CN104781970B - Battery - Google Patents

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Publication number
CN104781970B
CN104781970B CN201280076845.8A CN201280076845A CN104781970B CN 104781970 B CN104781970 B CN 104781970B CN 201280076845 A CN201280076845 A CN 201280076845A CN 104781970 B CN104781970 B CN 104781970B
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China
Prior art keywords
electrolyte
discharge
battery
electrolyte liquid
copper
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CN104781970A (en
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黄岚
出口洋成
山之内昭介
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Nissin Electric Co Ltd
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Nissin Electric Co Ltd
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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
    • 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
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The present invention provides a kind of battery.The battery of the present invention possesses the electrolyte liquid (32) of the redox system material containing copper and the amine represented by following formulas (1).In formula (1), n be 0~4 any integer, R1、R2、R3And R4Independently represent hydrogen atom, methyl or ethyl.Even if the battery of the present invention in the case where the pH value of electrolyte is more than 3, also easily uses the redox system material of copper in the electrolyte.

Description

Battery
Technical field
Present invention battery (electricity- such as being related to a kind of oxidation, reduction liquid (redox flow) type battery storage battery)。
Background technology
In the past, on electrolyte used in battery, it is known that the structure containing metal oxidation reduction system material and chelating agent Into (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 ethylenediamine tetra-acetic acid and specific containing iron redox system material and citric acid Example.In addition, in patent document 2, as electrolyte liquid, disclose specific containing titanium redox system material and citric acid Example, the concrete example containing titanium redox system material and ethylenediamine tetra-acetic acid, contain chromium redox system material and ethylenediamine tetraacetic The concrete example of acetic acid and the concrete example containing chromium redox system material and phosphoric acid.In non-patent literature 1, as electrolyte Liquid, disclose the concrete example containing iron redox system material and ethylenediamine tetra-acetic acid, containing iron redox system material and lemon The concrete example of lemon 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 publications
Patent document 2：Japanese Patent Laid-Open No. Sho 57-9072 publications
Non-patent literature
Non-patent literature 1：Y.H. literary (Y.H.Wen) et al.,《Iron (Fe in sodium acetate solution3+/Fe2+)-complex compound/bromine (Br2/Br-) redox flow batteries research (Studies on Iron (Fe3+/Fe2+)-Complex/Bromine(Br2/ Br-)Redox Flow Cell in Sodium Acetate Solution)》,《Electrochemical Society periodical (Journal ofThe Electrochemical Society)》, 153 (5) A929-A934 (2006)
The content of the invention
[the problem of invention is to be solved]
The electrolyte of highly acid is used generally in battery.In the electrolyte of highly acid, metal oxidation reduction ion Even if also stably being dissolved for of a relatively high concentration, therefore the energy density of battery can be improved.In addition, the electrolysis of highly acid In liquid, the carrier of ionic conduction turns into H+Ion or OH-Ion.Due to H+The mobility and OH of ion-The mobility of ion is homogeneous To higher, therefore the conductance of electrolyte uprises.Whereby, the resistance of battery diminishes, and as a result the efficiency of battery improves.Like this In the case of electrolyte using highly acid, the resistance to of electrolyte can tolerate to the material requirements for forming redox flow flow pattern battery Chemicals.In contrast, for example the material for forming battery can be reduced in the case where using the electrolyte that pH value is more than 3 Chemical-resistant necessary to material, it as a result can reduce the manufacturing cost of battery.However, in this case, metal oxidation reduction Ion is difficult to stably dissolve.It is believed that in the electrolyte that pH value is more than 3, the dissolubility of metal oxidation reduction ion reduces The shortcomings that can by make in electrolyte containing chelating agent, make up metal oxidation reduction ion forming complex.But close In the battery using chelating agent, actual conditions are that there is no practical report.
In addition, Fig. 4 of patent document 1 is the comparison figure of the redox system in hydrochloric acid solution, this, which compares, contains copper in figure Redox system paint point (plot).However, on using the redox system of copper as the electrolyte that pH value is more than 3 Battery, not yet report.
The present invention is in view of such a actual conditions form, its object is to provide a kind of battery, even if the battery In the case where the pH value of electrolyte is more than 3, the redox system material of copper is also easily used in the electrolyte.
[technological means for solving problem]
In order to reach the purpose, in one embodiment of the present invention, there is provided a kind of battery, the battery possess Redox system material containing copper, the electrolyte liquid with the amine represented by formula (1)：
[changing 1]
(wherein, in formula (1), n represents 0~4 any integer, R1、R2、R3And R4Independently represent hydrogen atom, methyl Or ethyl).
In the battery, preferably described amine contains selected from Diethylenetriamine (diethylenetriamine), three second In tetramine (triethylenetetramine) and N, N '-dimethyl-ethylenediamine (N, N-dimethylethylenediamine) At least one.
In the battery, the redox system thing preferably by the amine in the electrolyte liquid relative to copper The mol ratio of matter is set as in more than 1, less than 5 scope.
