H 2 SO 4 concentration 3mol/L, positive and negative electrolyte volume 60mL each; battery adopts constant current charge and discharge mode
  • the charge-discharge current density of the battery is 80 mA cm -2
  • the charge-discharge cut-off voltage is 1.55 V, 1 V).
  • the alkaline zinc-iron flow battery assembled with PBI is at a current density of 80 mA cm -2 , and the battery is used.
  • the CE is 99.61%, the EE is 89.90%, and the EE is 90.24% (Fig. 9a).
  • the ion conductive membrane is a polybenzimidazole ion exchange membrane (PBI) containing a nitrogen heterocyclic ring, the positive electrolyte is 0.6 mol/L Fe(CN) 6 4- +5 mol/L OH - solution; the negative electrolyte is 0.3 mol /L Zn(OH) 4 2- +5mol/L OH - solution; positive and negative electrolyte volume 60mL each; positive electrode using carbon felt electrode, negative electrode using zinc plate as electrode; battery using constant current charge and discharge mode, at 60mA cm The current density of -2 was charged for 12 min, then the voltage was cut off, and the current was discharged to 0 V at a current density of 60 mA cm -2 .
  • PBI polybenzimidazole ion exchange membrane
  • the coulombic efficiency of the battery is maintained at about 99%, and the voltage efficiency is about 81%. After 70 cycles, the capacity of the battery gradually decreases, and the Coulomb efficiency drops from 99% to 92%.
  • the battery was disassembled and found that the zinc uniformity deposited on the negative zinc sheet was very poor, and the surface of the PBI film had obvious metallic zinc, indicating that the metal electrode was used as the negative electrode of the alkaline zinc-iron battery, and the efficiency of the battery was The cycle performance and the deposition and dissolution of zinc have a negative impact.

