CN104335405B - Energy storage battery - Google Patents
Energy storage battery Download PDFInfo
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- CN104335405B CN104335405B CN201280073632.XA CN201280073632A CN104335405B CN 104335405 B CN104335405 B CN 104335405B CN 201280073632 A CN201280073632 A CN 201280073632A CN 104335405 B CN104335405 B CN 104335405B
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- electrolyte
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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
- H01M8/18—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- General Chemical & Material Sciences (AREA)
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Abstract
This energy storage battery is provided with a negative electrode electrolyte solution that contains a copper redox system material and a polyethylene imine. It is preferable that the molar ratio of the polyethylene imine to the copper redox system material in the negative electrode electrolyte solution is within the range from 1 to 5 (inclusive) if the molar concentration of CH2CH2NH structures, which is the basic unit of the polyethylene imine, is considered as the molar concentration of the polyethylene imine.
Description
Technical field
The present invention is for example related to a kind of batteries such as oxidation, reduction liquid (redox flow) type battery.
Background technology
In the past, as electrolyte used in battery it is known that the structure containing metal oxidation reduction system material and chelating agent
Become (with reference to patent document 1, patent document 2, non-patent literature 1).In patent document 1, as electrolyte liquid, disclose containing
The concrete example of iron redox system material and edathamil and concrete containing iron redox system material and citric acid
Example.In addition, in patent document 2, as electrolyte liquid, disclose concrete containing titanium redox system material and citric acid
Example, the concrete example containing titanium redox system material and edathamil, contain chromium redox system material and ethene two
The concrete example of amine tetraacethyl and the concrete example containing chromium redox system material and phosphoric acid.In non-patent literature 1, as negative pole
Electrolyte, discloses the concrete example containing iron redox system material and edathamil, contains iron redox system thing
Matter and the concrete example of citric acid and the concrete example containing iron redox system material and oxalic acid.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open No. Sho 56-42970 publication
Patent document 2：Japanese Patent Laid-Open No. Sho 57-9072 publication
Non-patent literature
Non-patent literature 1：Y.H.Wen et al.：《Iron (Fe in sodium acetate solution3+/Fe2+)-complexing/bromine (Br2/Br-) oxygen
Change research (the Studies on Iron (Fe of reduction flow battery3+/Fe2+)-Complex/Bromine(Br2/Br-)Redox
Flow Cell in Sodium Acetate Solution)》, (ECS's will (Journal of The
Electrochemical Society)), 153 (5) A929-A934 (2006)
Content of the invention
[inventing the problem to be solved]
Generally, using highly acid electrolyte in battery.In highly acid electrolyte, although metal oxidation reduction ion
Concentration is of a relatively high but also stably dissolves, and therefore can improve the energy density of battery.In addition, in highly acid electrolyte,
The carrier of ionic conduction becomes H+Ion or OH-Ion.H+The mobility of ion and OH-The mobility of ion is all of a relatively high, because
The conductance of this electrolyte improves.Thus, the resistance of battery diminishes, and the efficiency of result battery improves.Like this using strong acid
Property electrolyte in the case of, the chemical-resistant of electrolyte be can tolerate to the material requirements constituting redox flow batteries.
In contrast, resistance toization of the material constituting battery in the case of using pH value being more than 2, less than 8 electrolyte, can be reduced
Learn moral character, result can reduce the manufacturing cost of battery.But in the case of being somebody's turn to do, the carrier not H of ionic conduction+Ion and OH-
Any one of ion, and become such as Na+Ion, K+Ion, C1-Ion, SO4 2-Ion etc..The mobility of this ion is less than H+Ion and OH-The conductance step-down of ion, therefore electrolyte.Thus, the resistance of battery becomes big, and the efficiency of result battery reduces.
In addition, in the electrolyte of described pH value, metal oxidation reduction ion is difficult to stably dissolve.Accordingly, it is difficult to make metal aoxidize also
Former ion dissolves in the electrolytic solution with high concentration, and the energy density of result battery reduces.
It can be said that resistance becomes big shortcoming or the dissolubility of metal oxidation reduction ion reduces in the electrolyte of described pH value
Shortcoming metal oxidation reduction ion can be made complex compound and make up by making electrolyte contain chelating agent.But, close
In the battery using chelating agent, actual conditions are to there is no practical report.
With regard to this respect, if for example the table 2 with reference to non-patent literature 1 to contrast the solubility of iron ion, Fe2(SO4)3
In the case of be 1.6mol/L, in contrast, being limited to 0.2mol/L, iron-lemon in the case of iron-edathamil complex compound
It is limited to 0.8mol/L in the case of lemon acid complex, in the case of iron-oxalate complex, be limited to 0.1mol/L.That is, iron ion
Solubility because formed complex compound and become less than half, therefore iron redox system possibly cannot obtain practicality energy close
Degree.
In addition, the redox system of copper is to represent in Fig. 4 of patent document 1.Fig. 4 of patent document 1 is hydrochloric acid solution
In redox system comparison diagram.On the other hand, Fig. 3 of patent document 1 is the comparison of the redox system in sulfuric acid solution
Figure.In this Fig. 3, there is not the curve (plot) of copper ion.Enlighten in this patent document 1：The redox of copper ties up to sulphur
Do not work well in acid solution, and work well in hydrochloric acid solution.Additionally, the redox system in hydrochloric acid solution
In, chlorine may be produced in positive pole.From this respect, in electrolyte liquid using copper redox system material situation
Under, if using the redox system material that electromotive force is high in anode electrolyte, easily producing chlorine.Therefore, using copper
It is difficult to obtain the high battery of electromotive force in the case of redox system.Like this, actual conditions are to exist by the oxidation of copper also
Former system material is used for the technical problem of battery.