In the battery, make preferably by copper sulphate is dissolved in water in the electrolyte liquid containing State the redox system material of copper.
In the battery, the content of the redox system material of the copper in preferably described electrolyte liquid is 0.2 mole/more than L, in 1.0 moles/below L scope.
In the battery, the pH value of preferably described electrolyte liquid is in more than 3, less than 11 scope.
In the battery, preferably described electrolyte liquid is the oxygen by making the copper in the presence of the amine It is that material carries out electroreduction reaction and prepared to change reduction.
Brief description of the drawings
Fig. 1 is the skeleton diagram for the redox flow flow pattern battery for representing the embodiment of the present invention.
Fig. 2 is the figure of the result for the solubility test for representing Cu (II)-amine complex.
Fig. 3 is the result of the charge and discharge electric test of embodiment 1, for expression time and the figure of the relation of voltage.
Fig. 4 is the result of the charge and discharge electric test of embodiment 2, for expression time and the figure of the relation of voltage.
Embodiment
Hereinafter, the redox flow flow pattern battery of the battery of the embodiment as the present invention is illustrated.
<The 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 Positive pole side unit 21 and negative pole side unit 31 are divided into by barrier film 12.Redox flow flow pattern battery possesses storage positive pole Negative pole used in the anode electrolyte storage tank 23 and storage negative pole side unit 31 of anode electrolyte 22 used in side unit 21 The electrolyte liquid storage tank 33 of electrolyte 32.In redox flow flow pattern battery, optionally and provided with regulation charge/discharge unit 11 The temperature-adjusting device of the temperature on periphery.
In positive pole side unit 21, positive pole 21a and side of the positive electrode collector plate 21b are configured with the state being in contact.Negative In pole side unit 31, negative pole 31a and negative side collector plate 31b are configured with the state being in contact.Positive pole 21a and negative pole 31a E.g. it is made up of the felt (felt) of carbon.Side of the positive electrode collector plate 21b and negative side collector plate 31b is, for example, by vitreous carbon Plate is formed.Each collector plate 21b, collector plate 31b are electrically connected to charge and discharge device 10.
On positive pole side unit 21, anode electrolyte storage tank 23 is connected to via supply pipe 24 and recovery tube 25.Supplying To being equipped with pump 26 on pipe 24.By the work of pump 26, the anode electrolyte 22 in anode electrolyte storage tank 23 passes through supply pipe 24 and be supplied to positive pole side unit 21.Now, the anode electrolyte 22 in positive pole side unit 21 is returned by recovery tube 25 Receive in anode electrolyte storage tank 23.Like this, anode electrolyte 22 is made in anode electrolyte storage tank 23 and positive pole side unit 21 Middle circulation.
On negative pole side unit 31, electrolyte liquid storage tank 33 is connected to via supply pipe 34 and recovery tube 35.Supplying To being equipped with pump 36 on pipe 34.By the work of pump 36, the electrolyte liquid 32 in electrolyte liquid storage tank 33 passes through supply pipe 34 and be supplied to negative pole side unit 31.Now, the electrolyte liquid 32 in negative pole side unit 31 is returned by recovery tube 35 Receive in electrolyte liquid storage tank 33.Like this, electrolyte liquid 32 is made in electrolyte liquid storage tank 33 and negative pole side unit 31 Middle 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.By lazy Property gas supply pipe 13 inert gas is supplied to positive pole electrolyte reservoir 23 and electrolyte liquid storage tank 33, thus suppress positive pole electricity Solution liquid 22 and electrolyte liquid 32 contact with the oxygen in air.Inert gas can for example use nitrogen.Supply to anolyte The inert gas of liquid storage tank 23 and electrolyte liquid storage tank 33 is discharged by blast pipe 14.In the discharge side of blast pipe 14 Front end, provided with the water seal portion 15 that the opening of blast pipe 14 is subject to water seal.Water seal portion 15 prevents air adverse current from arriving in blast pipe 14, And the pressure in anode electrolyte storage tank 23 and in electrolyte liquid storage tank 33 is held in certain pressure.
During charging, oxidation reaction is carried out in the anode electrolyte 22 contacted with positive pole 21a, and connect with negative pole 31a Reduction reaction is carried out in tactile electrolyte liquid 32.That is, positive pole 21a disengages electronics, and negative pole 31a receives electronics.Now, just Pole side collector plate 21b supplies the electronics disengaged by positive pole 21a to charge and discharge device 10.Negative side collector plate 31b will be from charge and discharge The electronics that electric installation 10 receives is supplied to negative pole 31a.Negative side collector plate 31b is collected by the negative pole 31a electronics disengaged and confession To charge and discharge device 10.
During electric discharge, reduction reaction is carried out in the anode electrolyte 22 contacted with positive pole 21a, and connect with negative pole 31a Oxidation reaction is carried out in tactile electrolyte liquid 32.That is, positive pole 21a receives electronics, and negative pole 31a disengages electronics.Now, just Pole side collector plate 21b supplies the electronics received from charge and discharge device 10 to positive pole 21a.