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Abstract

一种碱性锌铁液流电池，其离子传导膜由含氮杂环的芳香型聚合物制备而成，电极为碳毡或碳纸；正极电解液为亚铁氰化物作和强碱的混合水溶液，负极电解液为锌盐或/和锌的氧化物与强碱的混合水溶液，正、负电解液中的强碱在水溶液中的浓度为0.001～10mol/L，正、负极电解液中活性物质的浓度为0.001～3mol/L。所述碱性锌铁液流电池具有高能量密度、高功率密度、长寿命的特点，表现出的电池性能与目前成熟的全钒液流电池的电池性能相当甚至更优，表现出很好的应用前景。

Description

一种碱性锌铁液流电池 技术领域
本发明涉及液流电池领域，特别涉及一种锌铁液流电池技术领域。
背景技术
液流电池是一种电化学储能新技术，与其它储能技术相比，具有系统设计灵活、蓄电容量大、选址自由、能量转换效率高、可深度放电、安全环保、维护费用低等优点，可以广泛应用于风能、太阳能等可再生能源发电储能、应急电源系统、备用电站和电力系统削峰填谷等方面。全钒液流电池(Vanadium flow battery,VFB)由于安全性高、稳定性好、效率高、寿命长(寿命>15年)、成本低等优点，被认为具有良好的应用前景，但VFB的电解质溶液价格较贵，这在一定程度上限制了其大规模应用。因此开发性能优异，成本低廉的电化学储能电池对可再生能源普及应用非常重要。
除了全钒液流电池以外，目前发展较为成熟的液流电池主要还有锌溴液流电池、多硫化钠溴和锌镍电池体系。其中锌溴液流电池和多硫化钠溴电池由于正极侧电解液在充电时会生成溴单质而造成环境污染，制约了其大规模应用；而锌镍电池体系的电解液需用10～14mol/L的强碱作为支持电解质，这种高浓度的碱溶液对设备腐蚀严重。
锌铁液流电池由于具有电解液成本低的优势，在大规模液流电池中具有较好的应用前景。专利201180016873.6公开了一类碱性锌铁液流电池组是由导电网孔和非导电网孔；筛网；带；泡沫结构；圆锥体、圆柱体或角锥体的阵列；和线或管子的其他布置做成，电极为多孔网孔金属电极，尽管表现出较好的性能，但其结构较为复杂，电化学性能较低，此外膜材料选择全氟磺酸膜(Nafion)，成本较高，稳定性较差。
发明内容
为解决上述技术问题，开发一种低成本、结构简单、电化学性能优异的锌铁液流电池尤为重要，为达到上述目的，
本发明开发一种碱性锌铁液流电池，具体技术方案如下：
电池包括一节单电池或二节以上单电池串/并联而成的电池模块、装有正、负极电解液的储液罐、循环泵和循环管路，所述单电池包括正极集流板、负极集流板、电极、离子传导膜，离子传导膜由含氮杂环的芳香型聚合物制备而成，优选致密膜，电极为碳毡或碳纸；正极电解液为亚铁氰化物和强碱的混合水溶液，负极电解液为锌盐 或/和锌的氧化物与强碱的混合水溶液，正、负电解液中的强碱在水溶液中的浓度为0.001～10mol/L，正极电解液中活性物质为铁氰化物(Fe(CN)6 3-)或亚铁氰化物(Fe(CN)6 4-)中的一种或两种，负极电解液中活性物质为Zn(OH)4 2-；正、负极电解液中活性物质的浓度为0.001～3mol/L；其中含有氮杂环的芳香族聚合物为聚苯并咪唑、聚乙烯咪唑、聚吡啶、聚乙烯吡啶、聚吡唑、聚嘧啶、聚噻唑、聚苯并噻唑、聚噁唑、聚苯并噁唑、聚噁二唑、聚喹啉、聚喹喔啉、聚噻二唑、聚四嘌呤中的一种或多种聚合物。优选聚苯并咪唑致密膜，其超高的机械强度(弹性模量>2.9GPa)及极低的溶胀作用(溶胀率：4.348％)，可有效解决电池充电过程中锌的不均匀沉积造成锌枝晶刺穿隔膜导致电池短路的问题。
