CN100438190C - All-vanadium ion flow battery electrolyte and preparation method thereof - Google Patents
All-vanadium ion flow battery electrolyte and preparation method thereof Download PDFInfo
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- CN100438190C CN100438190C CNB2005100756081A CN200510075608A CN100438190C CN 100438190 C CN100438190 C CN 100438190C CN B2005100756081 A CNB2005100756081 A CN B2005100756081A CN 200510075608 A CN200510075608 A CN 200510075608A CN 100438190 C CN100438190 C CN 100438190C
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910001456 vanadium ion Inorganic materials 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 83
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 9
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 9
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 9
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims description 13
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 6
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims description 5
- -1 salt sulfate Chemical class 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- ZMFKXOMVFFKPEC-UHFFFAOYSA-D [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZMFKXOMVFFKPEC-UHFFFAOYSA-D 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 235000015424 sodium Nutrition 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 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
Landscapes
- Fuel Cell (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte of an all-vanadium ion flow battery, which consists of a vanadium sulfate salt, sulfuric acid, water, ethanol and an additive, wherein the additive is one or more of sodium sulfate, sodium pyrophosphate, sodium fluosilicate and hydrogen peroxide. The invention also provides a preparation method of the electrolyte, which comprises the steps of pumping qualified vanadium liquid of a vanadium plant into a reaction tank, adjusting the pH value of the solution by using sulfuric acid, and introducing liquid SO2After reduction, the pH value of the solution is adjusted by sodium carbonate to obtain VO2Precipitating, dissolving the precipitate in a solution containing sulfuric acid, water and ethanol, adding an additive, and placing the solution in an electrolytic cell for electrolysis to obtain vanadium electrolyte for the vanadium battery, wherein the vanadium with valence 3 and the vanadium with valence 4 respectively account for 50% of the total vanadium, and the concentration of the total vanadium is 1.0-4.2 mol/L. The vanadium electrolyte provided by the invention has high fluidity, stability, electrochemical reaction activity and low-temperature environment resistance of the battery, and the electrolyte for the vanadium battery is directly produced by using an intermediate process product of a vanadium plant, so that the process cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of accumulation energy type fluid flow pattern battery---all-vanadium ionic liquid flow battery, particularly relate to a kind of electrolyte of all-vanadium ionic liquid flow battery.
Background technology
Vanadium cell is one of powerful environmental protection storage battery of present growth momentum, its manufacturing, uses and discarded process does not all produce harmful substance.It has special battery structure, and its active material is similar with fuel cell with the design feature that pile separates, and manufacturing cost is lower than fuel cell, and production technology is relative with fuel cell simple than lead-acid battery.All-vanadium ionic liquid flow battery is because different valence state ion comparative electrode current potential is higher, but degree of depth high current density discharge, charging rapidly, the energy transformation ratio height, can prepare the MW class battery pack, the large power long time provides electric energy, application is very wide, can be used as mansion, airport, programme-controlled exchange station stand-by power supply, the supporting energy storage device of clean electric power generation systems such as solar energy, and, have lithium ion battery, the incomparable superiority of effectiveness of Ni-MH battery in extensive energy storage field for ocean-going ship provides electric power and is used for peak load regulation network etc.Its production technology is simple, price economy, and the electrical property excellence,, expensive fuel cell complicated with manufacturing compared, and no matter is aspect the extensive energy storage or the application prospect of electric powered motor power supply, all has more competitive strength.
All-vanadium ionic liquid flow battery adopts and contains vanadium solution as positive and negative electrode electrolyte, finishes electron exchange on positive and negative electrode, realizes its charge and discharge; Wherein mainly adopt the active material of vanadic sulfate, i.e. electrolyte as battery.Vanadic sulfate, sulfuric acid and water are prepared V electrolyte in proportion, form vanadium cell jointly with suitable electrode material, conductive diaphragm material, battery container, electrolyte storage tank and electrolyte delivery system.Prior art is with V
2O
5Be dissolved in sulfuric acid, use liquid SO
2Deng the reducing agent reduction, vanadium concentration is adjusted in the back that reacts completely, and adds additive, places the electrolysis tank electrolysis, obtains the vanadium cell V electrolyte.The V that uses in this technology
2O
5Be to obtain after the precipitation of qualified vanadium liquid process, filtration, drying and 500 ℃ of high-temperature roastings, the V electrolyte cost is higher; In addition, sulfuric acid dissolution V
2O
5Reaction under 300 ℃ of high temperature, carry out, to the equipment requirements height.