<Electrolyte>
Redox flow flow pattern battery possesses the electrolyte liquid 32 of the redox system material containing copper and amine.
In electrolyte liquid 32, copper plays function as active material, such as it could be speculated that occurs in charging by Cu (II) to Cu (I) reduction, and oxidation of the generation from Cu (I) to Cu (II) in electric discharge.
From the viewpoint of energy density is improved, the redox system material (copper ion) of the copper in electrolyte liquid 32 Concentration preferably 0.1 mole/more than L, more preferably 0.2 mole/more than L, and then preferably 0.4 mole/more than L.Suppress from further From the viewpoint of the precipitation of the redox system material of copper, the redox system material (copper ion) of the copper in electrolyte liquid 32 Concentration preferably 2.5 moles/below L, more preferably 1.5 moles/below L.
Amine contained by electrolyte liquid 32 is represented by following formulas (1).
[changing 2]
Wherein, in formula (1), n represents 0~4 any integer, R1、R2、R3And R4Independently represent hydrogen atom, methyl or Ethyl.
Amine represented by formula (1) is one kind of chelating agent, is had the effect that：Generated with the redox system material of copper Complex compound, suppress the precipitation of the redox system material of copper in electrolyte liquid 32.
The example of amine represented by formula (1) can for example be enumerated：Ethylenediamine (EDA, n=0), Diethylenetriamine (DETA, n =1), three second tetramines (TETA, n=2), tetren (TEPA, n=3), five second hexamines (PEHA, n=4), tetramethylethylenediamine (TMEDA, n=0), N- methyl ethylenediamines (n=0), N, N '-dimethyl-ethylenediamine (DMEDA, n=0), N, N- dimethyl second two Amine (n=0), NEED (n=0), N, N '-diethyl ethylenediamine (n=0) and N, N- diethyl ethylenediamine (n=0).
Electrolyte liquid 32 can also contain a variety of containing only one kind in the amine represented by formula (1).
Electrolyte liquid 32, which preferably contains, to be selected from Diethylenetriamine, three second tetramines and N, N '-dimethyl-ethylenediamine At least one amine.
The amine represented by formula (1) in electrolyte liquid 32 is preferred relative to the mol ratio of the redox system material of copper Be set in more than 1, less than 5 scope.In the case where the mol ratio is more than 1, it is easier to suppress the oxidation of copper Reduction is the precipitation of material.In the case where the mol ratio is less than 5, there are reactivity or charge/discharge cycle characteristics (invertibity) The tendency of raising.
In the scope of the pH value of electrolyte liquid 32 preferably more than 3, less than 11.Electrolyte liquid 32 pH value for 3 with In the case of upper, it is easy to ensure that corrosion resistance.In the case where the pH value of electrolyte liquid 32 is less than 11, easily further suppress The precipitation of the redox system material of copper.
In electrolyte liquid 32, optionally also contain the salt of such as inorganic acid or the salt of organic acid, except formula (1) institute table Chelating agent beyond the amine shown.
Active material used is not particularly limited in anode electrolyte 22, such as can be enumerated：The redox system of iron Material, the redox system material of chromium, the redox system material of manganese, the redox system material of copper and the redox system of vanadium Material.
From the viewpoint of energy density is improved, the redox system material of the metal in anode electrolyte 22 (metal from Son) concentration preferably 0.1 mole/more than L, more preferably 0.2 mole/more than L, and then preferably 0.4 mole/more than L.
From the viewpoint of the precipitation of redox system material for suppressing metal, the oxidation of the metal in anode electrolyte 22 Reduction is concentration preferably 2.5 moles/below the L, more preferably 1.5 moles/below L of material (metal ion).
The active material used such as suitably redox system material of manganese in anode electrolyte 22.Make positive pole electric When containing manganese in solution liquid 22, for not chloride ion-containing, such as be preferably dissolved in water manganese sulfate.It could be speculated that positive pole is electric Contained manganese is oxidized to Mn (IV) in charging by Mn (III) in solution liquid 22, and Mn is reduced into by Mn (IV) in electric discharge (III)。
In anode electrolyte 22, preferably further contain chelating agent.The example of chelating agent can for example be enumerated：Formula (1) amine, polyethyleneimine and amino carboxylic acid system chelating agent represented by.
Chelating agent in anode electrolyte 22 is relative to the molar ratio of the redox system material of metal as preferably It is set as in more than 0.5, less than 10 scope, is more preferably set in more than 1, less than 5 scope.
In anode electrolyte 22, optionally also contain the salt of such as inorganic acid or the salt of organic acid.
In the scope of the pH value of anode electrolyte 22 preferably more than 3, less than 11.
