CN101572319B - Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte - Google Patents
Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte Download PDFInfo
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- CN101572319B CN101572319B CN2009101482180A CN200910148218A CN101572319B CN 101572319 B CN101572319 B CN 101572319B CN 2009101482180 A CN2009101482180 A CN 2009101482180A CN 200910148218 A CN200910148218 A CN 200910148218A CN 101572319 B CN101572319 B CN 101572319B
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- 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
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- Y02E60/10—Energy storage using 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
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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
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Abstract
The invention provides an electrolyte for an all-vanadium redox flow battery and a preparation method thereof, and an all-vanadium redox flow battery including the electrolyte. The electrolyte for an all-vanadium redox flow battery comprises anode electrolyte and cathode electrolyte which contain vanadiferous ions and sulfate ions, concentration of the sulfate ions in the anode electrolyte is morethan that of the sulfate ions in the cathode electrolyte, the total vanadium concentration of the anode electrolyte and the cathode electrolyte is 2.0-8.0mol/L respectively. The preparation method of the electrolyte for an all-vanadium redox flow battery comprises the following steps: dissolving one or more vanadium oxides and optional reducers in sulfuric acid solution with a first concentration and a second concentration respectively to obtain an anode electrolyte precursor and a cathode electrolyte precursor with the total vanadium concentration of 2.0-8.0mol/L respectively, wherein, the f irst concentration is larger than the second concentration; and electrolyzing the anode electrolyte precursor and the cathode electrolyte precursor respectively to obtain the anode electrolyte and thecathode electrolyte of the all-vanadium redox flow battery.
Description
Technical field
The all-vanadium flow battery that the present invention relates to a kind of electrolyte that is used for all-vanadium flow battery and preparation method thereof and comprise this electrolyte; Particularly, the all-vanadium flow battery that relates to a kind of anodal electrolyte that is used for all-vanadium flow battery and negative pole electrolyte and preparation method thereof and comprise this positive pole electrolyte and this negative pole electrolyte.
Background technology
All-vanadium flow battery has energy conversion efficiency height, long service life, capacity can be become regenerative resource and electric energy peak clippings such as wind energy, solar energy according to customer requirements adjusting, high security and advantages of environment protection, fill out one of the most promising method of scale energy storage such as paddy.
Different with other chemical power sources; The electroactive material of all-vanadium flow battery exists with ion or the ionic associate form that is dissolved in the electrolyte in the charge and discharge process of battery; The both positive and negative polarity active material is stored in respectively in two fluid reservoirs; In running, flow through from anodal half-cell and negative pole half-cell respectively, can realize that capacity and power controls respectively through outer force urges electrolyte.Electrolyte is the core of all-vanadium liquid flow energy storage system.In the flow battery system; Electrolyte is the medium that electric charge transmits between two electrodes with ionic species or ionic associate; The active material vanadium is that V (V), IV valency vanadium are that V (IV), III valency vanadium are that V (III) and II valency vanadium are that V four kinds of valence states such as (II) are present in wherein with V valency vanadium, and battery carries out energy storage and release through the variation of vanadium valence state in the ion that contains vanadium.In energy-storage system, the electrolyte solution of high concentration can be realized the high-energy-density of battery, so electrolyte solution requires to have high stability and high electrochemical activity.Thus, what of all-vanadium flow battery unit volume (or quality) storage power the height of concentration of electrolyte determine, the composition of electrolyte and performance decision liquid energy-storage system multiplying power discharging characteristic, voltage efficiency and energy efficiency etc.
At present, the stable all-vanadium redox flow battery electrolyte of domestic and foreign literature report is the sulfuric acid solution system that total V density is the 2.0-5.0mol/L of 1.4-2.0mol/L.The stability of V (II), V (III), V (IV) strengthens with temperature; Yet V (V) is 40 ℃ and above meeting generation thermoprecipitation effect; So be used for the restriction that the preparation method of the electrolyte of all-vanadium flow battery receives different valence state vanadium solubility in 10 ℃ of-40 ℃ of scopes; The total V density of electrolyte generally in the 2.0mol/L scope, has restricted the raising of liquid energy-storage system specific energy in the all-vanadium flow battery.How to obtain high stability, high concentration electrolyte and become one of bottleneck of high-energy-density all-vanadium flow battery development.