The present invention is in view of this actual conditions form, and its object is to provide a kind of battery, even if described battery
Using pH value be more than 2, less than 8 scope in electrolyte in the case of, it is possible to use the redox system material of copper,
And it is easy to ensure that the energy density of the efficiency of battery and battery.
[means to solve the problem]
In order to reach described purpose, in one embodiment of the present invention, provide a kind of battery, described battery possesses
Redox system material containing copper and the electrolyte liquid of polyethyleneimine.
In described battery, with regard to the described polyethyleneimine in described electrolyte liquid with respect to copper redox
It is the mol ratio of material, the molar concentration of polyethyleneimine is being set as the elementary cell as this polyethyleneimine
CH2CH2In the case of the molar concentration of NH structure, preferably it is set as in more than 1, less than 5 scope.
In described battery, described electrolyte liquid is prepared preferably by the following manner：In described polyethyleneimine
In the presence of, will be anti-as 1 circulation using the electroreduction reaction of the redox system material of described copper and electrolytic oxidation reaction
More than 10 circulations should be carried out.
In described battery, so that copper sulphate is dissolved in the water, thus make to contain in described electrolyte liquid
State the redox system material of copper.
In described battery, the content of the redox system material of described copper in preferably described electrolyte liquid is
In more than 0.2mol/L, the scope of below 1.0mol/L.
In described battery, the pH value of preferably described electrolyte liquid is more than 2, in less than 8 scope.
Brief description
Fig. 1 is the skeleton diagram of the redox flow flow pattern battery of embodiment representing the present invention.
Fig. 2 is the result of the 1st of the embodiment 1 charge and discharge electric test being recycled to the 30th circulation, for representing time and voltage
The chart of relation.
Fig. 3 is the result of the 31st of the embodiment 1 charge and discharge electric test being recycled to the 50th circulation, for representing time and voltage
The chart of relation.
Fig. 4 is the chart of the result that the CV at 20 DEG C of expression embodiment 2 measures.
Fig. 5 is the chart of the result that the CV at 60 DEG C of expression embodiment 2 measures.
Fig. 6 is the chart of the result that the CV at 20 DEG C of expression embodiment 3 measures.
Fig. 7 is the chart of the result that the CV at 60 DEG C of expression embodiment 3 measures.
Fig. 8 is the chart of the result that the CV at 20 DEG C of expression embodiment 4 measures.
Fig. 9 is the chart of the result that the CV at 60 DEG C of expression embodiment 4 measures.
Figure 10 is the chart of the result that the CV at 20 DEG C of expression embodiment 5 measures.
Figure 11 is the chart of the result that the CV at 60 DEG C of expression embodiment 5 measures.
Reference：
10：Charge and discharge device
11：Charge/discharge unit
12：Barrier film
13：Inert gas supply pipe
14：Blast pipe
15：Water seal portion
21：Positive pole side unit
21a：Positive pole
21b：Side of the positive electrode collector plate
22：Anode electrolyte
23：Anode electrolyte storage tank
24、34：Supply pipe
25、35：Recovery tube
26、36：Pump
31：Negative pole side unit
31a：Negative pole
31b：Negative side collector plate
32：Electrolyte liquid
33：Electrolyte liquid storage tank
Specific embodiment
Hereinafter, the redox flow flow pattern battery of the battery of the embodiment as the present invention is illustrated.
Structure ＞ of ＜ redox flow flow pattern battery
As shown in FIG. 1, redox flow flow pattern battery possesses charge/discharge unit 11.The inside of charge/discharge unit 11 is
It is divided into positive pole side unit 21 and negative pole side unit 31 by barrier film 12.Redox flow flow pattern battery possesses storage positive pole
Negative pole used in the anode electrolyte storage tank 23 of anode electrolyte 22 used in side unit 21 and storage negative pole side unit 31
The electrolyte liquid storage tank 33 of electrolyte 32.In redox flow flow pattern battery, optionally it is provided with regulation charge/discharge unit 11
The temperature-adjusting device of the temperature of periphery.
In positive pole side unit 21, it is configured with positive pole 21a and side of the positive electrode collector plate 21b with the state contacting.Negative side
In unit 31, it is configured with negative pole 31a and negative side collector plate 31b with the state contacting.Positive pole 21a and negative pole 31a is for example
It is to be made up of carbon felt (felt).Side of the positive electrode collector plate 21b and negative side collector plate 31b is, for example, by glassy carbon plate institute structure
Become.Each collector plate 21b, collector plate 31b are electrically connected to charge and discharge device 10.
On positive pole side unit 21, it is connected to anode electrolyte storage tank 23 via supply pipe 24 and recovery tube 25.In supply
On pipe 24, it is equipped with pump 26.By the work of pump 26, the anode electrolyte 22 in anode electrolyte storage tank 23 is through supply pipe 24
And it is supplied to positive pole side unit 21.Now, the anode electrolyte 22 in positive pole side unit 21 is recovered through recovery tube 25
To in anode electrolyte storage tank 23.Like this, make anode electrolyte 22 in anode electrolyte storage tank 23 with positive pole side unit 21
Circulation.