In V electrolyte charge and discharge when operation in vanadium cell,, the viscosity of electrolyte, conductivity and the stability under the varying environment temperature have bigger influence to the performance of battery.Existing V electrolyte main body composition is V salt sulfate [anodal (VO
2)
2SO
4And VOSO
4, negative pole V
2(SO
4)
3And VSO
4] and sulfuric acid and water, there is the high defective of viscosity, influence its stability and conductivity, especially be difficult to adapt to low temperature environment.Add stabilizer such as alcohols, organic acid, salt or macromolecular compound in the described V electrolyte of Chinese patent (publication number CN 1507103) " the static vanadium cell of high energy ", " pentavalent and the divalent vanadium ion concentration concentration that oversteps the extreme limit can not precipitated or separate out; can form colloid or keep solution state; " add stabilizer purpose only be precipitation or separate out when preventing the vanadium ion high concentration, and this application does not disclose the charge-discharge performance of this electrolyte.The article of Xu Qian etc. the stability of electrolyte of vanadium redox battery " improve " (power technology vol.26 No.1Feb.2002) has been introduced and has been added stability and the conductivity that 2% sodium sulphate has improved V electrolyte (sulfuric acid, aqueous systems), at sulfuric acid, water, ethanol system stability and conductivity with the research of low temperature serviceability is kind does not report.
Therefore, all-vanadium ionic liquid flow battery press for new can the low-cost preparation method who obtains V electrolyte, and new electrolyte prescription system is improving the stability and the electric conductivity of solution, and the performance used under low temperature environment of battery.
Summary of the invention
In order to address the above problem, the invention provides the preparation method of a kind of V electrolyte and V electrolyte.
V electrolyte provided by the invention consists of: V salt sulfate, sulfuric acid, ethanol, water and additive, described additive is one or more in sodium sulphate, sodium pyrophosphate, prodan, the hydrogen peroxide, and the additive proportion is 0%～5%w/w of electrolyte total weight.
Total V density is in the described full vanadium ion fluid cell electrolyte: 1.0～4.2mol/L, sulfuric acid concentration is: 1.5～3.5mol/L, concentration of alcohol is: 15%～50%v/v, additive level are 0%～5%w/w.
Further, total V density is in the described full vanadium ion fluid cell electrolyte: 1.5～3.0mol/L, sulfuric acid concentration is: 2.0～3.5mol/L, concentration of alcohol is: 20～40%v/v, additive level are 0%～5%w/w.
The preparation method of V electrolyte provided by the invention is:
A, (total V density is 0.29～0.35mol/L) to pump into retort, and pH value to 0.2～2.0 with sulfuric acid regulation solution feed liquid SO with the qualified vanadium liquid of vanadium factory
2Reduction;
B, react completely after, with pH value to 3.5～5.5 of manganese hydrogen sodium regulating solution, acquisition VO
2Precipitation;
C, above-mentioned precipitation is dissolved in the solution that contains sulfuric acid, water and ethanol, adds other additive, place the electrolysis tank electrolysis, obtain the vanadium cell V electrolyte that 3 valency vanadium and 4 valency vanadium respectively account for total vanadium 50%, total V density 1.0mol/L～4.2mol/L.With this electrolyte fluid reservoir of packing into, pump into the vanadium cell pile and can carry out the charge and discharge operation.
Further, a step is regulated pH value 4～5 with pH value to 0.8～1.5 of sulfuric acid regulation solution, b step sodium acid carbonate.
The present invention uses the pilot process product " qualified vanadium solution " of vanadium factory, than using V
2O
5More can simplify production technology, reduce cost.The main body composition of V electrolyte is V salt sulfate, sulfuric acid, water and ethanol.The adding of a large amount of ethanol has reduced the viscosity of solution, has improved the stability of solution, has improved the electric conductivity of solution, has improved the performance that battery uses under low temperature environment greatly.Use additive further to improve the stability and the conductivity of electrolyte.
The invention will be further described below by the mode of specific embodiment, but should not be construed as is limitation of the invention further, according to foregoing of the present invention, the technology that modification, replacement or change realized of making other various ways all belongs to scope of the present invention.