Summary of the invention
The object of the invention is the all-vanadium flow battery that a kind of electrolyte that is used for all-vanadium flow battery and preparation method thereof is provided and comprises this electrolyte.The preparation method who is used for the electrolyte of all-vanadium flow battery according to the present invention can obtain the electrolyte of high concentration, high stability, thereby can improve the specific energy and the energy density of the all-vanadium flow battery that comprises this electrolyte.
The object of the invention realizes through following technical scheme.
According to an aspect of the present invention, a kind of all-vanadium flow battery that is used for the electrolyte of all-vanadium flow battery and comprises this electrolyte is provided.This electrolyte comprises the ion that contains vanadium and the anodal electrolyte and the negative pole electrolyte of sulfate ion; It is characterized in that: the sulfate ion concentration in the said anodal electrolyte is greater than the sulfate ion concentration in the said negative pole electrolyte, and the total V density in said anodal electrolyte and the said negative pole electrolyte is 2.0-8.0mol/L.
Preferably, the sulfate ion concentration in the said anodal electrolyte is 3.0-9.0mol/L, and the sulfate ion concentration in the said negative pole electrolyte is 0.05-3.0mol/L.Further preferably, the sulfate ion concentration in the said anodal electrolyte is 4.0-8.0mol/L, and the sulfate ion concentration in the said negative pole electrolyte is 0.1-2.0mol/L.
Said negative pole electrolyte comprises and is selected from by LiNO
3, NaNO
3, KNO
3, LiCl, NaCl, KCl, Li
2SO
4, Na
2SO
4, and K
2SO
4At least a additive in the group of forming.
According to another aspect of the present invention; A kind of preparation method who is used for the electrolyte of all-vanadium flow battery is provided; May further comprise the steps: one or more barium oxides and optional reducing agent are dissolved in obtain anodal electrolyte presoma and the negative pole electrolyte presoma that total V density is 2.0-8.0mol/L in the sulfuric acid solution with first concentration and second concentration respectively, wherein said first concentration is greater than said second concentration; And respectively the said anodal electrolyte presoma of electrolysis and said negative pole electrolyte presoma to obtain to be used for the anodal electrolyte and the negative pole electrolyte of all-vanadium flow battery.
Preferably, said first concentration is 3.0-9.0mol/L, and said second concentration is 0.05-3.0mol/L.
Said anodal electrolyte presoma comprises the mixture of III valency vanadium or IV valency vanadium or III valency vanadium and IV valency vanadium or the mixture of IV valency vanadium and V valency vanadium, and said negative pole electrolyte presoma comprises the mixture of III valency vanadium or IV valency vanadium or III valency vanadium and IV valency vanadium.
Said reducing agent is selected from least a in the group of being made up of oxalic acid, hydrogen peroxide solution and sulfur dioxide.
Said negative pole electrolyte comprises and is selected from by LiNO
3, NaNO
3, KNO
3, LiCl, NaCl, KCl, Li
2SO
4, Na
2SO
4, and K
2SO
4At least a additive in the group of forming.
Be used for the electrolyte that the preparation method of the electrolyte of all-vanadium flow battery obtains according to the present invention and have higher total V density, good stable property and electro-chemical activity.
Embodiment
Below will be to according to electrolyte that is used for all-vanadium flow battery of the present invention and preparation method thereof and comprise that the all-vanadium flow battery of this electrolyte specifically describes; Those skilled in the art should understand; Following specific descriptions are for the ease of understanding the present invention, not being used for limiting protection scope of the present invention.