On negative pole side unit 31, it is connected to electrolyte liquid storage tank 33 via supply pipe 34 and recovery tube 35.In supply
On pipe 34, it is equipped with pump 36.By the work of pump 36, the electrolyte liquid 32 in electrolyte liquid storage tank 33 is through supply pipe 34
And it is supplied to negative pole side unit 31.Now, the electrolyte liquid 32 in negative pole side unit 31 is recovered through recovery tube 35
To in electrolyte liquid storage tank 33.Like this, make electrolyte liquid 32 in electrolyte liquid storage tank 33 with negative pole side unit 31
Circulation.
On charge/discharge unit 11, anode electrolyte storage tank 23 and electrolyte liquid storage tank 33, it is connected to supply indifferent gas
The inert gas supply pipe 13 of body.Inert gas is supplied to inert gas supply pipe 13 by inert gas generation device.Through lazy
Property gas supply pipe 13 positive pole electrolyte reservoir 23 and electrolyte liquid storage tank 33 are supplied with inert gas, thus suppression positive pole electricity
Solution liquid 22 and electrolyte liquid 32 contact with the oxygen in air.Inert gas for example can use nitrogen.Supply to positive pole electricity
The inert gas of solution liquid storage tank 23 and electrolyte liquid storage tank 33 is discharged through blast pipe 14.Discharge side in blast pipe 14
Top, be provided with the water seal portion 15 of the opening of blast pipe 14 water seal in addition.Water seal portion 15 prevents air adverse current to blast pipe 14
Interior, and certain pressure will be held in anode electrolyte storage tank 23 and in electrolyte liquid storage tank 33.
During charging, in the anode electrolyte 22 contacting with positive pole 21a, carry out oxidation reaction, and contact with negative pole 31a
Carry out reduction reaction in electrolyte liquid 32.That is, positive pole 21a disengages electronics, and negative pole 31a accepts electronics.Now, side of the positive electrode
Collector plate 21b will be supplied in charge and discharge device 10 by the electronics that positive pole 21a disengages.Negative side collector plate 31b will be from charge and discharge Denso
The electronics putting 10 acceptance is supplied in negative pole 31a.Negative side collector plate 31b collects the electronics that disengaged by negative pole 31a being supplied in and fills
Electric discharge device 10.
During electric discharge, in the anode electrolyte 22 contacting with positive pole 21a, carry out reduction reaction, and contact with negative pole 31a
Carry out oxidation reaction in electrolyte liquid 32.That is, positive pole 21a accepts electronics, and negative pole 31a disengages electronics.Now, side of the positive electrode
The electronics accepting from charge and discharge device 10 is supplied in positive pole 21a by collector plate 21b.
＜ electrolyte ＞
Redox flow flow pattern battery possesses the electrolyte liquid of the redox system material containing copper and polyethyleneimine
32.It could be speculated that copper, as contained active material in electrolyte liquid 32, is reduced into Cu (I) when charging by Cu (II),
During electric discharge, Cu (II) is oxidized to by Cu (I).In making electrolyte liquid 32 during the redox materials containing copper, such as from obtaining
From the viewpoint of trying to please easily, preferably make copper sulphate (CuSO4) be dissolved in water.
From the viewpoint of improving energy density, the redox system material (copper ion) of the copper in electrolyte liquid 32
Preferred more than the 0.1mol/L of concentration, more preferably more than 0.2mol/L, and then preferred more than 0.4mol/L.From suppressing copper further
From the viewpoint of the precipitation of redox system material, the redox system material (copper ion) of the copper in electrolyte liquid 32 dense
Spend preferred below 2.5mol/L, more preferably below 1.5mol/L.
Polyethyleneimine (PEI) is one kind of chelating agent, generates complex compound with the redox system material of copper, in negative electricity
There is in solution liquid 32 effect of the precipitation of redox system material of suppression copper.Polyethyleneimine has CH2CH2NH structure conduct
Elementary cell, can be straight-chain, also can have branched structure.Have branched structure polyethyleneimine comprise one-level amine, two grades
Amine and tertiary amine.
(20 DEG C) preferably with the solubility in water of polyethyleneimine is the polyethyleneimine of more than 0.2mol/L.
The weight average molecular weight of polyethyleneimine such as preferably more than 200, less than 100000, more preferably more than 300, less than 10000.
Polyethyleneimine in electrolyte liquid 32 is with respect to the mol ratio preferably example of the redox system material of copper
As being set as more preferably being set to more than 1, less than 5 scope in more than 0.5, less than 10 scope.Wherein, polyethylene
The molar concentration of imines is set to the CH of the elementary cell as polyethyleneimine2CH2The molar concentration of NH structure.Described
It is easier to suppress the precipitation of the redox system material of copper in the case that mol ratio is more than 0.5.Described mol ratio be 10 with
In the case of lower, there is reactivity or charge/discharge cycle characteristics (invertibity) improve.
In the pH value of electrolyte liquid 32 preferably more than 2, less than 8 scope, more preferably more than 2, in less than 5 scope.
In the case that the pH value of electrolyte liquid 32 is more than 2, it is easy to ensure that corrosion resistance.Electrolyte liquid 32 pH value be 8 with
In the case of lower, easily suppress the precipitation of the redox materials of copper further.