Embodiment:
Embodiment 1
Take by weighing 2000 gram qualified vanadium liquid (0.349mol/L), adding the concentrated sulfuric acid to pH value is 1.0, feeds SO
2Reaction, adding sodium carbonate to pH value is 4.5, filters, and precipitation is dissolved in (sulfuric acid 60mL, water 200mL) in sulfuric acid, the water, obtains the vanadic sulfate aqueous sulfuric acid of the blue look of 300mL, and test: sulfuric acid concentration 2mol/L, the concentration of vanadium is 2mol/L.Above-mentioned vanadium solution places cathode of electrolytic tank; Preparation 2mol/L sulfuric acid, 1.2mol/L Na
2SO
4Solution places electrolytic cell anode; Adopt the current constant mode electrolysis, current density 50mA/cm
2Electrolysis to the potential value of V electrolyte is 200mV, and electrolyte is carried out Potential Titration Analysis, and the ratio of 4 valency vanadium concentration and 3 valency vanadium concentration is 1: 1.Power taking is separated each 35mL of electrolyte of preparation in the positive pole and the negative pole of vanadium cell model, discharges and recharges test, and this is the V electrolyte of sulfuric acid+aqueous systems.
Take by weighing 2000 gram qualified vanadium liquid (0.349mol/L), adding the concentrated sulfuric acid to pH value is 1.0, feeds S0
2Reaction, adding sodium carbonate to pH value is 4.2, filter, filtrate is returned qualified vanadium liquid and is reused, precipitate in the solution that is dissolved in sulfuric acid, water and ethanol (sulfuric acid 60mL, water 80mL and ethanol 120mL), obtain the vanadic sulfate ethanol solution of sulfuric acid of the blue look of 300mL, test: sulfuric acid concentration 2mol/L, the concentration of vanadium is 2mol/L.Above-mentioned vanadium solution places cathode of electrolytic tank; Preparation 2mol/L sulfuric acid, 1.2mol/L Na
2SO
4Solution places electrolytic cell anode; Adopt the current constant mode electrolysis, current density 50mA/cm
2Electrolysis to the potential value of V electrolyte is 200mV, and electrolyte is carried out Potential Titration Analysis, and the ratio of 4 valency vanadium concentration and 3 valency vanadium concentration is 1: 1.Power taking is separated each 35mL of electrolyte of preparation in the positive pole and the negative pole of vanadium cell model, discharges and recharges test, and this is the V electrolyte that sulfuric acid+ethanol (40%) system does not contain additive.
Electrolyte (total V density 2mol/L) viscosity and conductivity contrast and experiment under different temperatures see Table 1.
Battery electrode adopts graphite felt, and collector material adopts the high-density graphite plate, and conductive diaphragm adopts the Nafion proton exchange membrane after the activation processing, and polyurethane sheet is made liquid flow frame plate, cathode pool 100 * 100 * 5mm, anode pond 100 * 100 * 5mm.Electrolyte vanadium concentration 2mol/L, sulfuric acid concentration 2mol/L.Battery charge and discharge performance test the results are shown in Table 2.
Embodiment 2
Take by weighing 2000 gram qualified vanadium liquid (0.349mol/L), adding the concentrated sulfuric acid to pH value is 1.0, feeds SO
2Reaction, adding sodium carbonate to pH value is 4.2, filters, filtrate is returned qualified vanadium liquid and is reused, and precipitates in the solution that is dissolved in sulfuric acid, water and ethanol (sulfuric acid 60mL, water 80mL and ethanol 120mL), adds Na
2SO
46 grams, sodium pyrophosphate 4 restrain, and obtain the vanadic sulfate ethanol solution of sulfuric acid of the blue look of 300mL, and test: sulfuric acid concentration 2mol/L, the concentration of vanadium is 2mol/L.Above-mentioned vanadium solution places cathode of electrolytic tank; Preparation 2mol/L sulfuric acid, 1.2mol/LNa
2SO
4Solution places electrolytic cell anode; Adopt the current constant mode electrolysis, current density 50mA/cm
2Electrolysis to the potential value of V electrolyte is 200mV, and electrolyte is carried out Potential Titration Analysis, and the ratio of 4 valency vanadium concentration and 3 valency vanadium concentration is 1: 1.Power taking is separated each 35mL of electrolyte of preparation in the positive pole and the negative pole of vanadium cell model, discharges and recharges test, and this is the V electrolyte of sulfuric acid+ethanol (40%) system.