In the present invention, V (V) can be with VO
2 +, VO
3 -, V
2O
3 4+, V
2O
4 2+Exist etc. form, V (IV) can be with VO
2+Exist etc. form, V (III) can be with V
3+Exist etc. form, V (II) can be with V
2+Exist etc. form.The ion that contains vanadium can be VO
2 +, VO
3 -, V
2O
3 4+, V
2O
4 2+, VO
2+, V
3+, V
2+Deng." total V density " in the present invention be meant different valence state (as+divalent ,+3 valencys ,+4 valencys ,+5 valencys) the ion that contains vanadium and same valence state in the different ions that contain vanadium (like VO
2 +, VO
3 -Deng) in the concentration of all vanadium add with.
In the present invention, the described material of " optional " expression can exist also and can not exist." first concentration " and " second concentration " only is in order to distinguish the difference of concentration, and does not have other implications.
The preparation method of the electrolyte that is used for all-vanadium flow battery of the present invention is according to the dissolubility difference of different valence state vfanadium compound at the variable concentrations sulfuric acid solution, and preparation is used for the anodal electrolyte presoma and the negative pole electrolyte presoma of all-vanadium flow battery respectively; Then, obtain the anodal electrolyte and the negative pole electrolyte of high concentration, high stability respectively through the method for electrolysis.
In embodiments of the present invention, the preparation method who is used for the electrolyte of all-vanadium flow battery comprises following concrete steps: at first, and with the oxide such as the V of V valency vanadium
2O
5Deng with a kind of reducing agent such as oxalic acid, hydrogen peroxide solution, sulfur dioxide etc. or will be such as V
2O
3With V
2O
5Multiple barium oxide to add concentration be in the sulfuric acid solution of 3.0-9.0mol/L, obtain to comprise III valency vanadium and be V (III) or IV valency vanadium and be V (IV) anodal electrolyte presoma, or to comprise IV valency vanadium be V (IV) and V valency vanadium is that mixture or the III valency vanadium of V (V) is that V (III) is the anodal electrolyte presoma of the mixture of V (IV) with IV valency vanadium; And, with a kind of barium oxide such as V
2O
5Or V
2O
3Deng with optional a kind of reducing agent such as oxalic acid, hydrogen peroxide solution, sulfur dioxide etc. or will be such as V
2O
3With V
2O
5Multiple barium oxide to add concentration be in the sulfuric acid solution of 0.05-3.0mol/L, obtaining to comprise III valency vanadium and be V (III) or IV valency vanadium and be the negative pole electrolyte presoma of V (IV) or comprising III valency vanadium is that V (III) is the negative pole electrolyte presoma of the mixture of V (IV) with IV valency vanadium.Wherein, be V at barium oxide
2O
3Situation under, when preparation negative pole electrolyte presoma, can not add reducing agent.Then, with above-mentioned anodal electrolyte presoma and negative pole electrolyte presoma, placing the electrolysis tank that separates with amberplex respectively, is anode electrode with the platinized titanium net, is negative electrode with carbon element class materials such as graphite, at 0.5-260mAcm
-2Current density under carry out electrolysis, obtain respectively total V density all>=anodal electrolyte that is used for all-vanadium flow battery and the negative pole electrolyte of 2.0mol/L.
In the above-described embodiment; Be utilized in and redox reaction perhaps take place between barium oxide and the reducing agent between the barium oxide of different valence state to obtain the vanadium of desired valence state; And since III valency vanadium is V (III), IV valency vanadium be V (IV) and V valency vanadium be V (V) concentration be 3.0-9.0mol/L than concentrated sulfuric acid solution in have higher solubility, so electrolysis contain V (III) or V (IV) sulfuric acid solution, or the sulfuric acid solution of the mixture or the V (III) that contain V (IV) and V (V) and the mixture of V (IV) can obtain to have the anodal electrolyte that contains V (IV) or V (V) or V (IV) and the mixture of V (V) of higher total V density.And since V (II), V (III) and V (IV) concentration be 0.05-3.0mol/L than dilution heat of sulfuric acid in have higher solubility, so the sulfuric acid solution that electrolysis contains the sulfuric acid solution of V (III) or V (IV) or contains V (III) and the mixture of V (IV) can obtain to have the negative pole electrolyte that contains V (II) or V (III) or V (II) and the mixture of V (III) of higher total V density.
