CN100459269C - Iron composite/halogen electrochemical system for flow electric storage - Google Patents
Iron composite/halogen electrochemical system for flow electric storage Download PDFInfo
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Abstract
A Fe-matched matter-halogen electrochemical system used on liquid flow energy storage is prepared as separating positive/negative electrode electrolyte by positive ion exchange film and storing said electrolyte in external container, generating charge/discharge process by making oxidation/reduction reaction on inert carbon felt electrode through pump stream via battery, applying soluble Fe(III)/Fe(II) -matched matter oxidation/reduction electric pair as negative electrode and applying halogen oxidation/reduction electric pair as positive electrode.
Description
Technical field
The present invention relates to the liquid flow energy storage battery in the electrochemical energy storage field, specifically be used for the iron-halogen model electrochemical system of liquid stream electric power storage; Mainly be applicable to large-scale electric energy storage, peak load regulation network and stand-by power supply etc.
Background technology
Be accompanied by the day by day in short supply of traditional fossil energy supply, Ecological environment worsening, research and utilize regenerative resource to become the Critical policies of Chinese energy safety and sustainable development on a large scale.Regenerative resource is subjected to as wind energy, solar energy and wave-energy power generation that the variable effect with weather is bigger round the clock, presses for scale energy storage technology that exploitation matches with it and guarantees the continuity and the stationarity of generating electricity, powering.In addition, develop extensive energy storage, also can be used for accent " peak ", large electricity consumer's electric power storage, the military electric power storage of electrical network, reach the generating capacity that makes full use of all kinds of power stations, the purpose that increases electric power supply.The flow battery that grows up by fuel cell (claim again liquid stream redox cell) in recent years, it is long to have a charge and discharge circulation life, the reliability height, airtight nothing discharging, environmental friendliness is not subjected to the restriction in geographical position, advantages such as the construction period is short, and operation and fees of maintenance are lower.In all kinds of storage batterys, liquid flow energy storage battery becomes one of storage battery of the extensive energy storage of optimum with its many exclusive characteristic and high property/price ratio.
Traditional secondary energy storage cell active materials and electrode material are one, discharge and recharge often that solid phase with complexity changes and pattern changes, and easily leak electricity, and depth of discharge are limited.And liquid flow energy storage battery, original text is Flow Redox Cell or Redox flow cell energy storage systems, is Thaller in 1974, L.H. (NASA Lewis Research Center, Cleveland, United States) a kind of electrochemical energy storage device that proposes.Its active material just is being dissolved in/electrolyte of negative pole fluid reservoir in, each makes flow of solution through battery by a pump, on the porous electrode of high selectivity amberplex both sides oxidation/reduction reaction takes place, and returns fluid reservoir then.Realized the storage of active material and separating of electrode reaction place thus, but made the power and the capacity independent design of battery; Do not have electric leakage, but deep discharge is suitable for long-term storage; The electrolyte that contains active material simultaneously is flow regime, has reduced the mass transfer polarization of electrochemical reaction, the efficient height; It is a kind of effectively extensive energy storage device.And to the electrochemical system of forming the basis of flow battery energy storage by the electricity of different valence state.Used electrochemical system requires the electric right invertibity of oxidation/reduction good, just/and the right potential difference of negative electricity is big, and is fast in the electrode surface charge transfer, be not subjected to liberation of hydrogen, analyse the oxygen side reaction and influence, solvable in supporting electrolyte, and concentration is high as much as possible and stable, low price.In 1973, NASA (NASA) set up the Lewis research center, and possible oxidation/reduction electricity to having carried out a large amount of explorations and selection, has finally been determined the Fe/Cr system." iron-chromium system " becomes the early stage research of liquid flow energy storage battery electrochemical system the most widely.In when charging, the right active material of high potential electricity at positive pole by Fe
+ 2Be oxidized to Fe
+ 3On the negative pole of amberplex opposite side, the right active material of electronegative potential electricity is by Cr
+ 3Be reduced into Cr
+ 2During discharge, above-mentioned two processes are reversed.U.S. NASA developed the 1kW Fe/Cr pile that is used for solar photovoltaic generation system through long-term effort in 1981.After the American, the Japanese develops the Fe/Cr pile of 10KW, and energy efficiency reaches 80%.But the Fe/Cr system exists the two big shortcomings that self are difficult to overcome: Cr in (1) negative pole electrolyte
+ 3/ Cr
+ 2Kinetics slow excessively; The preparation of its eelctro-catalyst is difficulty comparatively, and eelctro-catalyst easily poisons by the impurity in the electrolyte, causes the energy loss of electrode reaction overpotential to produce a large amount of liberation of hydrogen side reactions greatly and easily.(2) along with the prolongation of circulation timei, the cross pollution of electrolyte takes place in the cation permeation amberplex, needs independent rebalance cell.Therefore, fail to realize commercialization for a long time.