Electrolyte liquid 32 and anode electrolyte 22 can be prepared using known method.In electrolyte liquid 32 is made During redox system material containing copper, such as from the point of view of in terms of easily obtaining, preferably make copper sulphate (CuSO4) dissolving In water.
Electrolyte liquid 32 is preferably by the redox system thing for making copper in the presence of the amine represented by formula (1) Matter carries out electroreduction reaction and prepared.If such as cupric is carried out electroreduction in aqueous in the presence of amine anti- Should, then it can obtain the electrolyte liquid 32 reduced relative to the current potential of silver-silver chloride (saturation KCl) electrode.Electrolyte liquid 32 Current potential it is lower, become higher as the voltage obtained by discharge and recharge.It could be speculated that copper in electrolyte liquid 32 in charging by Cu (I) Cu (0) is reduced into, and Cu (I) is oxidized to by Cu (0) in electric discharge.In addition, suitably by electrolyte liquid 32 In the molal quantity of redox system material of contained copper be multiplied by calculated by Faraday constant (Faraday ' s constant) Coulomb amount is when being set as 100%, and electroreduction reaction is carried out with more than 100% coulomb amount.
Water used preferably has equal or higher with distilled water in electrolyte liquid 32 and anode electrolyte 22 Purity.Redox flow flow pattern battery is preferably the ring that electrolyte liquid 32 and anode electrolyte 22 are set as to inert gas Border, which is got off, carries out discharge and recharge.
<The effect of redox flow flow pattern battery>
In the electrolyte liquid 32 of the amine represented by the redox system material containing copper and formula (1), the oxidation of copper Reduction is that material forms complex compound with the amine, thus suppresses the precipitation of copper.In addition, by using the electrolyte liquid 32, and Play good battery performance.
The performance of redox flow flow pattern battery for example can by charge/discharge cycle characteristics (invertibity), coulombic efficiency, Voltage efficiency, energy efficiency, the utilization rate of electrolyte, the current potential of electromotive force and electrolyte are evaluated.Hereinafter, by redox flow 1 discharge and recharge of flow pattern battery is referred to as 1 circulation.
Charge/discharge cycle characteristics (invertibity) are by by the coulomb amount (A) of the electric discharge of the 5th circulation and the 90th circulation or the The coulomb amount (B) of the electric discharge of 100 circulations is updated in following formula (1) and calculated.
Charge/discharge cycle characteristics [%]=B/A × 100 ... (1)
Such as in the value calculated according to the coulomb amount of the 90th circulation, charge/discharge cycle characteristics preferably more than 80%.
Coulombic efficiency is by the way that the coulomb amount (D) of the coulomb amount (C) of the charging of given cycle and electric discharge is updated to down State in formula (2) and calculate.
Coulombic efficiency [%]=D/C × 100 ... (2)
Such as in the value calculated according to the coulomb amount of the 3rd circulation, coulombic efficiency preferably more than 80%.
Voltage efficiency be by by the average terminal voltage (E) of the charging of given cycle and electric discharge average terminal voltage (F) it is updated in following formula (3) and calculates.
Voltage efficiency [%]=F/E × 100 ... (3)
Such as in the value calculated according to the terminal voltage of the 2nd circulation, voltage efficiency preferably more than 40%.
Energy efficiency is by the way that the quantity of power (H) of the quantity of power (G) of the charging of given cycle and electric discharge is updated to down State in formula (4) and calculate.
Energy efficiency [%]=H/G × 100 ... (4)
In the value calculated according to the quantity of power of the 2nd circulation, energy efficiency preferably more than 40%.
The utilization rate of electrolyte is to calculate in the following manner：It is fed to the electrolyte of positive pole 21a sides or negative pole 31a sides The molal quantity of active material be multiplied by Faraday constant (96500 coulomb/mole) and obtain coulomb amount (I), and obtain the 1st and follow The coulomb amount (J) of the electric discharge of ring, coulomb amount (I) and coulomb amount (J) are updated in following formula (5).In addition, in supply to positive pole The molal quantity of the molal quantity of the active material of the electrolyte of 21a sides and the active material of the electrolyte of supply to negative pole 31a sides is not With in the case of, the wherein less molal quantity of use.The utilization rate of the electrolyte later on the 1st circulation, can also be similarly Calculate.
The utilization rate [%] of electrolyte=J/I × 100 ... (5)
In the value calculated according to the coulomb amount of the 1st circulation, the utilization rate preferably more than 55% of electrolyte.
Terminal electricity when electromotive force is set to switch to electric discharge by charging in given cycle (when electric current is 0mA) Pressure.
In the terminal voltage of the 1st circulation, preferred more than the 0.8V of electromotive force.
The current potential of electrolyte is to be previously inserted graphite respectively in anode electrolyte storage tank 23 and electrolyte liquid storage tank 33 When electrode and silver-silver chloride (saturation KCl) electrode, the current potential with the graphite electrode in discharge and recharge relative to silver-silver chloride electrode To represent.
According to discussed above embodiment, following effect is played.