其中所述离子传导膜用于阻隔正负极电解液，防止正负极短路和传递离子形成内部回路；所述的循环泵用于使电解液循环通过所述的正、负半电池的电化学反应区域。
负极侧的锌盐或/和锌的氧化物在强碱中溶解后生成Zn(OH)4 2-后在电极上发生沉积溶解的电化学反应，反应方程式如下：
Figure PCTCN2017111224-appb-000001
正极侧的亚铁氰化物或/和铁氰化物在电极上发生铁的变价反应，反应方程式如下：
Figure PCTCN2017111224-appb-000002
充电过程中，负极侧，锌盐或锌的氧化物在强碱中溶解后生成Zn(OH)4 2-后在碳毡或碳纸电极上得到两个电子被还原成锌单质；对应的在正极侧，Fe(CN)6 4-在碳毡或碳纸电极上失去电子被氧化为Fe(CN)6 3-。
正极电解液中的活性物质为铁氰化物(Fe(CN)6 3-)或亚铁氰化物(Fe(CN)6 4-)中的一种或两种；
负极电解液中锌的氧化物为氧化锌(ZnO)，锌盐为氯化锌(ZnCl2)、硫酸锌(ZnSO4)中的一种。
强碱为氢氧化钠(NaOH)，氢氧化钾(KOH)或氢氧化锂(LiOH)中的一种或两种以上作为支持电解质。
强碱的浓度为0.001mol/L～10mol/L，优选2-5mol/L；也可向上述电解质溶液中加入一定量的辅助电解质(辅助电解质的浓度为0.1～6mol/L，优选2～4mol/L) 如氯化钾(KCl)、硫酸钠(Na2SO4)、氯化钠(NaCl)、硫酸钾(K2SO4)等可溶性盐，以提高支持电解质的电导率。
正、负极电解液储液罐经液体输送泵通过管路单电池或电堆的正、负极入口和出口相连。
优选负极电解液中活性物质的浓度为正极电解液中活性物质浓度的1/2～在所对应的强碱溶液中的饱和浓度。
所述的电解质溶液根据浓度的不同须在不同温度下配置,所述的温度范围在5～90℃之间。
单电池或电堆充电时，电解液经由泵从正负极储液罐分别输送至正、负极，正极储液罐中的活性物质Fe(CN)6 4-发生电化学氧化反应生成Fe(CN)6 3-，Zn(OH)4 2-离子在碳毡或碳纸负极上直接以锌单质形式沉积；放电时，负极锌单质在碱溶液环境下氧化为Zn(OH)4 2-离子经由泵回到负极储液罐中，与之对应的正极电解液中活性物质Fe(CN)6 3-发生电化学还原反应生成Fe(CN)6 4-，经由泵回到正极储液罐中。
所述的离子传导膜可以(或不需要)在0mol/L<碱的水溶液的浓度<10mol/L中活化。
可以在负极电解液中加入适量的季铵盐、硫脲、聚乙烯醇、Bi3+、Ti+、Pd2+、Pb2+的枝晶形成抑制剂来调控锌的沉积形貌，所加入的枝晶形成抑制剂浓度范围为0～0.02mol/L。
负极发生的电化学氧化还原电位随着电解质溶液中碱浓度的不同而不同，其电化学氧化还原电位范围在-0.74V vs.Hg/HgO～-1.44V vs.Hg/HgO之间。
碱性锌铁液流电池，其工作电流密度在1mA cm-2～200mA cm-2之间。
碱性锌铁液流电池，其充放电时间可以根据电解质浓度的大小，电解液体积的多少来控制。
其中，含氮杂环的离子传导膜在碱性锌铁电池中的传输机理如下图10所示：通过区域内吸附的自由水溶液进行传导或通过离子交换基团与水溶液之间的交替解离吸附进行传导。
通过筛选电极和离子传导膜，优化电解液组成，组装出的碱性锌铁液流电池可以在1mA cm-2～200mA cm-2的工作电流密度之间连续稳定运行，表现出与全钒液流电池相当甚至更优的电池性能。
本发明的有益成果：
1.本专利首次将含氮杂环离子交换膜、碳毡类电极以及高浓度高稳定性电解液用于碱性锌铁电池中，发明了一类高能量密度、高功率密度、长寿命的碱性锌铁液流电池。所提出的碱性锌铁液流电池采用导电碳毡或碳纸作为电极，用含氮杂环一类的离子交换膜和含氮杂环一类的离子传导膜作为电池隔膜，表现出的电池性能与目前成熟的全钒液流电池的电池性能相当甚至更优，且碱性锌铁液流电池正负极氧化还原电对分别为Fe(CN)6 3-/Fe(CN)6 4-和Zn(OH)4 2-/Zn，锌铁储量丰富，成本远低于全钒液流电池，满足大规模应用的需求，表现出很好的应用前景。