In electrolyte liquid 32, optionally can also contain the salt of such as inorganic acid or the salt of organic acid, polyethyleneimine
Chelating agent in addition.
From the viewpoint of improving charge/discharge capacity and coulombic efficiency, electrolyte liquid 32 is preferably by the following manner
Preparation：In the presence of polyethyleneimine, by with the electroreduction reaction of the redox system material of copper and electrolytic oxidation reaction
Reaction as 1 circulation carries out more than 10 circulations.For improving the viewpoint of manufacture efficiency, the described conduct of electrolyte liquid 32
Reaction preferably 30 circulation of 1 circulation is following.
The active material of anode electrolyte 22 is not particularly limited, for example, can enumerate：The redox system material of iron, chromium
Redox system material, the redox system material of the redox system material of manganese, the redox system material of copper and vanadium.
From the viewpoint of improving energy density, the redox system material of the metal in anode electrolyte 22 (metal from
Son) preferred more than the 0.1mol/L of concentration, more preferably more than 0.2mol/L, and then preferred more than 0.4mol/L.
From the viewpoint of the precipitation of the redox system material of suppression metal, the oxidation of the metal in anode electrolyte 22
Reduction is preferred below the 2.5mol/L of concentration, more preferably below 1.5mol/L of material (metal ion).
The active material of anode electrolyte 22 for example can be suitably using the redox system material of manganese.Make positive pole electricity
When in solution liquid 22 containing manganese, for not chloride ion-containing, such as manganese sulfate is preferably made to be dissolved in water.It could be speculated that manganese conduct
Contained active material in anode electrolyte 22, is oxidized to Mn (IV) when charging by Mn (III), in electric discharge by Mn (IV)
It is reduced into Mn (III).
In anode electrolyte 22, preferably contain chelating agent further.Chelating agent is e.g. selected from amino-carbon system chelating
In agent and polyethyleneimine.In anode electrolyte 22, the redox system material preferably containing manganese and polyethyleneimine.Close
In the explanation of polyethyleneimine, above already described, therefore omit.Polyethyleneimine in anode electrolyte 22 is with respect to the oxygen of manganese
Change the mol ratio that reduction is material to be preferably for example set as in more than 0.5, less than 10 scope, be more preferably set to
More than 1, less than 5 scope.
In anode electrolyte 22, optionally also can contain the salt of such as inorganic acid or the salt of organic acid.
Electrolyte liquid 32 and anode electrolyte 22 can be prepared using well-known method.Electrolyte liquid 32 and
In anode electrolyte 22, water used preferably has the purity equal or higher with distilled water.Redox flow flow pattern battery
Carry out discharge and recharge in the environment of preferably electrolyte liquid 32 and anode electrolyte 22 being set as inert gas.
The effect ＞ of ＜ redox flow flow pattern battery
In the electrolyte liquid 32 with polyethyleneimine for the redox system material containing copper, the redox system thing of copper
Matter forms complex compound with polyethyleneimine, thus suppresses the precipitation of copper.In addition, by using this electrolyte liquid 32, and play
Good battery performance, and suppress self discharge.
The performance of redox flow flow pattern battery for example can by charge/discharge cycle characteristics (invertibity), coulombic efficiency,
Voltage efficiency, energy efficiency, the current potential of the utilization rate of electrolyte, electromotive force and electrolyte are evaluating.Hereinafter, by redox
1 discharge and recharge of liquor stream type battery is as 1 circulation.
Charge/discharge cycle characteristics (invertibity) are by putting of circulating the coulomb amount (A) of the electric discharge of the 31st circulation and the 50th
The coulomb amount (B) of electricity is updated in following formula (1) and calculates.
Charge/discharge cycle characteristics [%]=B/A × 100 ... (1)
Charge/discharge cycle characteristics preferably more than 80%.
Coulombic efficiency is following by being updated to the coulomb amount (D) of the coulomb amount (C) of the charging of the 50th circulation and electric discharge
Calculate in formula (2).
Coulombic efficiency [%]=D/C × 100 ... (2)
Coulombic efficiency preferably more than 80%.
Voltage efficiency be by by the 2nd circulation charging average terminal voltage (E) and electric discharge average terminal voltage (F)
It is updated in following formula (3) and calculate.
Voltage efficiency [%]=F/E × 100 ... (3)
Voltage efficiency preferably more than 60%.
Energy efficiency be by by the 2nd circulation charging electric energy (electric energy) (G) and electric discharge electric energy
(H) it is updated in following formula (4) and calculate.
Energy efficiency [%]=H/G × 100 ... (4)
Energy efficiency preferably more than 60%.
The utilization rate of electrolyte is to calculate in the following manner：To the electrolyte being supplied in positive pole 21a side or negative pole 31a side
The molal quantity of active material be multiplied by faraday (Faraday) constant (96500 coulomb/mole) and obtain coulomb amount (I), and
Obtain the coulomb amount (J) of the electric discharge of the 1st circulation, coulomb is measured (I) and coulomb amount (J) is updated in following formula (5).Additionally,
It is supplied in the molal quantity of the active material of electrolyte of positive pole 21a side and the active material of the electrolyte being supplied in negative pole 31a side
Molal quantity difference in the case of, using less molal quantity.Utilization rate with regard to the 1st later electrolyte of circulation it is also possible to
Similarly calculate.