(1) the redox flow flow pattern battery of this embodiment possesses the redox system material containing copper and formula (1) The electrolyte liquid 32 of represented amine.In this case, when even if the pH value of electrolyte liquid 32 is more than 3, it can also suppress copper Redox system material precipitation.Therefore, even if in the case where the pH value of electrolyte is more than 3, also easily in the electrolysis The redox system of copper is used in liquid.
(2) electrolyte liquid 32 preferably contains and is selected from Diethylenetriamine, three second tetramines and N, N '-dimethyl-ethylenediamine At least one amine.In this case, for example easily suppress self discharge, or charge/discharge cycle characteristics improve, therefore turn into practicality Higher redox flow flow pattern battery.Though its mechanism is indefinite, it could be speculated that because the amine is relatively low molecule, And there is the structure of the two level amine type represented by 1 or 2 C-NH-C in its intramolecular, therefore in the redox materials with copper Between form more stable complex compound.
(3) amine represented by the formula (1) in electrolyte liquid 32 relative to the redox system material of copper mol ratio Preferably it is set as in more than 1, less than 5 scope.In this case, it is easier to suppress the analysis of the redox system material of copper Go out.
(4) redox system containing copper in electrolyte liquid 32 is made preferably by copper sulphate is dissolved in water Material.In this case, because copper sulphate easily obtains, therefore electrolyte liquid 32 can be readily available.Such as with using chlorine The situation for changing copper compares, and can easily suppress to cause to produce being mixed into for the chlorion of chlorine at positive pole.
(5) content of the redox system material of the copper in electrolyte liquid 32 be 0.2 mole/more than L, 1.0 moles/L In following scope, energy density is thus easily improved, and further suppresses the precipitation of the redox system material of copper.
(6) pH value of electrolyte liquid 32 is in more than 3, less than 11 scope, thus it is easy to ensure that corrosion resistance, and is held Easily further suppress the precipitation of the redox system material of copper.
(7) electrolyte liquid 32 is preferably by the redox for making copper in the presence of the amine represented by formula (1) It is that material carries out electroreduction reaction and prepared.In this case, it can further improve the voltage of gained.
(modification)
The embodiment can also change as following.
Shape, configuration or the quantity or anolyte of charge/discharge unit 11 possessed by redox flow flow pattern battery The capacity of liquid storage tank 23 and electrolyte liquid storage tank 33 can also become according to required performance of redox flow flow pattern battery etc. More.In addition, on anode electrolyte 22 and the quantity delivered of electrolyte liquid 32 to charge/discharge unit 11, such as also can be according to filling Capacity of discharge cell 11 etc. and set.
Or the battery beyond redox flow flow pattern battery.
Embodiment
Then, the present invention is described in more detail by embodiment and comparative example.
(solubility test of Cu (II)-amine complex)
The three second tetramines (TETA) of 0.1 mole (14.4g) are made to be dissolved in distilled water 50mL.Make 0.1 mole (15.96g) CuSO4After being dissolved in the aqueous solution, distilled water is added in a manner of total amount turns into 90mL.Then, stir the aqueous solution until CuSO4After untill being completely dissolved, 2.5 moles/L dilute sulfuric acid is added, pH value is thus adjusted to 4.6.In the aqueous solution with Total amount adds distilled water as 100mL mode, and the concentration for being derived from Cu (II)-TETA complex compounds is 1.0 moles/L water Solution.
The solubility test for standing 10 days with the condition under room temperature (about 25 DEG C), air, knot are carried out to the aqueous solution of gained It is unconfirmed in the fruit aqueous solution to arrive precipitate.
Operated same as described abovely, prepare the concentration or different water-soluble of pH value of Cu (II)-TETA complex compounds Liquid, carry out solubility test.It the results are shown in Fig. 2.
Fig. 2 point A1 that paints is represented in Cu and TETA mol ratio to be set as to 1: 1 solubility test of the aqueous solution not Precipitate is confirmed, point B2 is painted and represents in Cu and TETA mol ratio to be set as to 1: 1 solubility test of the aqueous solution really Recognize precipitate.Fig. 2 point B1 that paints is represented in Cu and TETA mol ratio to be set as to 1: 2 solubility test of the aqueous solution It is unconfirmed to arrive precipitate, paint point A2 and represent in Cu and TETA mol ratio to be set as to 1: 2 solubility test of the aqueous solution Confirm precipitate.
As shown in FIG. 2, learn Cu (II) even if-TETA complex compound aqueous solution pH value for more than 3 also ensure that it is molten Xie Xing, thus it is high as the value of the electrolyte of redox flow flow pattern battery.
