CN101572319A - 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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- CN101572319A CN101572319A CNA2009101482180A CN200910148218A CN101572319A CN 101572319 A CN101572319 A CN 101572319A CN A2009101482180 A CNA2009101482180 A CN A2009101482180A CN 200910148218 A CN200910148218 A CN 200910148218A CN 101572319 A CN101572319 A CN 101572319A
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- flow battery
- concentration
- negative pole
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 170
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 27
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910013553 LiNO Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 abstract description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 12
- 239000012528 membrane Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 5
- 238000005341 cation exchange Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 2
- -1 Li + Chemical class 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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 more than 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 first 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 the cathode 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, promote electrolyte and flow through from anodal half-cell and negative pole half-cell respectively, can realize that capacity and power controls respectively by external force.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 store energy and release by 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 is subjected to 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 is achieved through the following technical solutions.
According to an aspect of the present invention, provide a kind of all-vanadium flow battery that is used for the electrolyte of all-vanadium flow battery and comprises this electrolyte.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 described anodal electrolyte is greater than the sulfate ion concentration in the described negative pole electrolyte, and the total V density in described anodal electrolyte and the described negative pole electrolyte is 2.0-8.0mol/L.
Preferably, the sulfate ion concentration in the described anodal electrolyte is 3.0-9.0mol/L, and the sulfate ion concentration in the described negative pole electrolyte is 0.05-3.0mol/L.Further preferably, the sulfate ion concentration in the described anodal electrolyte is 4.0-8.0mol/L, and the sulfate ion concentration in the described negative pole electrolyte is 0.1-2.0mol/L.
Described 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 are dissolved in optional reducing agent 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 described second concentration; And respectively the described anodal electrolyte presoma of electrolysis and described negative pole electrolyte presoma to obtain to be used for the anodal electrolyte and the negative pole electrolyte of all-vanadium flow battery.
Preferably, described first concentration is 3.0-9.0mol/L, and described second concentration is 0.05-3.0mol/L.
Described 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 described negative pole electrolyte presoma comprises the mixture of III valency vanadium or IV valency vanadium or III valency vanadium and IV valency vanadium.
Described reducing agent is selected from least a in the group of being made up of oxalic acid, hydrogen peroxide and sulfur dioxide.
Described 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 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
34+, 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 differently contain the ion of vanadium (as VO
2 +, VO
3 -Deng) in the concentration of all vanadium add and.
In the present invention, the described material of " optionally " 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 by 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, 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, obtaining to comprise III valency vanadium and be V (III) or IV valency vanadium and be the anodal electrolyte presoma of V (IV) or comprising IV valency vanadium is 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, 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, redox reaction is taking place to obtain the vanadium of desired valence state between barium oxide and the reducing agent or between the barium oxide in different valence state in utilization, and because III valency vanadium is V (III), IV valency vanadium is 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 contains the sulfuric acid solution of V (III) or V (IV), what the sulfuric acid solution that perhaps contains the mixture of V (IV) and V (V) or V (III) and the mixture of V (IV) can obtain to have higher total V density contains V (IV), perhaps V (V), the perhaps anodal electrolyte of the mixture of V (IV) and V (V).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 and electro-chemical activity.After placing 45 days down, 25 ℃ of normal temperature do not find precipitation for the electrolyte of 2.0mol/L yet with utilizing the total V density of preparation method's preparation of the present invention, and will utilize the total V density of the method preparation of prior art after 25 ℃ of normal temperature are placed 1 day down, just to begin to occur precipitation for the electrolyte of 2.0mol/L, illustrate and utilize the preparation method who is used for the electrolyte of all-vanadium flow battery of the present invention, even obtain the electrolyte of total V density same as the prior art, also has good stable.
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 1: 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 as 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 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 as 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 as 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 as perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
To find that after placing 100 days under 30 ℃ precipitation produces, and illustrates that this electrolyte has good stable by 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 be that the aqueous sulfuric acid of 3.0mol/L washs with the concentration of about 30mL.Filtrate 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 as perfluoro sulfonic acid membrane, also can be anion-exchange membrane.
To, find yellow mercury oxide in anodal electrolyte, to occur, and the purple precipitation in negative pole electrolyte, occur after 2 days in placement under 30 ℃ by 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 ℃ place 10 days down after, find all that in anodal electrolyte and negative pole electrolyte precipitation occurs, this has illustrated 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 and spirit of the present invention, embodiment is changed or revises.
Claims (10)
1. electrolyte that is used for all-vanadium flow battery, comprise 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 described anodal electrolyte is greater than the sulfate ion concentration in the described negative pole electrolyte, and the total V density in described anodal electrolyte and the described negative pole electrolyte is 2.0-8.0mol/L.
2. the electrolyte that is used for all-vanadium flow battery according to claim 1, wherein, the sulfate ion concentration in the described anodal electrolyte is 3.0-9.0mol/L, the sulfate ion concentration in the described negative pole electrolyte is 0.05-3.0mol/L.
3. the electrolyte that is used for all-vanadium flow battery according to claim 2, wherein, the sulfate ion concentration in the described anodal electrolyte is 4.0-8.0mol/L, the sulfate ion concentration in the described negative pole electrolyte is 0.1-2.0mol/L.
4. the electrolyte that is used for all-vanadium flow battery according to claim 1, wherein, described 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.
5. one kind comprises the all-vanadium flow battery according to each described electrolyte among the claim 1-4.
6. preparation method who is used for the electrolyte of all-vanadium flow battery may further comprise the steps:
Respectively with the oxide of one or more vanadium and optionally reducing agent be 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 greater than described second concentration; And
Described anodal electrolyte presoma of electrolysis and described 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.
7. the preparation method who is used for the electrolyte of all-vanadium flow battery according to claim 6, wherein, described first concentration is 3.0-9.0mol/L, described second concentration is 0.05-3.0mol/L.
8. the preparation method who is used for the electrolyte of all-vanadium flow battery according to claim 6, wherein, described 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 described negative pole electrolyte presoma comprises the mixture of III valency vanadium or IV valency vanadium or III valency vanadium and IV valency vanadium.
9. the preparation method who is used for the electrolyte of all-vanadium flow battery according to claim 6, wherein, described reducing agent is selected from least a in the group of being made up of oxalic acid, hydrogen peroxide and sulfur dioxide.
10. the preparation method who is used for the electrolyte of all-vanadium flow battery according to claim 6, wherein, described 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.
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