The utilization rate [%] of electrolyte=J/I × 100 ... (5)
The utilization rate of electrolyte preferably more than 55%.
The terminal voltage of (when electric current is 0mA) when electromotive force is set to switch to electric discharge by charging in the 1st circulation.Electricity
Preferred more than the 1.0V of kinetic potential.
The current potential of electrolyte is to be represented with following current potential：In anode electrolyte storage tank 23 and electrolyte liquid storage tank 33
When being previously inserted graphite electrode and silver-silver chloride (saturation KCl) electrode respectively, the graphite electrode in discharge and recharge is with respect to silver-chlorine
Change the current potential of silver electrode.
According to discussed above embodiment, play following effect.
(1) in the redox flow flow pattern battery of this embodiment, possess the redox system material containing copper and gather
The electrolyte liquid 32 of aziridine.For this electrolyte liquid 32, even if in the scope that pH value is set as more than 2, less than 8
In the case of interior, the also precipitation of the redox system material of suppression copper.It is, therefore, possible to provide a kind of battery, described battery
Even if using pH value be more than 2, less than 8 scope in electrolyte in the case of, it is possible to use the redox system of copper,
And it is easy to ensure that the energy density of the efficiency of battery and battery.
(2) with regard to the polyethyleneimine in electrolyte liquid 32 with respect to the redox system material of copper mol ratio,
The molar concentration of polyethyleneimine is set as the CH of the elementary cell as polyethyleneimine2CH2The molar concentration of NH structure
In the case of, preferably it is set as in more than 1, less than 5 scope.It is easier to suppress the redox system thing of copper in the case of being somebody's turn to do
The precipitation of matter, and have the tendency of reactivity or charge/discharge cycle characteristics (invertibity) improve.
(3) electrolyte liquid 32 is prepared preferably by the following manner：In the presence of polyethyleneimine, by with copper
The electroreduction reaction of redox system material and electrolytic oxidation reaction carry out more than 10 circulations as the reaction of 1 circulation.This feelings
Under condition, easily improve charge/discharge capacity and coulombic efficiency.In addition it could be speculated that the redox system material of copper and polyethyleneimine
The formation of complex compound is promoted because of described reaction, is accompanied by this, charge/discharge capacity and coulombic efficiency improve.
(4) make the redox system containing copper in electrolyte liquid 32 preferably by making copper sulphate be dissolved in water
Material.In the case of being somebody's turn to do, because copper sulphate easily obtains, therefore can be readily available electrolyte liquid 32.For example, with use chlorine
The situation changing copper compares, and can easily suppress to lead to being mixed into of the chlorion producing chlorine in positive pole.
(5) content of the redox system material of the copper in electrolyte liquid 32 be more than 0.2mol/L, 1.0mol/L with
Under scope in, thus easily improve energy density, and further suppression copper redox system material precipitation.
(6) pH value of electrolyte liquid 32 is more than 2, in less than 8 scope, thus it is easy to ensure that corrosion resistance, and holds
Easily suppress the precipitation of the redox materials of copper further.
(modification)
Described embodiment can also change as following.
The shape of charge/discharge unit 11, configuration or quantity or anolyte that redox flow flow pattern battery has
The capacity of liquid storage tank 23 and electrolyte liquid storage tank 33 can also be according to performance required for redox flow flow pattern battery etc.
Change.In addition, with regard to the anode electrolyte 22 of charge/discharge unit 11 and the quantity delivered of electrolyte liquid 32, for example can also root
Capacity according to charge/discharge unit 11 etc. and set.
Battery alternatively beyond redox flow flow pattern battery.That is, described amberplex is using described pH
In the battery of the electrolyte of scope of value effectively.
Embodiment
Then, by embodiment and comparative example, the present invention is described in more detail.
(embodiment 1)
＜ redox flow flow pattern battery ＞
Positive pole and negative pole are using carbon felt (trade name：GFA5, SGL company manufactures) and electrode area is set as 10cm2.
Side of the positive electrode collector plate is the pure titanium using thickness 6mm.Negative side collector plate is using glassy carbon plate (trade name：SG carbon, thickness
For 0.6mm, the manufacture of Showa electrician limited company).Barrier film is using cation-exchange membrane (CMS, A Si Tom (Astom)
Company manufactures).
Anode electrolyte storage tank and electrolyte liquid storage tank are the glass containers using capacity 30mL.Supply pipe, recovery tube,
Inert gas supply pipe and blast pipe are using silicone tubulation (tube).Pump is using micro-pipe pump (MP-1000, Tokyo physics and chemistry device
Tool limited company manufactures).Charge and discharge device is using charge-discharge battery verifier (battery tester) system
(PFX200, chrysanthemum aqueous electron Industries, Inc manufactures).
The preparation ＞ of ＜ Mn (II)-PEI complex solution
Make polyethyleneimine (PEI, the weight average molecular weight of 0.02 mole (0.86g)：600, and Wako Pure Chemical Industries share
Co., Ltd manufactures) it is dissolved in distilled water 50mL.Add the dilute sulfuric acid about 3mL of 2.5mol/L in this aqueous solution, thus will
PH value is adjusted to 6.The MnSO of 0.02 mole (3.38g) is dissolved in this aqueous solution4·H2After O, and then dissolve 0.05 mole
(7.1g) Na2SO4.Then, add the dilute sulfuric acid of 2.5mol/L in this aqueous solution, after thus pH value being adjusted to 5, with total
The mode that amount becomes 100mL adds distilled water.The concentration obtaining manganese (II)-PEI complex compound whereby is the aqueous solution of 0.2mol/L.