(embodiment 1)
<Redox flow flow pattern battery>
As positive pole and negative pole, carbon felt (trade name is used：GFA5, Xi Geli (SGL) company manufactures) and by electrode area It is set as 10cm2.Side of the positive electrode collector plate is the pure titanium using thickness 0.6mm.Negative side collector plate is to use glassy carbon plate (business The name of an article：SG carbon, thickness 0.6mm, the manufacture of Showa electrician limited company).Barrier film is to use 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 to use silicone tubulation.Pump is to use micro-pipe pump (MP-1000, Tokyo physics and chemistry apparatus share Co., Ltd manufactures).Charge and discharge device is that (PFX200, chrysanthemum aqueous electron industry share are limited using charge-discharge battery test system Company manufactures).
<The preparation of Mn (II)-TETA complex solutions>
The three second tetramines (TETA) of 0.02 mole (2.92g) are made to be dissolved in distilled water 50mL.Added in the aqueous solution 2.5 moles/L dilute sulfuric acid, is thus adjusted to 6 by pH value.Make the MnSO of 0.02 mole (3.38g)4·H2It is water-soluble that O is dissolved in this After in liquid, and then make the Na of 0.05 mole (7.1g)2SO4Dissolving.Then, 2.5 moles/L dilute sulphur is added in the aqueous solution Acid, after pH value thus is adjusted into 5, distilled water is added in a manner of total amount turns into 100mL.It is derived from manganese (II)-TETA networks The concentration of compound is the 0.2 mole/L aqueous solution.
<The preparation of Cu (II)-TETA complex solutions>
The three second tetramines (TETA) of 0.02 mole (2.92g) are made to be dissolved in distilled water 50mL.Make 0.02 mole (3.19g) CuSO4After being dissolved in the aqueous solution, and then make the Na of 0.05 mole (7.1g)2SO4Dissolving.Then, add in the aqueous solution Add 2.5 moles/L dilute sulfuric acid, after pH value thus is adjusted into 6, distilled water is added in a manner of total amount turns into 100mL.Thus The concentration for obtaining copper (II)-TETA complex compounds is the 0.2 mole/L aqueous solution.
<The electrolytic oxidation of Mn (II)-TETA complex solutions>
Electrolytic oxidation is carried out to Mn (II)-TETA complex solutions using the redox flow flow pattern battery, thus Prepare anode electrolyte.Mn (II)-TETA complex solution 20mL are added first in anode electrolyte storage tank, and negative Cu (II)-TETA complex solutions 20mL is added in the electrolyte reservoir of pole.Then, oxidation is gone back with 100mA constant current Stoste flow pattern battery charges 60 minutes (total 386 coulombs).In addition, before charging starts and in period, supplied by inert gas Pipe supplies nitrogen.
Thus, it will be added to Mn (II)-TETA complex compounds electrolysis oxygen contained in the aqueous solution in anode electrolyte storage tank Change, the concentration for preparing Mn (III)-TETA complex compounds is the 0.2 mole/L aqueous solution, as anode electrolyte.In addition, this In it is believed that divalent manganesetion generates Manganic ion by electrolytic oxidation, therefore be recited as Mn (III), but valence mumber is not in detail Clearly.
<Charge and discharge electric test>
It is used as anode electrolyte using by Mn (III)-TETA complex solutions obtained by electrolytic oxidation reaction, and Charge and discharge electric test is carried out using Cu (II)-TETA complex solutions as electrolyte liquid.In charge and discharge electric test, from charging Start, first with 100mA constant current charge 40 minutes (total 240 coulombs).Then, with 100mA constant current and general Electric discharge end voltage is set as 0V to be discharged.In addition, before discharge and recharge on-test and in period, supplied by inert gas Pipe supplies nitrogen.
Discharge and recharge by more than is set as 1 circulation, repeats the discharge and recharge of 100 circulations.
The redox reaction that presumption carries out discharge and recharge is as follows.
Positive pole：
Negative pole：
The passage of cell voltage during the discharge and recharge for being recycled to the 58th circulation by the 56th is shown in Figure 3.
In charge and discharge electric test, obtain charge/discharge cycle characteristics (invertibity), coulombic efficiency, voltage efficiency, energy efficiency, The current potential of the utilization rate of electrolyte, electromotive force and electrolyte.
Charge/discharge cycle characteristics (invertibity) are the electric discharges of the coulomb amount (A) and the 100th circulation according to the electric discharge of the 5th circulation Coulomb amount (B) and obtain.
Coulombic efficiency is obtained according to the coulomb amount of the 56th circulation.
Voltage efficiency is obtained according to the average terminal voltage of the 2nd circulation.
Energy efficiency is obtained according to the quantity of power of the 2nd circulation.
The utilization rate of electrolyte is obtained according to the coulomb amount of the 1st circulation.
Electromotive force is set to the terminal voltage of the 1st circulation.
It the results are shown in " discharge and recharge result of the test " column of table 1.