Electrolyte (total V density 2mol/L) viscosity and conductivity contrast and experiment under different temperatures see Table 1.
Battery electrode adopts graphite felt, and collector material adopts the high-density graphite plate, and conductive diaphragm adopts the Nafion proton exchange membrane after the activation processing, and polyurethane sheet is made liquid flow frame plate, cathode pool 100 * 100 * 5mm, anode pond 100 * 100 * 5mm.Electrolyte vanadium concentration 2mol/L, sulfuric acid concentration 2mol/L.Battery charge and discharge performance test the results are shown in Table 2.
The viscosity and the conductivity of electrolyte under the table 1 varying environment temperature
Battery electrode adopts graphite felt, and collector material adopts the high-density graphite plate, and conductive diaphragm adopts the Nafion proton exchange membrane after the activation processing, and polyurethane sheet is made liquid flow frame plate, cathode pool 100 * 100 * 5mm, anode pond 100 * 100 * 5mm.Electrolyte vanadium concentration 2mol/L, sulfuric acid concentration 2mol/L.Battery charge and discharge performance test the results are shown in Table 2.
Battery charge and discharge performance comparison under the table 2 varying environment temperature
The adding of a large amount of ethanol of The above results explanation the present invention, reduced the viscosity of solution, improved the stability of solution, improved the electric conductivity of solution, improved the performance that battery uses greatly under low temperature (～-14 ℃) environment, low temperature-14 ℃, circulating still can keep 70% voltage efficiency 20 times.The use of additive has further improved the stability and the conductivity of electrolyte.
Embodiment 3
Qualified vanadium liquid (climb steel and climb grand company) total V density is 0.349mol/L
H
2SO
4: analyze pure, d=1.84
Liquid SO
2: analyze pure
Sodium carbonate: analyze pure
Ethanol: analyze pure
Na
2SO
4: analyze pure
Sodium pyrophosphate: analyze pure
Prodan: analyze pure
Hydrogen peroxide: analyze pure, 30%
The vanadium cell modelling: polyurethane sheet is made deckle board, and conductive diaphragm adopts the Nafion proton exchange membrane after the activation processing, cathode pool 100 * 100 * 5mm, anode pond 100 * 100 * 5mm, the self-control graphite electrode of 100 * 100 * 1.5mm.
Take by weighing the qualified vanadium liquid of 2000 grams, adding the concentrated sulfuric acid to pH value is 1.0, feeds SO
2Reaction, adding sodium carbonate to pH value is 4.2, filters, filtrate is returned qualified vanadium liquid and is reused, and precipitates in the solution that is dissolved in sulfuric acid, water and ethanol (sulfuric acid 60mL, water 100mL and ethanol 120mL), adds Na
2SO
46 grams, sodium pyrophosphate 4 restrain, and obtain the vanadic sulfate ethanol solution of sulfuric acid of the blue look of 300mL, and test: sulfuric acid concentration 2mol/L, the concentration of vanadium is 1.5mol/L.Above-mentioned vanadium solution places cathode of electrolytic tank; Preparation 2mol/L sulfuric acid, 1.2mol/L Na
2SO
4Solution places electrolytic cell anode; Adopt the current constant mode electrolysis, current density 50mA/cm
2Electrolysis to the potential value of V electrolyte is 200mV, and electrolyte is carried out Potential Titration Analysis, and the ratio of 4 valency vanadium concentration and 3 valency vanadium concentration is 1: 1.Power taking is separated each 35mL of electrolyte of preparation in the positive pole and the negative pole of vanadium cell model, discharges and recharges test, and stability and conductivity height, anti-low temperature environment ability are strong, and charging platform is 1.7V, and discharge platform is 1.2V, voltage efficiency 85%.
Embodiment 4
Qualified vanadium liquid (climb steel and climb grand company) total V density is 0.343mol/L
H
2SO
4: analyze pure, d=1.84
Liquid SO
2: analyze pure
Sodium carbonate: analyze pure
Ethanol: analyze pure
Na
2SO
4: analyze pure
Sodium pyrophosphate: analyze pure
Prodan: analyze pure
Hydrogen peroxide: analyze pure, 30%
The vanadium cell modelling: polyurethane sheet is made deckle board, and conductive diaphragm adopts the Nafion proton exchange membrane after the activation processing, cathode pool 100 * 100 * 5mm, and anode pond 100 * 100 * 5mm, 100 * 100 * 1.5mm makes graphite electrode by oneself.