Because sulfate ion concentration is lower in negative pole electrolyte, so can add alkali metal such as Li
+, Na
+, K
+, Rb
+Deng sulfate and nitrate be supporting electrolyte, this not only can strengthen the electric conductivity of electrolyte, can increase the osmotic pressure of negative pole electrolyte again, reduces the migration of water in amberplex.
Adopt the anodal electrolyte of the all-vanadium flow battery that above-mentioned preparation method obtains and the total V density in the negative pole electrolyte all can reach 2.0-8.0mol/L, and this electrolyte have good stable property and electro-chemical activity.The total V density that utilizes preparation method's preparation of the present invention is not found deposition for the electrolyte of 2.0mol/L in 25 ℃ of held of normal temperature yet after 45 days; And will utilize the total V density of the method preparation of prior art just to begin to occur deposition after 1 day in 25 ℃ of held of normal temperature for the electrolyte of 2.0mol/L; Explain and utilize the preparation method who is used for the electrolyte of all-vanadium flow battery of the present invention; Even obtain the electrolyte with the identical total V density of prior art, also have good stable property.
Because the concentration of active material has determined the energy density of battery in all-vanadium flow battery; And higher as the total V density in the ion that contains vanadium of active material in the electrolyte that utilizes above-mentioned preparation method to obtain, have high energy density so comprise the all-vanadium flow battery of above-mentioned electrolyte.
Embodiment
Embodiment 1
With mol ratio is l: 1 V
2O
5And V
2O
3Mixture 332.0g to be dissolved in the 1.5L temperature be that 60 ℃, concentration are in the aqueous sulfuric acid of 3.0mol/L, filter while hot, obtaining total V density is the anodal electrolyte presoma of the mixture that comprises V (IV) and V (V) of 2.7mol/L.
With mol ratio 1: 2 V
2O
5And V
2O
3Mixture 241.0g to be dissolved in the 1.0L temperature be that 60 ℃, concentration are in the aqueous sulfuric acid of 0.05mol/L, filter while hot, obtaining total V density is the negative pole electrolyte presoma of the mixture that comprises V (IV) and V (III) of 3.0mol/L.
With above-mentioned anodal electrolyte presoma and negative pole electrolyte presoma, place the electrolysis tank that separates with amberplex respectively, be anode electrode with the platinized titanium net, be negative electrode with carbon element class materials such as graphite, at 0.5-260mAcm
-2Current density under carry out electrolysis, obtaining total V density respectively is anodal electrolyte that is used for all-vanadium flow battery and the negative pole electrolyte of 2.7mol/L and 3.0mol/L.Wherein amberplex can be the cation-exchange membrane like perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
Embodiment 2
Take by weighing the V of 182.0g respectively
2O
5Evenly mix with the oxalic acid of 360.0g; Be dissolved in temperature then and be 90 ℃, concentration and be in the aqueous sulfuric acid of 1000.0mL of 3.0mol/L; Filter while hot, obtaining total V density is the negative pole electrolyte presoma of the mixture that comprises V (IV) and V (III) of 2.0mol/L.
Take by weighing the V of 182.0g
2O
5Be dissolved in the aqueous sulfuric acid that 500.0mL concentration is 9.0mol/L, be heated to 90 ℃, and slowly to drip concentration be 20.0% hydrogen peroxide solution 250mL.Be stirred to V
2O
5Dissolving fully, obtaining total V density is the anodal electrolyte presoma of 4.0mol/L.