After, multinational scholar is right by two OR electricity of conversion, has proposed many other different flow battery system (Fe
3+/ Fe
2+-Ti
4+/ Ti
3+, VO
2 +/ VO
2+-Sn
2+/ Sn
4+, VO
2 +/ VO
2+-Cu/Cu
2+, Zn-Cl, Zn-Br, Zn-Cl, the Zn/ iron cyanide etc.).The research of recently relevant new system is still continuous, as cerium vanadium system, full chromium system, vanadium-bromine system, full uranium system flow battery etc.But what be expected to realize extensive electric power storage only has sodium polysulfide/bromine (PSB) system and full vanadium (VRB) system.Countries such as Britain, Japan, Australia and the U.S. have built many MW level demonstration demo systems.Yet, just/cross-contamination issue between the negative solution is still the biggest obstacle that flow battery is able to extensive use, even active material is the full vanadium cell with element of appraising at the current rate, also just existing to a certain extent/the interpenetrating of negative electrode active ion, when particularly adopting cation-exchange membrane by for serious.In addition, the anodal sodium bromide solution corrosivity of PSB system is strong, easily produces the S precipitation in the negative pole sodium polysulfide solution; VRB system highly concentrated solution (＞2mol/L) instability.
Summary of the invention
The purpose of this invention is to provide a kind of iron-halogen model electrochemical system that is used for liquid flow energy storage battery.Ion coordination chemistry and the complex ion electrochemistry of will appraising at the current rate combines, and the oxidation/reduction electricity that obtains new suitable liquid flow energy storage battery is right, forms efficient, a stable model electrochemical system.Pass through ligand complex, adjusted the electrode potential of (significantly reducing) original electricity to Fe (III)/Fe (II), make it be applicable to the negative pole of liquid flow energy storage battery, form efficient, stable model electrochemical system with the halogen of high potential, and reduced the cross pollution of positive and negative electrode solution, improve the open circuit voltage of battery, reach the effect that reduces cost, improves stability and energy density and gain, have a good application prospect.
For achieving the above object, the technical solution used in the present invention is:
Iron-halogen model electrochemical the system that is used for liquid flow energy storage battery, just/(this film only allows H to negative pole electrolyte by the cation-exchange membrane of the high stability of a kind of similar Nafion, CMV
+, Na
+Or K
+Pass through Deng cation, with the conducting electric current, form current circuit, and the infiltration of obstruct halogen and iron-complex active ion) separate, and be stored in the container of peripheral hardware, by the pump battery of flowing through, need not on the inertia porous carbon felt electrode of supported catalyst oxidation, reduction reaction to take place, carry out the charge/discharge process, be not subjected to liberation of hydrogen/analyse the oxygen side reaction to influence, negative pole adopts solubility Fe (III)/Fe (II)-complex oxidation/reduction electricity right, and the anodal halogen oxidation/reduction electricity that adopts is to (as: iodide-many iodide, chloride-chlorine or bromine thing-bromine).