The preparation ＞ of ＜ Cu (II)-PEI complex solution
Make the polyethyleneimine (weight average molecular weight of 0.02 mole (0.86g)：600, and Wako Pure Chemical Industries share is limited
Company manufactures) it is dissolved in distilled water 50mL.Add the dilute sulfuric acid about 3mL of 2.5mol/L in this aqueous solution, thus by pH value
It is adjusted to 6.The CuSO of 0.02 mole (3.19g) is dissolved in this aqueous solution4Afterwards, and then dissolve 0.05 mole (7.1g)
Na2SO4.Then, add distilled water in the way of total amount becomes 100mL.The concentration of acquisition copper (II)-PEI complex compound is whereby
The aqueous solution of 0.2mol/L.The pH value of this aqueous solution is 3.
The electrolytic oxidation ＞ of ＜ Mn (II)-PEI complex solution
Using described redox flow flow pattern battery by Mn (II)-PEI complex solution electrolytic oxidation, just thus prepare
Pole electrolyte.First, add Mn (II)-PEI complex solution 15mL in anode electrolyte storage tank, and in electrolyte
Described Cu (II)-PEI complex solution 15mL is added in liquid storage tank.Then, with the constant current of 100mA to redox flow
Flow pattern battery charges 80 minutes (total 480 coulombs).Additionally, before the beginning charged and in period, from inert gas supply pipe
Supply nitrogen.
Whereby, will be added to Mn (the II)-PEI complex compound electrolytic oxidation contained by the aqueous solution in anode electrolyte storage tank,
The concentration preparing Mn (III)-PEI complex compound is the aqueous solution of 0.2mol/L, as anode electrolyte.Additionally, being believed that here
Divalent manganesetion generates Manganic ion because of electrolytic oxidation, is therefore recited as Mn (III), but the details of valence mumber is failed to understand.
＜ charge and discharge electric test ＞
Mn (II)-PEI complex solution through electrolytic oxidation is used as anode electrolyte, and using Cu (II)-
PEI complex solution, as electrolyte liquid, carries out charge and discharge electric test.In charge and discharge electric test, from the beginning of charging, first with
The constant current charge of 100mA 40 minutes (total 240 coulombs).Then, final discharging voltage is set as 0.0V and with 100mA
Constant current electric discharge.Additionally, before the beginning of charge and discharge electric test and in period, supplying nitrogen from inert gas supply pipe.
Using above discharge and recharge as 1 circulation, electricity repeated for charge and discharge 30 are circulated.
Then, by discharge and recharge 20 circulation repeatedly further, thus by electricity repeated for charge and discharge total 50 circulations.
The redox reaction carrying out discharge and recharge can be presumed as follows.
Positive pole：Mn (III)-PEI complex compoundMn (IV)-PEI complex compound+e-
Negative pole：Cu (II)-PEI complex compound+e- Cu (I)-PEI complex compound
The passage of the cell voltage during discharge and recharge that will circulate up to 30 is shown in Figure 2.Arrow shown in Fig. 2 represents and fills
Discharge curve starts the direction of the discharge and recharge passage to the later stage from initial discharge and recharge.
Result according to Fig. 2, along with repeated charge, confirms charge/discharge capacity and charge/discharge cycle characteristics
Improve.Here, charge and discharge electric test is carried out 1 circulation, be equivalent to and carry out with the electrolytic oxidation reaction of redox system material and electricity
Solution reduction reaction is as the reaction of 1 circulation.With regard to the electrolyte liquid of the redox system material containing copper and polyethyleneimine,
By the reaction as 1 circulation is carried out more than 10 circulations, can be from the state improving charge/discharge capacity and charge/discharge cycle characteristics
Begin to use redox flow flow pattern battery.
The passage of cell voltage when circulating from 31 cycle charge-discharges to 50 is shown in Figure 3.
Result according to Fig. 3 is learnt, even if electricity repeated for charge and discharge 50 are circulated, also maintains cycle characteristics.
In charge and discharge electric test, will obtain charge/discharge cycle characteristics (invertibity), coulombic efficiency, voltage efficiency, energy efficiency,
The result of the current potential of the utilization rate of electrolyte, electromotive force and electrolyte is shown in " discharge and recharge result of the test " hurdle of table 1.
＞ is tested in ＜ self discharge
Add Mn (II)-PEI complex solution 20mL in the anode electrolyte storage tank of redox flow flow pattern battery,
Cu (II)-PEI complex solution 20mL is added in electrolyte liquid storage tank.In addition, in anode electrolyte storage tank and negative pole
It is previously inserted graphite electrode and silver-silver chloride (saturation KCl) electrode respectively in electrolyte reservoir.Then, with the constant electricity of 100mA
Current charge 30 minutes (total 180 coulombs), measures the voltage that the graphite electrode after charging is with respect to silver-silver chloride electrode.Then,
Redox flow flow pattern battery is stood after the night (about 18 hours) under room temperature (about 25C), measure graphite electrode with respect to silver-
The voltage of silver chloride electrode, compares two voltages.