<Self discharge is tested>
Mn (II)-TETA complex solutions are added in the anode electrolyte storage tank of the redox flow flow pattern battery 20mL, and Cu (II)-TETA complex solutions 20mL is added in electrolyte liquid storage tank.In addition, in electrolyte liquid Graphite electrode and silver-silver chloride (saturation KCl) electrode are previously inserted in storage tank.Then, with 100mA constant current charge 120 Minute (total 772 coulombs), determine voltage of the graphite electrode after charging relative to silver-silver chloride electrode.Then, by oxidation also After stoste flow pattern battery stands about 24 hours under room temperature (about 25 DEG C), measure graphite electrode is relative to silver-silver chloride electrode Voltage, compare two voltages.
Speculate when being charged with the condition, in anode electrolyte after charging, contained with about 0.2 mole/L concentration There are Mn (IV)-TETA complex compounds.Speculate in electrolyte liquid after charging, Cu is contained with about 0.2 mole/L concentration (II)-TETA complex compounds.
In addition, before self discharge on-test and in period, nitrogen is supplied by inert gas supply pipe.
The result that self discharge is tested is shown in " result of self discharge experiment " column of table 1.
[table 1]
The result of charge and discharge electric test as shown in Table 1 is learnt, good battery behavior can be obtained in embodiment 1.By the institute of table 1 The result for the self discharge experiment shown is learnt, can fully suppress self discharge in embodiment 1.
(embodiment 2)
In embodiment 2, anode electrolyte is changed to Fe (II)-citric acid complex aqueous solution.
<The preparation of Fe (II)-citric acid complex aqueous solution>
The citric acid of 0.02 mole (3.84g) is set to be dissolved in distilled water 50mL.Sodium hydroxide is added in the aqueous solution 2.4g, pH value is thus adjusted to 6.Make the FeSO of 0.02 mole (5.56g)4·7H2After O is dissolved in the aqueous solution, and then make The Na of 0.1 mole (14.2g)2SO4Dissolving.Then, 2.5 moles/L dilute sulfuric acid is added in the aqueous solution, thus adjusts pH value It is whole be 5 after, by total amount turn into 100mL in a manner of add distilled water.The concentration of acquisition Fe (II)-citric acid complex is whereby 0.2 mole/L the aqueous solution.
<The preparation of Cu (II)-TETA complex solutions>
Operated similarly to Example 1, the concentration for obtaining copper (II)-TETA complex compounds is the water-soluble of 0.2 mole/L Liquid.
<The electrolysis of the electrolytic oxidation and Cu (II)-TETA complex solutions of Fe (II)-citric acid complex aqueous solution Reduction>
The electrolytic oxidation of Fe (II)-citric acid complex aqueous solution is carried out using the redox flow flow pattern battery, Thus anode electrolyte is prepared, carries out the electroreduction of Cu (II)-TETA complex solutions, thus prepares negative pole electrolysis Liquid.
First, Fe (II)-citric acid complex aqueous solution 20mL is added in anode electrolyte storage tank, and in negative electricity Solve and Cu (II)-TETA complex solutions 20mL is added in liquid storage tank.Then, with 100mA constant current to redox flow Flow pattern battery charges 60 minutes (total 386 coulombs).In addition, before charging starts and in period, supplied by inert gas supply pipe To nitrogen.
Whereby, it will be added to Fe (II) contained in the aqueous solution in anode electrolyte storage tank-citric acid complex electrolysis Oxidation, the concentration for preparing Fe (III)-citric acid complex is the 0.2 mole/L aqueous solution, as anode electrolyte.Separately Outside, Cu (II)-TETA complex compound electroreductions contained in the aqueous solution in electrolyte liquid storage tank are will be added to, prepare Cu (I) concentration of-TETA complex compounds is the 0.2 mole/L aqueous solution, as electrolyte liquid.
<Charge and discharge electric test>
It is used as anode electrolyte using by Fe (III)-citric acid complex aqueous solution obtained by electrolytic oxidation reaction, and And use Cu (I)-TETA complex solutions by electroreduction reaction gained to be used as electrolyte liquid, carry out discharge and recharge examination Test.In charge and discharge electric test, since charging, first with 50mA constant current charge 80 minutes (total 240 coulombs).Then, 0.2V is set as with 50mA constant current and the end voltage that will discharge and discharged.In addition, before discharge and recharge on-test And in period, nitrogen is supplied by inert gas supply pipe.
Discharge and recharge by more than is set as 1 circulation, and the discharge and recharge of 100 circulations is repeated.
The redox reaction that presumption carries out discharge and recharge is as follows.
Positive pole：
Negative pole：
The passage of cell voltage during the discharge and recharge for being recycled to the 4th circulation by the 2nd is shown in Figure 4.
In charge and discharge electric test, obtain charge/discharge cycle characteristics (invertibity), coulombic efficiency, voltage efficiency, energy efficiency, The current potential of the utilization rate of electrolyte, electromotive force and electrolyte.
Charge/discharge cycle characteristics (invertibity) are the electric discharges of the coulomb amount (A) and the 90th circulation according to the electric discharge of the 5th circulation Coulomb amount (B) and obtain.
Coulombic efficiency is obtained according to the coulomb amount of the 3rd circulation.