Fe (III)/Fe (II)-complex electricity as active material in the negative pole electrolyte is right, and its standard oxidationreduction potential should be preferably lower than 0 volt of person near standard hydrogen current potential (0 volt), and will guarantee not have negative pole side reaction such as liberation of hydrogen influence; Fe (III)/Fe (II)-complex electricity as active material in the negative pole electrolyte is right, the stability constant of the complex that part and Fe (III) form is higher than the stability constant of the complex that forms with Fe (II), and both difference should be big as far as possible, and the part that satisfies this requirement comprises NH
3, CN
-Deng multidentate ligands such as monodentate ligand and ethylenediamine, citric acid, triethanolamine, EDTA, DTPA, oxalic acid; Active material Fe (III) in the negative pole electrolyte/Fe (II)-complex concentration range is 0.1-1M (concentration of promptly preparing negative pole Fe that electrolyte adopts (III) is 0.1-1M); Anodal electrolyte adopts the aqueous solution of the halide of high concentration such as NaBr, NaI or polyhalide (be dissolved in inhomogeneity halide form by halogen simple substance) itself, and concentration is between 1-3M;
In negative pole electrolyte, can add soluble-salt compounds such as NaAC with supporting electrolyte and buffering solution double action, KCl, NaCl etc. reduce the solution resistance of system, and make it the required pH value of maintenance system (becoming) according to used part difference, improve the stability of complex; Significantly reduce the cross pollution of positive and negative electrode solution thus, obtain to be used for the low cost of liquid energy-storage, efficient, high voltage, high-energy-density and stable electrochemical system.Fe (III)/Fe (II)-complex solvent for use is a water, and can add the salt compounds as supporting electrolyte or cushioning liquid, as K
2SO
4, Na
2SO
4, NaCl, KCl and/or sodium acetate etc., concentration is between 0.4-3M; Its concentration range in the aqueous solution of above-mentioned soluble-salt compounds that also can go into to have the effect of inertia supporting electrolyte in anodal electrolyte is 0.5-2M.
During charging, the halogen solution middle or low price attitude halide ion that the electric energy of input will be flowed through anodal is oxidized to high valence state halogen, and Fe (III) complex ion is reduced to Fe (II) complex ion in Fe (the III)-complex aqueous solution of the negative pole of flowing through simultaneously; During discharge, above-mentioned course of reaction is reverse carries out.Just/and negative pole electrolyte separated by cation-exchange membrane, and this film only allows H
+, Na
+Or K
+Pass through Deng cation, form current circuit, and intercept the infiltration of halogen and iron-complex active ion.Thereby realized the circulation of charge and discharge, just reduced/cross pollution of negative solution that its stability is improved, and reaches useful life that prolongs battery and the purpose that reduces cost.
It is barrier film that iron of the present invention-halogen liquid flow energy storage battery adopts cation-exchange membrane, two kinds of electrolyte are stored in respectively in the storage tank of peripheral hardware, and the capacity of battery is changeable, and the energy conversion efficiency height, long service life, and can operate at normal temperatures, no self discharge, preparation cost is low, environmental friendliness, can combine with regenerative resources such as solar energy, wind energies, build up the scale energy-accumulating power station of MW level, generate electricity by way of merging two or more grid systems when to be needed.
" iron-halogen system that is used for the electric power storage of liquid stream " of the present invention, electricity is to the identical (document: Remick R J with above-mentioned sodium polysulfide/bromine system flow battery of electrochemical reaction of ion in the anodal electrolyte, Ang P G P.Electrically rechargeable anionically active reduction-oxidationelectrical storage-supply system.US:4485154,1984.), negative pole electrolyte has then adopted Fe (III)/Fe (II) electricity of coordination to ion.Fe (III)/Fe (II) electricity to since with the complexing of suitable part, electrode potential greatly reduces, and makes it to satisfy as the right current potential requirement of liquid flow energy storage battery negative electricity; Because coordination is anhydrated and turned usefulness into, electricity might be accelerated the kinetics of ion; In alkaline solution, Fe (III)/Fe (II) electricity is to after the complexing, and current potential might decline to a great extent and not be subjected to the influence of liberation of hydrogen side reaction, can improve cell voltage; What is more important because the coordination ion radius greatly and comparatively stable, is difficult for just seeing through/amberplex between negative pole, just reducing/cross-contamination issue of negative solution, just improving/stability of negative pole redox solution.In addition, iron and bromine two elements are abundant in occurring in nature source, very cheap, form the model electrochemical system that liquid flow energy storage battery is used, for the reduction of cost provides bigger space.