2.含氮杂环一类的离子传导膜作为电池隔膜在碱性电解液体系中表现出优异的化学稳定性和机械稳定性，特别是优选的聚苯并咪唑类离子传导膜，具有极高的机械稳定性(弹性模量>2.9GPa)，配合具有3D网络结构的多孔碳毡，有效缓解了锌沉积过程中锌枝晶刺穿隔膜造成的电池短路问题。由于聚苯并咪唑类离子传导膜的超高机械强度，锌沿着膜方向的沉积过程受到阻力，转而沿着向着多孔碳毡内部沉积，形成金属锌/3D多孔碳毡复合电极。在这种复合电极内部，金属锌与3D多孔碳毡具有优异的结合能力，放电过程中，锌逐渐由外部向内部溶解，内部金属锌与3D多孔碳毡依然保持良好的接触，有效缓解了电池放电过程中金属锌的累积。
3.碳毡电极在碱性电解液可以被原位活化，有效的提高其电化学性能，此外，碳毡电极可以有效缓解锌枝晶与锌累积对膜造成的破坏，带来的电池寿命短的问题。该类电池表现出与全钒液流电池相媲美甚至高于全钒的能量密度和功率密度的电池性能，但成本远远低于全钒液流电池，在大规模储能领域具有很好的应用前景。
4.负极电对Zn(OH)4 2-/Zn的电位可根据电解液中碱浓度的大小来调控，在高pH值下，负极电对Zn(OH)4 2-/Zn的电位更负，与正极Fe(CN)6 3-/Fe(CN)6 4-配对后组装的单电池具有更高的开路电压，因而具有更高的功率密度。
5.这种碱性锌铁液流电池具有安全性高、稳定性好、成本低、结构及制造工艺简单的特点。
6.可以通过调控支持电解质强碱的浓度来提高正负极活性物质的浓度，从而提高电池的能量密度。
附图说明
图1碱性锌铁液流电池结构示意图；
图2正负极活性物质的电化学性能测试。(a)0.1mol/L Zn(OH)4 2-+3mol/L NaOH溶液及0.2mol/L Fe(CN)6 3-+0.2mol/L Fe(CN)6 4-+3mol/L NaOH溶液的循环伏安 测试；(b)0.1mol/L Zn(OH)4 2-+3mol/L NaOH溶液在10～60mV s-1扫速下的循环伏安图；(c)0.2mol/L Fe(CN)6 3-+0.2mol/L Fe(CN)6 4-+3mol/L NaOH溶液在10～60mV s-1扫速下的循环伏安图；(d)与图c对应的氧化还原峰电流ip与扫速的二分之一次方(v1/2)的线性图。
图3几种用于碱性锌铁液流电池的含氮杂环类的离子传导膜的结构示意图；
图4为对比例1用Nafion 115离子交换膜组装的碱性锌铁液流电池在80mA cm-2的电流密度条件下的电池性能。(a)第5个循环的充放电曲线；(b)循环性能测试。正极电解液组成：0.6mol/L Fe(CN)6 4-+5mol/L OH-溶液；负极电解液组成：0.3mol/L Zn(OH)4 2-+5mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在80mA cm-2的电流密度条件下充电10min，然后电压截止为条件，80mA cm-2的电流密度条件下放电至0V。
图5为实施例4用PBI离子交换膜组装的碱性锌铁液流电池的电池性能测试。(a)第5个循环的充放电曲线；(b)部分充放电循环曲线(电压随时间的变化关系)；(c)长循环性能测试；(d)循环测试过程中放电容量及放电能量随循环数的变化关系曲线。正极电解液组成：0.6mol/L Fe(CN)6 4-+5mol/L OH-溶液；负极电解液组成：0.3mol/L Zn(OH)4 2-+5mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在60mA cm-2的电流密度条件下充电12min，然后电压截止为条件，60mA cm-2的电流密度条件下放电至0V。