With above-mentioned anodal electrolyte presoma and negative pole electrolyte presoma, place the electrolysis tank that separates with amberplex respectively, be anode electrode with the platinized titanium net, be negative electrode with carbon element class materials such as graphite, at 0.5-260mAcm
-2Current density under carry out electrolysis, obtaining total V density respectively is anodal electrolyte that is used for all-vanadium flow battery and the negative pole electrolyte of 4.0mol/L and 2.0mol/L.Wherein amberplex can be the cation-exchange membrane like perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
Embodiment 3
Take by weighing the V of 182.0g
2O
5Be dissolved in the aqueous sulfuric acid that 250.0mL concentration is 3.0mol/L, be heated to 90 ℃, feed SO
2Gas 45L also constantly is stirred to V
2O
5Dissolving fully, obtaining total V density is the anodal electrolyte presoma of 4.0mol/L.
With mol ratio 1: 2 V
2O
5And V
2O
3Mixture 120.5g to be dissolved in the 500.0mL temperature be that 40 ℃, concentration are in the aqueous sulfuric acid of 0.05mol/L, filter while hot, obtaining total V density is the negative pole electrolyte presoma of the mixture that comprises V (IV) and V (III) of 3.0mol/L.
In negative pole electrolyte presoma, add LiNO
3, make the LiNO in the solution
3Concentration reach 1.0mol/L.With above-mentioned anodal electrolyte presoma and negative pole electrolyte presoma, place the electrolysis tank that separates with amberplex respectively, be anode electrode with the platinized titanium net, be negative electrode with carbon element class materials such as graphite, at 0.5-260mAcm
-2Current density under carry out electrolysis, obtain anodal electrolyte that is used for all-vanadium flow battery and negative pole electrolyte that total V density is about 4.0mol/L and 3.0mol/L respectively.Wherein amberplex can be the cation-exchange membrane like perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
Embodiment 4
With mol ratio 1: 2 V
2O
5And V
2O
3Mixture 120.5g to be dissolved in the 750.0mL temperature be that 40 ℃, concentration are in the aqueous sulfuric acid of 3.0mol/L, filter while hot, obtaining total V density is the anodal electrolyte presoma of the mixture that comprises V (IV) and V (III) of 2.0mol/L.
Take by weighing 112.5g V
2O
3Being dissolved in the 750.0mL temperature and being 90 ℃, concentration is in the aqueous sulfuric acid of 0.05mol/L, filters while hot, and obtaining total V density is the negative pole electrolyte presoma that contains V (III) of 3.0mol/L.
In negative pole electrolyte presoma, add KNO
3, make the KNO in the solution
3Concentration reach 1.0mol/L.With above-mentioned anodal electrolyte presoma and negative pole electrolyte presoma, place the electrolysis tank that separates with amberplex respectively, be anode electrode with the platinized titanium net, be negative electrode with carbon element class materials such as graphite, at 260mAcm
-2Current density under carry out electrolysis, obtaining total V density respectively is anodal electrolyte that is used for all-vanadium flow battery and the negative pole electrolyte of 2.0mol/L and 3.0mol/L.Wherein amberplex can be the cation-exchange membrane like perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
To not find after 100 days that 30 ℃ of held deposition produces, and explains that this electrolyte has good stable property through the electrolyte that said method obtains.
Comparative example 1
With mol ratio 1: 2 V
2O
5And V
2O
3Mixture 241.0g mix after, placing volume is the beaker of 2L, slowly adds the aqueous sulfuric acid that 1.2L concentration is 3.0mol/L, is heated to 90 ℃, constant temperature.Constantly be stirred to oxide and dissolve fully, filter, and the concentration of using about 30mL is washed as the aqueous sulfuric acid of 3.0mol/L.Filtrating is transferred in the volumetric flask of 1.5L, the aqueous sulfuric acid that adds concentration and be 3.0mol/L obtains the electrolyte presoma that total V density is about 2.0mol/L to scale.