Description of drawings
Fig. 1 is for adopting the liquid flow energy storage battery assembling schematic diagram of iron-halogen system; Wherein: 1 is negative pole electrolyte, and 2 is anodal electrolyte, and 3 is inert electrode, and 4 is selective ion exchange membrane, and 5 is battery, and 6 is pump;
Fig. 2 is the constant current charge curve of embodiment 1;
Fig. 3 is the constant current charge/discharge curve of embodiment 2;
Fig. 4 is the constant current charge curve of embodiment 3.
Embodiment
Flow out battery after being delivered to the electrolyte generation electrochemical reaction of iron-halogen energy-storage battery electrode surface, electrode only provides the place of reaction and does not participate in chemical reaction.Following positive pole is the charge and discharge process of example explanation battery with NaBr.When discharge, iron-complex/sodium bromide energy-storage battery anode electrode reaction is:
Fe(II)-L→Fe(III)-L+e
-
Wherein L represents part
Na
+Arrive negative electrode, Br by cation-exchange membrane
2Cathode reaction takes place, with Na
+Form NaBr:
Br
2+2Na
++2e
-→2NaBr
Under standard state, the open circuit voltage of battery is about 1.0～2.0V; When charging, electrode reaction is reverse carries out.
For embodiment in detail the present invention is described in detail below:
Take by weighing an amount of Fe
2(SO
4)
3And part-EDTA, both mol ratios are the 0.5 (Fe of 0.5mol
2(SO
4)
3Be equivalent to contain 1molFe
3+Ion), be dissolved in the aqueous sodium acetate solution of 1M, after the room temperature lower magnetic force stirring and dissolving, be made into Fe (III)-EDTA complex aqueous solution of 0.1M, the pH value of solution remains on about 5.5.It is soluble in water to take by weighing an amount of NaBr, after the room temperature lower magnetic force stirring and dissolving, is made into the NaBr aqueous solution of 1M.
Select for use Nafion117 film (U.S. DuPont company) as just separating/cation-exchange membrane of negative pole electrolyte, film need carry out following processing before use: heat treated 2h in the water-bath of 353K in the NaOH of the 1.0mol/L aqueous solution, then, use deionized water wash, then the film of Hydrogen is converted into Na type film, can be used for battery.
With prepared just/negative pole electrolyte places the peripheral hardware liquid storage bottle of battery both sides, is assembled into battery and sees accompanying drawing 1.The charge-discharge performance of test battery on the monocell evaluating apparatus of being adorned.The operating condition of battery is as follows: battery temperature is room temperature (～20 ℃), and anodal electrolyte is the NaBr solution 50mL of 1mol/L; Negative pole electrolyte is Fe (the III)-EDTA of 0.1mol/L and the sodium acetate mixed solution of 1mol/L; Positive and negative electrode electrolyte flows into battery through magnetic drive pump, on the porous carbon felt electrode of amberplex both sides oxidation/reduction reaction takes place, and flows back to after the reaction in the liquid storage bottle separately.The circular flow of positive and negative electrode electrolyte all remains 30mL/min.Before the charge and discharge, feed behind the nitrogen 30min more in addition airtightly in the negative pole liquid storage bottle, and guarantee that the charge/discharge process carries out in airtight system.Mode test battery performance with constant current.
Adopting 0.1M Fe (III)/Fe (II)-EDTA is the negative pole oxidation-reduction pair, and the charge and discharge cycle curve of its battery is seen accompanying drawing 2, and the charge/discharge current density is about 10mA/cm
2As can be seen, iron-complex/Br
2Liquid flow energy storage battery charge and discharge cycles operation 5 times, the charging interval is 3.96h, be 3.59h discharge time, coulombic efficiency remains on more than 90%, IR ohmmic drop during battery discharge is less, illustrates that battery positive and negative electrode electrolyte electrochemical reaction polarization is little, and internal resistance is lower, even under the lower condition of concentration of electrolyte, battery still has higher voltage efficient (～87%), makes its energy efficiency reach nearly 80%, and the about 1.03V of the open circuit voltage of battery, performance is comparatively stable, does not have obviously decay.