图6为实施例4用PBI离子交换膜组装的碱性锌铁液流电池的电池性能测试。(a)不同电流密度下的电池性能测试；(b)第5个循环的充放电曲线；(c)部分充放电循环曲线(电压随时间的变化关系)；(d)循环性能测试。正极电解液组成：0.6mol/L Fe(CN)6 4-+5mol/L OH-溶液；负极电解液组成：0.3mol/L Zn(OH)4 2-+5mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在60mA cm-2的电流密度条件下充电12min，然后电压截止为条件，60mA cm-2的电流密度条件下放电至0V；80mA cm-2的电流密度条件下充电10min，然后电压截止为条件，80mA cm-2的电流密度条件下放电至0V；100mA cm-2的电流密度条件下充电8min，然后电压 截止为条件，100mA cm-2的电流密度条件下放电至0V；120mA cm-2的电流密度条件下充电8min，然后电压截止为条件，120mA cm-2的电流密度条件下放电至0V。
图7用PBI离子交换膜组装的碱性锌铁液流电池的电池性能测试。(a)第5个循环的充放电曲线；(b)部分充放电循环曲线(电压随时间的变化关系)；(c)循环性能测试；(d)循环测试过程中放电容量及放电能量随循环数的变化关系曲线。正极电解液组成：1mol/L Fe(CN)6 4-+3mol/L OH-溶液；负极电解液组成：0.5mol/L Zn(OH)4 2-+3mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在60mA cm-2的电流密度条件下充电30min，然后电压截止为条件，60mA cm-2的电流密度条件下放电至0V。
图8为实施例4用PBI离子交换膜组装的碱性锌铁液流电池的电池性能测试。(a)第5个循环的充放电曲线；(b)部分充放电循环曲线(电压随时间的变化关系)；(c)循环性能测试；(d)循环测试过程中放电容量及放电能量随循环数的变化关系曲线。正极电解液组成：1mol/L Fe(CN)6 4-+3mol/L OH-溶液；负极电解液组成：0.5mol/L Zn(OH)4 2-+3mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在80mA cm-2的电流密度条件下充电20min，然后电压截止为条件，80mA cm-2的电流密度条件下放电至0V。
图9(a)用Nafion 115膜组装的全钒液流电池在80mA cm-2的电流密度条件下的电池性能与用PBI离子交换膜组装的碱性锌铁液流电池在80mA cm-2的电流密度条件下的电池性能的对比；(b)用Nafion 115膜组装的全钒液流电池在80mA cm-2的电流密度条件下的放电容量，放电能量与用PBI离子交换膜组装的碱性锌铁液流电池在80mA cm-2的电流密度条件下的放电容量，放电能量的对比。全钒液流电池：正负极电解液浓度各1.5mol/L，H2SO4浓度3mol/L，正负极电解液体积各60mL；电池采用恒电流充放电模式，充放电截止电压分别为1.55V，1V；碱性锌铁液流电池：正极电解液组成：1mol/L Fe(CN)6 4-+3mol/L OH-溶液；负极电解液组成：0.5mol/L Zn(OH)4 2-+4mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在80mA cm-2的电流密度条件下充电20min，然后电压截止为条件，80mA cm-2的电流密度条件下放电至0V。
图10为含氮杂环的离子传导膜在碱性锌铁电池中的传输机理。
具体实施方式
正极活性物质的循环伏安(CV)测试：将0.2mol/L Fe(CN)6 4-+0.2mol/L Fe(CN)6 3-溶于3mol/L NaOH中，分别以石墨板为工作电极(工作电极面积：1cm2)和对电极，Hg/HgO电极为参比电极，在10～60mV s-1扫速下测得电流和电位的曲线(图2c)，可以看出正极电对Fe(CN)6 3-/Fe(CN)6 4-表现出优异的电化学活性和电化学可逆性。通过对峰电流ip和扫速的二分之一次方(v1/2)作图(图2d)发现，Fe(CN)6 3-/Fe(CN)6 4-电对的电化学氧化还原反应属于扩散控制。