Voltage efficiency is obtained according to the average terminal voltage of the 2nd circulation.
Energy efficiency is obtained according to the quantity of power of the 2nd circulation.
The utilization rate of electrolyte is obtained according to the coulomb amount of the 1st circulation.
Electromotive force is set to the terminal voltage of the 3rd circulation.
It the results are shown in " discharge and recharge result of the test " column of table 2.
[table 2]
The result of charge and discharge electric test as shown in Table 2 is learnt, good battery behavior can be also obtained in embodiment 2.
(embodiment 3)
In embodiment 3, in the preparation of Cu (II)-TETA complex solutions of embodiment 1, TETA is changed to tetrem Five amine (TEPA), the concentration for similarly being operated and preparing copper (II)-TEPA complex compounds is the 0.2 mole/L aqueous solution.Make By the use of Cu (the II)-TEPA complex solutions of gained as electrolyte liquid, in addition, grasped similarly to Example 1 Make, carry out charge and discharge electric test and self discharge experiment.The result of the charge and discharge electric test of embodiment 3 is same as Example 1, but embodiment The result of 3 self discharge experiment is inferior to embodiment 1.
(embodiment 4)
<The preparation of Mn (II)-eda complex aqueous solution>
The ethylenediamine (EDA) of 0.1 mole (6.0g) is set to be dissolved in distilled water 70mL.Addition 2.5 rubs in the aqueous solution That/L dilute sulfuric acid, is thus adjusted to 7 by pH value.Make the MnSO of 0.02 mole (3.38g)4·H2O is dissolved in the aqueous solution Afterwards, and then the Na of 0.05 mole (7.1g) is made2SO4Dissolving.Then, distilled water is added in a manner of total amount turns into 100mL.Whereby The concentration for obtaining manganese (II)-eda complex is the 0.2 mole/L aqueous solution.EDA in the aqueous solution relative to Mn mol ratio For 5.
<The preparation of Cu (II)-eda complex aqueous solution>
The ethylenediamine (EDA) of 0.1 mole (6.0g) is set to be dissolved in distilled water 70mL.Addition 2.5 rubs in the aqueous solution That/L dilute sulfuric acid, is thus adjusted to 7 by pH value.Make the CuSO of 0.02 mole (3.19g)4After being dissolved in the aqueous solution, enter And make the Na of 0.05 mole (7.1g)2SO4Dissolving.Then, distilled water is added in a manner of total amount turns into 100mL.Copper is obtained whereby (II) concentration of-eda complex is the 0.2 mole/L aqueous solution.EDA in the aqueous solution is 5 relative to Cu mol ratio.
<Charge and discharge electric test>
Using Mn (II)-eda complex aqueous solution as anode electrolyte, and it is water-soluble using Cu (II)-eda complex Liquid in addition, is operated as electrolyte liquid, carries out charge and discharge electric test and self discharge experiment similarly to Example 1.
The redox reaction that presumption carries out discharge and recharge is as follows.
Positive pole：
Negative pole：
The result of the charge and discharge electric test of embodiment 4 is coulombic efficiency, voltage efficiency, energy efficiency, the utilization rate of electrolyte And electromotive force can obtain good result similarly to Example 1.But the charge/discharge cycle characteristics of embodiment 4 are with repeatedly Carry out discharge and recharge and gradually reduce, the redox flow flow pattern battery of embodiment 4 turns into the 60th circulation left and right without charge and discharge The result of electricity.Learnt according to the result, the charge/discharge cycle characteristics of embodiment 1 are better than embodiment 4.
In embodiment 4, the precipitation of the manganese at electrode after charge and discharge electric test is also more than embodiment 1.

Claims (7)

1. a kind of battery, it is characterised in that possess the electrolyte liquid of water system, the electrolyte liquid contains：
Copper ion and
Amine represented by formula (1)：
Wherein, in formula (1), n represents 1~4 any integer, R1、R2、R3And R4Independently represent hydrogen atom, methyl or ethyl.
2. battery according to claim 1, wherein the amine contains in Diethylenetriamine and three second tetramines at least It is a kind of.
3. battery according to claim 1 or 2, wherein the amine in the electrolyte liquid is relative to copper ion Mol ratio is set in more than 1, less than 5 scope.
4. battery according to claim 1 or 2, wherein making the electrolyte by being dissolved in water copper sulphate Contain the copper ion in liquid.
5. battery according to claim 1 or 2, wherein the content of the copper ion in the electrolyte liquid is 0.2 mole/more than L, in 1.0 moles/below L scope.
6. battery according to claim 1 or 2, wherein the pH value of the electrolyte liquid is more than 3, less than 11 model In enclosing.
7. battery according to claim 1 or 2, wherein the electrolyte liquid is by making in the presence of the amine The copper ion carries out electroreduction reaction and prepared.
CN201280076845.8A 2012-12-25 2012-12-25 Battery Expired - Fee Related CN104781970B (en)

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