Negative pole electrolyte prepares raw materials used Fe
2(SO
4)
3With embodiment 1: take by weighing an amount of Fe
2(SO
4)
3And part-natrium citricum, both mol ratios are 0.5, are dissolved in the aqueous sodium acetate solution of 1M, after the room temperature lower magnetic force stirring and dissolving, are made into Fe (III)-citric acid compound aqueous solution of 0.7M, the pH value of solution remains between the 5-6.Preserve the negative pole electrolyte of preparation standby.
The preparation of anodal electrolyte is with embodiment 1: it is soluble in water to take by weighing an amount of NaBr, after the room temperature lower magnetic force stirring and dissolving, is made into the NaBr aqueous solution of 2M.
With preparation just/negative pole electrolyte 50mL places the peripheral hardware liquid storage bottle of battery both sides respectively, is assembled into battery and sees accompanying drawing 1.The operating condition of battery is with embodiment 1, the concentration of negative electrode active material Fe (III)-citric acid reaches 0.7mol/L, when forming negative pole electrolyte with supporting electrolyte 1mol/L sodium acetate, the charge and discharge curve of battery is seen accompanying drawing 3, and the charge/discharge current density is about 10mA/cm
2Iron-citric acid compound/Br
2Liquid flow energy storage battery, the charging interval is 13.9h, and be 12.1h discharge time, and coulombic efficiency is 87.7%, and voltage efficiency reaches 83.8%, and the energy efficiency of battery is higher to be 73.5%; Compare with embodiment 1, complex solution concentration increases, the time that discharges and recharges is long, the discharge capacity height, and the IR ohmmic drop during battery discharge is slightly high, the electrochemical reaction polarization that battery is described is big slightly, but the working concentration height of battery electrolyte, open circuit voltage surpasses 1.2V, is beneficial to the energy density that improves battery, battery performance is also comparatively stable, does not have obviously decay.
Negative pole electrolyte prepares raw materials used Fe
2(SO
4)
3With embodiment 1, take by weighing appropriate amount of ligands-triethanolamine (TEA) and Fe
2(SO
4)
3, both mol ratios are 3, after the mixing, add appropriate amount of NaOH, and the pH value of regulator solution is about 13, and the room temperature lower magnetic force stirs, and is dissolved in the sodium chloride supporting electrolyte aqueous solution of 0.4M, is made into Fe (III)-TEA complex aqueous solution of 0.4M.Preserve the negative pole electrolyte of preparation standby.
The preparation of anodal electrolyte is with embodiment 1: it is soluble in water to take by weighing an amount of NaBr, after the room temperature lower magnetic force stirring and dissolving, is made into the NaBr aqueous solution of 2M.
With preparation just/negative pole electrolyte 50mL places the peripheral hardware liquid storage bottle of battery both sides respectively, is assembled into battery and sees accompanying drawing 1.The operating condition of battery is with embodiment 1, and when negative pole was the NaCl mixed solution of Fe (the III)-TEA of 0.4mol/L and 0.4mol/L, the charge and discharge cycle curve of battery was seen accompanying drawing 4, and the charge/discharge current density is about 20mA/cm
2Iron-TEA complex/NaBr liquid flow energy storage battery charge is moved 5 times, and the charging interval is 4.3h, and be 3.7h discharge time, and coulombic efficiency is more than 80%; IR ohmmic drop during battery discharge is less, discharge capacity is higher, illustrate that battery positive and negative electrode electrolyte electrochemical reaction polarization is less, internal resistance is lower, the voltage efficiency of battery can reach about 85%, its energy efficiency is about 70%, particularly because Fe (III)/Fe (II) electricity under alkali condition with the triethanolamine coordination after, oxidation/reduction potential significantly reduces, after forming full battery with NaBr, battery charging/discharging voltage increases, and the open circuit voltage of battery reaches nearly 2.0V, and battery performance is comparatively stable, does not have obviously decay.