负极活性物质的循环伏安(CV)测试：将0.1mol/L ZnO溶于3.2mol/L NaOH中，分别以石墨板为工作电极(工作电极面积：1cm2)和对电极，Hg/HgO电极为参比电极，在10～60mV s-1扫速下测得电流和电位的曲线(图2b)，可以看出负极电对Zn(OH)4 2-/Zn受扫速影响不大。
通过Zn(OH)4 2-/Zn电对和Fe(CN)6 3-/Fe(CN)6 4-电对在40mV s-1扫速下的半波电位分析可以看出，正负极电势差为1.74V(图2a)，远高于全钒的开路电压(1.2V)。
单电池组装：单电池按如下顺序组装：正极端板、石墨集流体、正极6x8cm2碳毡、离子传导膜(含氮杂环一类的离子交换膜和含氮杂环一类的多孔离子传导膜，部分结构式如图3)、负极6x8cm2碳毡、石墨集流体、负极端板。单电池结构见图1。
对比例1
以Nafion 115为离子交换膜，正负极均为碳毡，正极电解液为0.6mol/L Fe(CN)6 4-+5mol/L OH-溶液；负极电解液为0.3mol/L Zn(OH)4 2-+5mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在80mA cm-2的电流密度条件下充电10min，然后电压截止为条件，80mA cm-2的电流密度条件下放电至0V。从电池的充放电曲线(图4a)可以看出，电池的放电电压接近1.8V，电池初始的库伦效率(CE)接近100％，能量效率(EE)和电压效率(VE)接近80％。经过100个循环以后，电池的库伦效率基本保持不变，而电压效率和能量效率降至70％左右(图4b)。
实施例1
含氮杂环类的聚噁二唑(POD)致密膜，正极电解液为0.6mol/L Fe(CN)6 4-+3mol/L OH-溶液；负极电解液为0.3mol/L Zn(OH)4 2-+3mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在80mA cm-2的电流密度条件下充电10min，然后电压截止为条件，80mA cm-2的电流密度条件下放电至0V。通过电池 的充放电曲线可知，电池的放电电压在1.76V左右，电池的CE，EE和VE分别为99％，81％和82％左右。在70个循环以内，电池的充放电容量及充放电能量均保持稳定，电池性能未见明显衰减。
实施例2
支链含氮杂环类的咪唑交联的氯甲基化聚砜多孔离子传导膜(CMPSF-Im)，电池测试条件与用POD膜组装的电池测试条件一致。通过电池的充放电曲线可知，电池极化低于用POD膜组装的单电池，因而除了具有高的离子选择性以外(CE～99％)，其离子传导率也较高，VE为82％左右。这可能是因为多孔膜内的孔结构有利于膜内的持液率，因而有利于离子的传导。在100多个循环以内，电池的充放电容量及充放电能量均保持稳定，表现出较好的稳定性及电池性能。
实施例3
支链含氮杂环类的4,4’-联吡啶交联的氯甲基化聚砜离子交换膜(CMPSF-Biy)，电池测试条件与用POD膜组装的电池测试条件一致。通过电池的充放电曲线可知，电池极化高于用POD膜组装的单电池，用其组装的单电池的VE为78％左右，CE为99％左右。尽管这类膜在碱性锌铁电池中的VE较低，但用其组装的电池循环稳定性较好，经过100多个循环以后，电池的充放电容量及充放电能量均保持稳定。
实施例4