It could be speculated that in anode electrolyte after charging when being charged with described condition, being about 0.1mol/L containing concentration
Mn (III)-PEI complex compound and Mn (IV)-PEI complex compound that concentration is about 0.1mol/L.And it could be speculated that after charging
In electrolyte liquid, containing concentration be about 0.1mol/L DEG C u (II)-PEI complex compound and Cu that concentration is about 0.1mol/L
(I)-PEI complex compound.
Additionally, before the beginning of self discharge test and in period, supplying nitrogen from inert gas supply pipe.
The result that self discharge is tested is shown in " result of self discharge test " hurdle of table 1.
[table 1]
The result of the charge and discharge electric test according to table 1 is learnt, can obtain good battery behavior in embodiment 1.Root
Result according to the self discharge test shown in table 1 is learnt, fully suppression self discharge in embodiment 1.
(embodiment 2～embodiment 4)
In embodiment 2～embodiment 4, different Cu (the II)-PEI complex solution of preparation pH value as shown in table 2
As electrolyte liquid, to evaluate the performance of this electrolyte liquid using cyclic voltammetry (Cyclic Voltammetry, CV).
Cu (the II)-PEI complex solution of embodiment 2～embodiment 4 is the hydrogen of dilute sulfuric acid using 2.5mol/L or 1.0mol/L
Aqueous solution of sodium oxide, to adjust pH value, is prepared in addition similarly to Example 1.
The condition of cyclic voltammetry is as follows.
Sweep limits：- 1.0V～1.5V
Sweep speed：100mV/sec
Reference electrode：Silver-silver chloride (saturation KCl) electrode
Active electrode：Glass graphite (glassy carbon)
Period：50 times
As shown in table 2, in embodiment 2～embodiment 4, temperature of the measurement is set as that 20 DEG C and 60 DEG C are surveyed
Fixed, its result (cyclic voltammetry curve) is represented and makees Fig. 4～Fig. 9.The cyclic voltammetric of the 1st time and the 50th time shown in Fig. 4～Fig. 9
Curve, the arrow shown in figure represents the direction from the 1st time to the 50th time passage.
[table 2]
Learnt according to the result of embodiment 2～embodiment 4, it is possible to obtain good reactivity or invertibity.In addition learn,
In the case that the temperature that CV measures is 20 DEG C, pH value is lower, has the tendency of reactivity or invertibity is more excellent.Obtain with respect to this
Know, in the case that the temperature that CV measures is 60 DEG C, pH value is higher, has the tendency of reactivity or invertibity is more excellent.
(embodiment 5)
In embodiment 5, PEI is changed to 5 with respect to the mol ratio of the redox system material of copper by 1, prepares the oxygen of copper
Change Cu (the II)-PEI complex solution that the concentration that reduction is material is 0.2mol/L.That is, it is dissolved in distilled water 50mL
PEI 0.1 mole (4.3g) is changed to by 0.02 mole (0.86g).In addition, Cu (the II)-PEI complex compound of embodiment 5 is water-soluble
Liquid be the dilute sulfuric acid of 2.5mol/L be used or the sodium hydrate aqueous solution of 1.0mol/L pH value is adjusted to 3.39 after as negative pole
Electrolyte, is commented to the performance of this electrolyte liquid using cyclic voltammetry (CV) in the same manner as embodiment 2～embodiment 4
Valency.In embodiment 5, temperature of the measurement is set as that 20 DEG C and 60 DEG C to be measured, its result (cyclic voltammetry curve) is represented and makees
Figure 10 and Figure 11.
Learnt according to the result of embodiment 5, even if PEI is become by 1 with respect to the mol ratio of the redox system material of copper
More 5, also can obtain good reactivity or invertibity.
(deliquescent evaluation)
Cu (the II)-PEI complex compound being 1 to PEI with respect to the mol ratio of the redox system material of copper by following orders
The aqueous solution evaluates the dissolubility of its complex compound.
First, make the PEI (weight average molecular weight of 0.02 mole (0.86g)：600, and the limited public affairs of Wako Pure Chemical Industries share
Department manufactures) it is dissolved in distilled water 50mL.Add the dilute sulfuric acid about 3mL of 2.5mol/L in this aqueous solution, thus pH value is adjusted
Whole is 6.The CuSO of 0.02 mole (3.19g) is dissolved in this aqueous solution4Afterwards, add distillation in the way of total amount becomes 100mL
Water.Simultaneously utilize the aqueous solution of magnetic stirrer gained, simultaneously in the way of the aqueous solution becomes 20mL, make moisture evaporation.This
When, the precipitation to Cu (II)-PEI complex compound unconfirmed.Learnt according to this result, Cu (II)-PEI complex compound can with 1mol/L with
On concentration dissolving.
Then, add the Na of 0.02 mole (2.84g) in the aqueous solution of described 20mL2SO4Afterwards, 30mL is become with total amount
Mode add distilled water.Then, using the magnetic stirrer aqueous solution, result can make Na2SO4Dissolving.According to this result
Learn, Cu (the II)-PEI complex compound that PEI is 1 with respect to the mol ratio of Cu ion is in conducting salt (Na2SO4) in the presence of can be with
The concentration dissolving of more than 0.67mol/L.