Negative pole electrolyte prepares raw materials used Fe
2(SO
4)
3With embodiment 1, take by weighing part NaCN and an amount of Fe
2(SO
4)
3, both mol ratios are greater than 3, and after the mixing, the room temperature lower magnetic force stirs, and is dissolved in the sodium chloride supporting electrolyte aqueous solution of 0.5M, is made into Fe (III)-CN complex aqueous solution of 1M.Preserve the negative pole electrolyte of preparation standby.
The preparation of anodal electrolyte is with embodiment 1: it is soluble in water to take by weighing an amount of NaBr, after the room temperature lower magnetic force stirring and dissolving, is made into the NaBr aqueous solution of 2M.With preparation just/negative pole electrolyte 50mL places the peripheral hardware liquid storage bottle of battery both sides respectively, is assembled into battery and sees accompanying drawing 1.The operating condition of battery is with embodiment 1.
Negative pole electrolyte prepares raw materials used Fe
2(SO
4)
3With embodiment 1: take by weighing an amount of Fe
2(SO
4)
3And part-natrium citricum, both mol ratios are 1.0, are dissolved in the aqueous sodium acetate solution of 1M, after the room temperature lower magnetic force stirring and dissolving, are made into Fe (III)-citric acid compound aqueous solution of 0.6M, the pH value of solution remains between the 5-6.Preserve the negative pole electrolyte of preparation standby.
The preparation of anodal electrolyte is with embodiment 1: it is soluble in water to take by weighing an amount of NaBr and HCl, after the room temperature lower magnetic force stirring and dissolving, is made into the NaBr aqueous solution that is dissolved in 2M among the 1MHCl, then after the charging reaction, can form ClBr
2 -With BrCl
2 -Many halogen ion.
With preparation just/negative pole electrolyte 50mL places the peripheral hardware liquid storage bottle of battery both sides respectively, is assembled into battery and sees accompanying drawing 1.The operating condition of battery is with embodiment 1.
Embodiment 6
Negative pole electrolyte prepares raw materials used Fe
2(SO4)
3With embodiment 1: take by weighing an amount of Fe
2(SO4)
3And part-natrium citricum, both mol ratios are 1.5, are dissolved in the aqueous sodium acetate solution of 1M, after the room temperature lower magnetic force stirring and dissolving, are made into Fe (III)-citric acid compound aqueous solution of 0.5M, the pH value of solution remains on about 5.6.Preserve the negative pole electrolyte of preparation standby.
The preparation of anodal electrolyte is with embodiment 1: it is soluble in water to take by weighing an amount of NaBr and HCl, after the room temperature lower magnetic force stirring and dissolving, is made into the NaBr aqueous solution that is dissolved in 1.5M among the 1MHCl, then after the charging reaction, can form ClBr
2 -With BrCl
2 -Many halogen ion.
With preparation just/negative pole electrolyte 50mL places the peripheral hardware liquid storage bottle of battery both sides respectively, is assembled into battery and sees accompanying drawing 1.The operating condition of battery is with embodiment 1.
Embodiment 7
Negative pole electrolyte prepares raw materials used Fe
2(SO4)
3With embodiment 1: take by weighing an amount of Fe
2(SO4)
3And part-natrium citricum, both mol ratios are 0.5, are dissolved in the aqueous sodium acetate solution of 1M, after the room temperature lower magnetic force stirring and dissolving, are made into Fe (III)-citric acid compound aqueous solution of 0.8M, the pH value of solution remains between the 5-6.Preserve the negative pole electrolyte of preparation standby.
The preparation of anodal electrolyte is with embodiment 1: it is soluble in water to take by weighing an amount of NaBr, and adds the Na of 0.5M
2SO
4Supporting electrolyte after the room temperature lower magnetic force stirring and dissolving, is made into the Na of 2MNaBr
2SO
4The aqueous solution.With preparation just/negative pole electrolyte 50mL places the peripheral hardware liquid storage bottle of battery both sides respectively, is assembled into battery and sees accompanying drawing 1.The operating condition of battery is with embodiment 1.