离子传导膜为含氮杂环类的聚苯并咪唑离子交换膜(PBI)，正极电解液为0.6mol/L Fe(CN)6 4-+5mol/L OH-溶液；负极电解液为0.3mol/L Zn(OH)4 2-+5mol/L OH-溶液；正负极电解液体积各60mL；电池采用恒电流充放电模式，在60mA cm-2的电流密度条件下充电12min，然后电压截止为条件，60mA cm-2的电流密度条件下放电至0V。由于电流密度为60mA cm-2，因而充电时间由初始10min延长至12min，从图5a可以看出电池内部的欧姆极化较低，电池的电压效率和能量效率均接近90％，表现出优异的电池性能。随机选取部分电压随时间的变化曲线(图5b)可以看出，在长循环运行过程中(电池运行90h左右)，循环过程中的电压曲线无明显变化，表现出优异的稳定性。经过500多个循环以后，电池的CE，VE，EE(图5c)，放电容量和放电能量(图5d)未见明显衰减，表现出优异的稳定性。
通过变电流密度(60～120mA cm-2)实验可以看出，用PBI离子交换膜组装的碱性锌铁液流电池在120mA cm-2的电流密度条件下(图6a)，电池的CE保持在99％以上，EE保持在82％以上，VE保持在83％以上，表现出优异的倍率性能。且在80mA  cm-2的充放电电流密度条件下，用PBI组装的电池的初始放电电压可以达到1.8V以上(图6b)，充放电电压的变化趋势随着时间的变化保持一致(图6c)，表明电池运行过程中电池内部的极化作用基本保持不变，有利于得到稳定优异的电池性能。用PBI组装的碱性锌铁液流电池在80mA cm-2的电流密度条件下连续稳定性运行100多个循环后电池性能和电池容量未出现明显衰减(图6d)，进一步表现出优异的循环稳定性。
为进一步证实碱性锌铁液流电池的实用性，达到与目前处于示范阶段的全钒液流电池相媲美的电池性能(容量和功率密度)，将正极活性物质的浓度增加至1mol/L Fe(CN)6 4-，碱的浓度降低为3mol/L OH-，与之相对应的负极电解液为0.5mol/L Zn(OH)4 2-+3mol/L OH-溶液。正负极电解液体积各60mL；以PBI为离子交换膜组装成单电池，采用恒电流充放电模式，在60mA cm-2的电流密度条件下充电30min，然后电压截止为条件，60mA cm-2的电流密度条件下放电至0V。从图7a可以看出，电池的欧姆极化进一步减小，电池的初始放电电压接近1.9V，经过135余个小时的充放电循环考察，电池的初始放电电压始终保持在1.9V左右(图7b)，表明在高浓度的活性物质条件下，电池内部的欧姆极化也不会发生明显变化。经过150多个循环后，电池的CE始终保持在99％以上，VE和EE均始终保持在91％以上(图7c)，表现出优异的电池性能和循环稳定性。由于电解液中活性物质的增加，电池的放电比容量接近25Ah/L，而放电比能量接近40Wh/L(图7d)，且在150个循环以内基本保持不变，表现出很好的应用前景。
进一步将工作电流密度从60mA cm-2提高至80mA cm-2，由于电流密度的提高，电池内部的欧姆极化增大，电池的初始放电电压由1.9V降低至1.8V左右(图8a)，经过90余个小时的充放电循环考察，电池的初始放电电压始终保持在1.8V左右(图8b)，表明在高浓度的活性物质和高电流密度条件下，电池内部的欧姆极化也不会发生明显变化。经过200多个循环后，电池的CE始终保持在99％以上，VE和EE均始终保持在88％以上(图8c)，表现出优异的电池性能和循环稳定性。由于电解液中活性物质的增加，电池的放电比容量在200个循环以内始终保持在21Ah/L以上，而放电比能量始终保持在35Wh/L(图8d)。