Judged according to result above, Cu (II)-PEI complex compound has the electrolyte liquid for constituting battery applications
Dissolubility.
(comparative example 1)
In comparative example 1, EDTA complex solution is used as anode electrolyte and electrolyte liquid.
The preparation ＞ of ＜ Mn (II)-EDTA complex solution
Make the MnSO of 0.02 mole (3.38g)4·H2O is dissolved in distilled water 50mL.In this aqueous solution, dissolving 0.02 rubs
EDTA (4Na) 2H of your (8.32g)2After O, and then dissolve the Na of 0.05 mole (7.1g)2SO4.Become 100mL's with total amount
Mode adds distilled water.The concentration obtaining manganese (II)-EDTA complex compound whereby is the aqueous solution of 0.2mol/L.
The preparation ＞ of ＜ Cu (II)-EDTA complex solution
Make the CuSO of 0.02 mole (3.19g)4It is dissolved in distilled water 50mL.Dissolve 0.02 mole in this aqueous solution
(8.32g) EDTA (4Na) 2H2After O, and then dissolve the Na of 0.05 mole (7.1g)2SO4.Become the side of 100mL with total amount
Formula adds distilled water.The concentration obtaining Cu (II)-EDTA complex compound whereby is the aqueous solution of 0.2mol/L.
(comparative example 2)
In comparative example 2, prepare Cu (the II)-citric acid complex aqueous solution of 0.2mol/L, as electrolyte liquid, and
Using with comparative example 1 identical anode electrolyte.
<Charge and discharge electric test>
Except using Mn (II)-EDTA complex solution as anode electrolyte, with the complex solution of each comparative example
Beyond electrolyte liquid, carry out charge and discharge electric test similarly to Example 1.In table 3, with regard to the 1st circulation and the 21st circulation
Electrolyte utilization rate, the result that each comparative example is contrasted with embodiment 1 is shown.
[table 3]
In addition, when the utilization rate of the electrolyte of the 1st circulation is set as 100%, calculating the profit of the electrolyte of the 21st circulation
With the slip of rate, thus obtain the slip of charge/discharge capacity.The results are shown in table 3.Result according to table 3 obtains
Know, in charge and discharge electric test, the charge/discharge capacity of embodiment 1 does not reduce, but the charge/discharge capacity of comparative example 1 and comparative example 2
Reduce.
Claims (5)
1. a kind of battery it is characterised in that：Possesses the electrolyte of the redox system material containing copper and polyethyleneimine
Liquid, wherein makes by making copper sulphate be dissolved in water to contain the redox system material of described copper in described electrolyte liquid.
2. battery according to claim 1 it is characterised in that：With regard to the described polyethyleneimine in described electrolyte liquid
Amine, with respect to the mol ratio of the redox system material of copper, the molar concentration of polyethyleneimine is being set as described poly- second
The CH of the elementary cell of alkene imines2CH2In the case of the molar concentration of NH structure, it is set as in more than 1, less than 5 scope.
3. battery according to claim 1 and 2 it is characterised in that：Described electrolyte liquid is to make in the following manner
Standby：In the presence of described polyethyleneimine, by with the electroreduction reaction of the redox system material of described copper and electrolysis oxygen
The reaction changing reaction as 1 circulation carries out more than 10 circulations.
4. battery according to claim 1 and 2 it is characterised in that：The oxidation of the described copper in described electrolyte liquid
Reduction be material content be more than 0.2mol/L, in the scope of below 1.0mol/L.
5. battery according to claim 1 and 2 it is characterised in that：The pH value of described electrolyte liquid be more than 2,8 with
Under scope in.
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| CN108538634B (en) * | 2018-05-25 | 2020-04-28 | 北京化工大学 | Water-system compound electrolyte and preparation method and application thereof |
| CN110858659B (en) * | 2018-08-24 | 2021-08-10 | 江苏泛宇能源有限公司 | Method for flow battery waste gas treatment and flow battery system |
| CN109713349B (en) * | 2018-12-13 | 2020-08-04 | 浙江大学 | Non-mixed type no-storage-tank flow battery structure and method |
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| JPS5834911B2 (en) * | 1979-09-14 | 1983-07-29 | 工業技術院長 | redox battery |
| JPS5913153B2 (en) * | 1980-06-17 | 1984-03-28 | 工業技術院長 | redox battery |
| JPS58133788A (en) * | 1982-02-01 | 1983-08-09 | Semiconductor Energy Lab Co Ltd | Electrolyte solution |
| JPS6273577A (en) * | 1985-09-26 | 1987-04-04 | Babcock Hitachi Kk | Bromine-copper redox type fuel cell |
| JPH03287779A (en) * | 1990-04-04 | 1991-12-18 | Toyota Central Res & Dev Lab Inc | Electroless copper plating bath |
| US6824914B2 (en) * | 2001-08-20 | 2004-11-30 | Energetics, Inc. | Amine-based fuel cell/battery with high specific energy density |
| KR101638595B1 (en) * | 2010-01-29 | 2016-07-12 | 삼성전자주식회사 | Redox flow battery |
| EP2355223B1 (en) * | 2010-01-29 | 2019-04-17 | Samsung Electronics Co., Ltd. | Redox flow battery including an organic electrolyte soution |
| CN201845830U (en) * | 2010-11-11 | 2011-05-25 | 中国人民解放军63971部队 | Flow battery galvanic pile |
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