Claims (7)
1, the iron-halogen electrochemical system that is used for liquid flow energy storage battery, just/negative pole electrolyte separated by cation-exchange membrane, and be stored in the container of peripheral hardware, by the pump battery of flowing through, oxidation, reduction reaction take place on the inertia carbon felt electrode, carry out the charge/discharge process, it is characterized in that: negative pole adopts solubility Fe (III)/Fe (II)-complex oxidation/reduction electricity right, and the anodal halogen oxidation/reduction electricity that adopts is right; Described halogen oxidation/reduction electricity is right to being iodide-many iodide, chloride-chlorine or bromine thing-bromine oxidation/reduction electricity.
2, according to the described iron-halogen electrochemical system that is used for liquid flow energy storage battery of claim 1, it is characterized in that: solubility Fe (III)/Fe (II)-complex oxidation/right part of reduction electricity is monodentate ligand NH
3Or CN
-, perhaps be multidentate ligand ethylenediamine, citric acid, EDTA, DTPA, oxalic acid or triethanolamine.
3, according to the described iron-halogen electrochemical system that is used for liquid flow energy storage battery of claim 2, it is characterized in that: the solubility Fe of active material (III) in the negative pole electrolyte/Fe (II)-complex oxidation/reduction electricity is right, and the concentration of complex in the aqueous solution is 0.1-1M.
4, according to the described iron-halogen electrochemical system that is used for liquid flow energy storage battery of claim 1, it is characterized in that: add the soluble-salt compounds with supporting electrolyte and buffering solution double action in negative pole electrolyte, its concentration in the aqueous solution is 0.4-3M.
5, according to the described iron-halogen electrochemical system that is used for liquid flow energy storage battery of claim 1, it is characterized in that: anodal electrolyte is the halid aqueous solution of high concentration, and its concentration in the aqueous solution is 1-3M.
6, according to the described iron-halogen electrochemical system that is used for liquid flow energy storage battery of claim 1, it is characterized in that: add the soluble-salt compounds with supporting electrolyte and buffering solution double action in anodal electrolyte, its concentration range in the aqueous solution is 0.5-2M.
7. according to claim 4 or the 6 described iron-halogen electrochemical systems that are used for liquid flow energy storage battery, it is characterized in that: described soluble-salt compounds is K
2SO
4, Na
2SO
4, NaCl, KCl and/or sodium acetate.
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| CN111983482B (en) * | 2019-05-24 | 2021-05-28 | 江苏泛宇能源有限公司 | Detection method of environment-friendly all-vanadium redox flow battery |
| CN113363630A (en) * | 2020-03-03 | 2021-09-07 | 天津理工大学 | Photoelectrochemical energy storage battery |
| CN113451629B (en) * | 2021-07-14 | 2023-04-25 | 大连海事大学 | Low-cost ferrotitanium flow battery |
| CN117558957B (en) * | 2024-01-11 | 2024-03-15 | 西南石油大学 | Flow battery system for magnetically managing paramagnetic reaction ions and performance improvement method |
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| CN1087209A (en) * | 1992-09-01 | 1994-05-25 | 埃林能源应用有限公司 | Zinc-Zn-Br battery |
| US6475661B1 (en) * | 1998-01-28 | 2002-11-05 | Squirrel Holdings Ltd | Redox flow battery system and cell stack |
| US20040202915A1 (en) * | 2001-06-12 | 2004-10-14 | Hiroyuki Nakaishi | Cell frame for redox-flow cell and redox-flow cell |
| US20050158615A1 (en) * | 2002-02-14 | 2005-07-21 | Samuel John M.G. | Redox flow battery |
| CN1598063A (en) * | 2003-09-18 | 2005-03-23 | 攀枝花钢铁有限责任公司钢铁研究院 | Process for electrolyzing preparing electrolyte of full vanadium ion flow battery |
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