与用Nafion 115膜组装的全钒液流电池(正负极活性物质浓度各1.5mol/L，H2SO4浓度3mol/L，正负极电解液体积各60mL；电池采用恒电流充放电模式，电池的充放电电流密度为80mA cm-2，充放电截止电压分别为1.55V，1V)相比较，用 PBI组装的碱性锌铁液流电池在80mA cm-2的电流密度条件下，电池的CE为99.61％，EE为89.90％，EE为90.24％(图9a)，性能远优于用Nafion 115膜组装的全钒液流电池的电池性能(CE为96.62％，EE为83.55％，VE为86.47％)。且用Nafion 115膜组装的全钒液流电池在200个循环以后，电池的放电比容量由初始的26.5Ah/L衰减值8.7Ah/L(图9b)，而用PBI组装的碱性锌铁液流电池的放电比容量始终保持在21Ah/L以上(图9b)；另一方面，用PBI组装的碱性锌铁液流电池的放电比能量始终保持在35Wh/L左右(图9b)，用Nafion 115膜组装的全钒液流电池在200个循环以后，电池的放电比能量由初始的33.4Wh/L衰减值10.8Wh/L(图9b)，性能远优于全钒液流电池，表现出很好的应用前景。
Figure PCTCN2017111224-appb-000003
对比例2：
离子传导膜为含氮杂环类的聚苯并咪唑离子交换膜(PBI)，正极电解液为0.6mol/L Fe(CN)6 4-+5mol/L OH-溶液；负极电解液为0.3mol/L Zn(OH)4 2-+5mol/L OH-溶液；正负极电解液体积各60mL；正极采用碳毡电极，负极采用锌片作为电极；电池采用恒电流充放电模式，在60mA cm-2的电流密度条件下充电12min，然后电压截止为条件，60mA cm-2的电流密度条件下放电至0V。电池的库伦效率保持在99％左右，而电压效率为81％左右经过70个循环后，电池的容量逐渐降低，库伦效率有初始99％降至92％左右。电池充电末期，将电池拆开，发现负极锌片上沉积的锌均一性很差，且PBI膜表面有明显的金属锌，表明用金属电极作为碱性锌铁电池的负极电极，对电池的效率、循环性能及锌的沉积溶解反应负面影响较大。

Claims (6)

  1. 一种碱性锌铁液流电池，电池包括一节单电池、或二节以上单电池串和/或并联而成的电池模块，装有正、负极电解液的储液罐、循环泵和循环管路；所述单电池包括正极集流板、负极集流板、正极、负极、离子传导膜，其特征在于：离子传导膜由含氮杂环的芳香型聚合物制备而成，正极、负极分别为碳毡或碳纸；正极电解液为亚铁氰化物和强碱的混合水溶液，负极电解液为锌盐或/和锌的氧化物与强碱的混合水溶液，正、负电解液中的强碱在水溶液中的浓度为0.001～10mol/L，正极电解液中活性物质为铁氰化物(Fe(CN)6 3-)或亚铁氰化物(Fe(CN)6 4-)中的一种或两种，负极电解液中活性物质为Zn(OH)4 2-；正、负极电解液中活性物质的浓度为0.001～3mol/L；其中含有氮杂环的芳香族聚合物为主链含有氮杂环的芳香族聚合物或支链含有氮杂环的芳香族聚合物中的一种或二种以上。
  2. 根据权利要求1所述的碱性锌铁液流电池，其特征在于：主链含有氮杂环的芳香族聚合物为聚苯并咪唑、聚吡啶、聚吡唑、聚嘧啶、聚噻唑、聚苯并噻唑、聚噁唑、聚苯并噁唑、聚噁二唑、聚喹啉、聚喹喔啉、聚噻二唑、聚四嘌呤中的一种或二种以上聚合物；支链含有氮杂环的芳香族聚合物为聚乙烯咪唑、聚乙烯吡啶、支链含氮杂环类的咪唑交联的氯甲基化聚砜、支链含氮杂环类的4,4’-联吡啶交联的氯甲基化聚砜中的一种或二种以上。
  3. 根据权利要求1所述的碱性锌铁液流电池，其特征在于：负极电解液中活性物质的浓度为正极电解液中活性物质浓度的1/2～其在所对应的强碱溶液中的饱和浓度。
  4. 根据权利要求1所述的负的半电池，其特征在于：锌的氧化物为氧化锌，锌盐为氯化锌、硫酸锌中的一种或两种，强碱为氢氧化钠、氢氧化钾或氢氧化锂中的一种或两种以上。
  5. 根据权利要求1或3所述的碱性锌铁液流电池，其特征在于：正和/或负极电解液中还可加入氯化钾、硫酸钠、氯化钠、硫酸钾的可溶性盐中的一种或两种以上作为辅助电解质，以提高支持电解质的电导率；所述的辅助电解质的浓度为0.1～6mol/L，优选2～4mol/L。
  6. 根据权利要求1所述的碱性锌铁液流电池，其特征在于：所述的正、负极集流板分别为石墨板或铜板。
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