The electrolyte precursor solution that above-mentioned total V density is about 2.0mol/L is divided into 2 equal portions, places the electrolysis tank that separates with amberplex respectively, is anode electrode with the platinized titanium net, is negative electrode with carbon element class materials such as graphite, at 260mAcm
-2Current density under carry out electrolysis, obtain anodal electrolyte that is used for all-vanadium flow battery and negative pole electrolyte that total V density is about 2.0mol/L respectively.Wherein amberplex can be the cation-exchange membrane like perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
To, find in anodal electrolyte, yellow mercury oxide to occur, and the purple deposition in negative pole electrolyte, occur after 2 days 30 ℃ of held through the electrolyte that said method obtains.And the total V density that obtains according to the method described among the embodiment 1-4 more than or equal to the anodal electrolyte of 2.0mol/L and negative pole electrolyte 30 ℃ of held after 10 days; Find all that in anodal electrolyte and negative pole electrolyte deposition occurs, this has explained that the electrolyte that utilizes the preparation method who is used for the electrolyte of all-vanadium flow battery of the present invention to obtain has higher stability than the electrolyte that conventional method prepares.
Though described spirit of the present invention in detail with reference to specific embodiment, it only is used for illustration purpose and does not limit the present invention.Should be appreciated that those skilled in the art can be under the situation that does not deviate from scope of the present invention and spirit, embodiment is changed or revises.
Claims (3)
1. preparation method who is used for the electrolyte of all-vanadium flow battery may further comprise the steps:
Respectively the oxide of one or more vanadium and optional reducing agent are dissolved in and obtain anodal electrolyte presoma and the negative pole electrolyte presoma that total V density is 2.0-8.0mol/L in the sulfuric acid solution with first concentration and second concentration; Wherein said first concentration is 3.0-9.0mol/L, and said second concentration is 0.05-3.0mol/L;
In said negative pole electrolyte presoma, add and be selected from by LiNO
3, NaNO
3, KNO
3, LiCl, NaCl, KCl, Li
2SO
4, Na
2SO
4, and K
2SO
4At least a additive in the group of forming; And
Said anodal electrolyte presoma of electrolysis and said negative pole electrolyte presoma are to obtain to be used for the anodal electrolyte and the negative pole electrolyte of all-vanadium flow battery respectively.
2. the preparation method who is used for the electrolyte of all-vanadium flow battery according to claim 1; Wherein, Said anodal electrolyte presoma comprises the mixture of III valency vanadium or IV valency vanadium or III valency vanadium and IV valency vanadium or the mixture of IV valency vanadium and V valency vanadium, and said negative pole electrolyte presoma comprises the mixture of III valency vanadium or IV valency vanadium or III valency vanadium and IV valency vanadium.
3. the preparation method who is used for the electrolyte of all-vanadium flow battery according to claim 2, wherein, said reducing agent is selected from least a in the group of being made up of oxalic acid, hydrogen peroxide solution and sulfur dioxide.
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|---|---|---|---|
| CN2009101482180A CN101572319B (en) | 2009-06-18 | 2009-06-18 | Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte |
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|---|---|---|---|
| CN2009101482180A CN101572319B (en) | 2009-06-18 | 2009-06-18 | Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte |
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| CN101572319B true CN101572319B (en) | 2012-01-11 |
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| CN106505234B (en) * | 2015-09-08 | 2019-03-12 | 中国科学院大连化学物理研究所 | A kind of positive electrolyte for all-vanadiumredox flow battery of siliceous heteropoly acid |
| CN106960973B (en) * | 2015-10-21 | 2019-10-25 | 成都九十度工业产品设计有限公司 | A kind of preparation method of the three-phase composite electrode of vanadium cell |
| CN108123159B (en) * | 2016-11-26 | 2020-11-24 | 中国科学院大连化学物理研究所 | Method for improving stability of cathode electrolyte of all-vanadium redox flow battery |
| CN109841885B (en) * | 2017-11-28 | 2021-06-29 | 中国科学院大连化学物理研究所 | Method for improving stability of high-concentration negative electrolyte during operation of all-vanadium redox flow battery |
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