Take by weighing the qualified vanadium liquid of 2000 grams, adding the concentrated sulfuric acid to pH value is 1.2, feeds SO
2Reaction, adding sodium carbonate to pH value is 5.1, filters, filtrate is returned qualified vanadium liquid and is reused, and precipitates in the solution that is dissolved in sulfuric acid, water and ethanol (sulfuric acid 60mL, water 10mL and ethanol 40mL), adds Na
2SO
43 grams, sodium pyrophosphate 3 restrain, and obtain the vanadic sulfate ethanol solution of sulfuric acid of blue look, and test: sulfuric acid concentration 3.8mol/L, the concentration of vanadium is 4.2mol/L.Above-mentioned vanadium solution places cathode of electrolytic tank; Preparation 2mol/L sulfuric acid, 1.2mol/L Na
2SO
4Solution places electrolytic cell anode; Adopt the current constant mode electrolysis, current density 60mA/cm
2Electrolysis to the potential value of V electrolyte is 250mV, and electrolyte is carried out Potential Titration Analysis, and the ratio of 4 valency vanadium concentration and 3 valency vanadium concentration is 1: 1.Power taking is separated each 35mL of electrolyte of preparation in the positive pole and the negative pole of vanadium cell model, discharges and recharges test, and stability and conductivity height, anti-low temperature environment ability are strong, and charging platform is 1.7V, and discharge platform is 1.2v, voltage efficiency 85%.
In a word, the present invention uses the pilot process product of vanadium factory directly to produce electrolyte for vanadium cell, can reduce the technology cost, uses ethanol and other additive, can improve electrolyte flow, stability, the anti-low temperature environment ability of electrochemical reaction activity and battery.
Claims (9)
1, full vanadium ion fluid cell electrolyte is characterized in that: it is that 0～5%w/w additive is formed by V salt sulfate, sulfuric acid, water, ethanol and content, and described additive is one or more in sodium sulphate, sodium pyrophosphate, prodan, the hydrogen peroxide; Wherein, concentration of alcohol is in the described full vanadium ion fluid cell electrolyte: 20～40%v/v.
2, full vanadium ion fluid cell electrolyte according to claim 1 is characterized in that: total V density is in the described full vanadium ion fluid cell electrolyte: 1.0～4.2mol/L, sulfuric acid concentration is: 1.5～3.5mol/L.
3, full vanadium ion fluid cell electrolyte according to claim 2 is characterized in that: total V density is in the described full vanadium ion fluid cell electrolyte: 1.5～3.0mol/L, sulfuric acid concentration is: 2.0～3.5mol/L.
4, prepare the method for the described full vanadium ion fluid cell electrolyte of claim 1, it is characterized in that: it may further comprise the steps:
A, with total V density be the vanadium liquid of 0.29～0.35mol/L under the condition of pH value 0.2～2.0, be reduced into vanadic sulfate solution with reducing agent;
B, above-mentioned vanadic sulfate pH value of solution value is adjusted to 3.5～5.5, obtains the vanadium dioxide precipitation;
C, vanadium dioxide is dissolved in the system of sulfuric acid, second alcohol and water, add the additive of 0%～5%w/w, obtain full vanadium ion fluid cell electrolyte by electrolytic preparation, wherein, total V density is 1.0mol/L～4.2mol/L, and trivalent vanadium and tetravalence vanadium respectively account for 50% of total vanadium.
5, according to the said preparation method of electrolyte of claim 4, it is characterized in that: the acid condition that the described vanadium liquid of a step is reduced into vanadic sulfate is a pH value 0.8～1.5.
6, according to the said preparation method of electrolyte of claim 4, it is characterized in that: the reducing agent that the described vanadium liquid of a step is reduced into vanadic sulfate is liquid SO
2
7, according to the said preparation method of electrolyte of claim 4, it is characterized in that: the described pH value of b step is adjusted to 4～5.
8, according to the said preparation method of electrolyte of claim 4, it is characterized in that: in the b step, use sodium carbonate or sodium acid carbonate reagent to regulate the pH value.
9, according to the said preparation method of electrolyte of claim 4, it is characterized in that: the described additive of c step comprises: Na
2SO
4, at least a in the sodium pyrophosphate, prodan, hydrogen peroxide.
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