CN107658487A - A kind of electrolyte of vanadium redox battery - Google Patents
A kind of electrolyte of vanadium redox battery Download PDFInfo
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- CN107658487A CN107658487A CN201711036668.1A CN201711036668A CN107658487A CN 107658487 A CN107658487 A CN 107658487A CN 201711036668 A CN201711036668 A CN 201711036668A CN 107658487 A CN107658487 A CN 107658487A
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- molybdate
- oxalate
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- calcium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to battery electrolyte technical field, especially a kind of electrolyte of vanadium redox battery；The ion liquid addictive is selected from least one of sodium molybdate, ammonium molybdate, potassium molybdate, lithium molybdate, magnesium molybdate, zinc molybdate, iron molybdate, manganese molybdate, calcium molybdate from least one of inorganic molybdate, phosphate, oxalates, the inorganic molybdate；The oxalates is selected from least one of sodium oxalate, ammonium oxalate, potassium oxalate, lithium oxalate, magnesium oxalate, zinc oxalate, ferric oxalate, manganese oxalate, calcium oxalate；The additive of the present invention can improve the solubility of electrolyte, suppress the hydrolysis of pentavalent vanadium ion, greatly improve the stability of anolyte；Present invention uses inorganic molybdate as anolyte solution additive, the stability of anode electrolyte is improved, has widened the temperature range of operation of vanadium cell.Preparation technology of the present invention is simple to operate, cost is low while is easily achieved the high-temperature stable operation of vanadium cell.
Description
Technical field
The present invention relates to battery electrolyte technical field, especially a kind of electrolyte of vanadium redox battery.
Background technology
Vanadium redox battery possesses adjustable energy conversion efficiency height, capacity, service life length, high security
And advantages of environment protection, it is mainly used in the supporting energy storage devices of electricity generation system of the regenerative resources such as solar energy, wind energy, power network
Peak-clipping and valley-filling device and uninterrupted power source and emergency power system.
In vanadium cell, the energy content of battery is stored in the form of electrolyte, and it is made up of vanadium ion and sulfuric acid, and positive pole is
It is made up of VO2+/VO2+ oxidation-reduction pairs, negative pole is made up of V3+/V2+ group oxidation-reduction pairs.Improve the dense of electrolyte
Degree is the effective way for the ratio energy for improving battery.But because vanadium there are vacant d tracks, not only easily combined with ligand, vanadium
Also easily associated between atom.Concentration is bigger, and degree of association is bigger.Complicated ions participate in electrochemical reaction, corresponding reaction energy barrier
Increase, causes polarization to increase, and reaction speed is slow.And the raising of concentration will necessarily increase resistance, viscosity of electrolyte etc..Together
When, pentavalent vanadium ion solubility is little, and the positive solution of high concentration can separate out red vanadate and sink when close to fully charged state
Form sediment, porous electrode surface may be blocked, cause battery not use.Research also shows trivalent and divalent vanadium ion at low temperature
Also easily precipitate, there is also problem for the stability of this explanation electrolyte liquid.
The method of the stability of increase vanadium solution mainly includes improving solution acidity and adds two kinds of additive at present.Solution
The too high corrosion that can accelerate to battery component of acidity, improves the requirement to material.And for electrolyte liquid, due to homo-ion
The reason of effect, acidity increase can reduce the solubility of low price vanadium ion on the contrary.Therefore, the scheme of additive is introduced to electrolyte
It has been extensively studied.
But the solubility of current electrolyte of vanadium redox battery and the degree of corrosion to battery component also have optimization.
The content of the invention
The purpose of the present invention is：Overcome deficiency of the prior art, there is provided a kind of performance is more excellent, solubility is high, to part
The low electrolyte of vanadium redox battery of corrosivity additive.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the ion liquid addictive is from inorganic
At least one of molybdate, phosphate, oxalates,
The inorganic molybdate is selected from sodium molybdate, ammonium molybdate, potassium molybdate, lithium molybdate, magnesium molybdate, zinc molybdate, iron molybdate, molybdic acid
At least one of manganese, calcium molybdate；The oxalates is selected from sodium oxalate, ammonium oxalate, potassium oxalate, lithium oxalate, magnesium oxalate, oxalic acid
At least one of zinc, ferric oxalate, manganese oxalate, calcium oxalate；The phosphate is selected from sodium phosphate, ammonium phosphate, potassium phosphate, phosphoric acid
At least one of lithium, magnesium phosphate, trbasic zinc phosphate, ferric phosphate, manganese phosphate, calcium phosphate.
Preferably, the concentration of the vanadium ion is 1.6-2.8mol/l.
Preferably, for the ion liquid addictive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:
1.1-1.5。
Preferably, for the ion liquid addictive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:
1.2。
Preferably, the inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, its quality
Than for 1:0.2-1.2:1.2-1.8.
Preferably, the inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, its quality
Than for 1:0.8:1.5.
Preferably, the oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.2-
1.5:1-1.6。
Preferably, it is 1 that the oxalates, which is selected from zinc oxalate, ferric oxalate, the mass ratio of calcium oxalate,:1.3:1.3.
It is using the beneficial effect of technical scheme：
1st, additive of the invention can improve the solubility of electrolyte, suppress the hydrolysis of pentavalent vanadium ion, greatly improve positive pole
The stability of electrolysis.
2nd, present invention uses inorganic molybdate as anolyte solution additive, improves the stabilization of anode electrolyte
Property, widen the temperature range of operation of vanadium cell.Preparation technology of the present invention is simple to operate, cost is low while is easily achieved vanadium electricity
The high-temperature stable operation in pond.
Embodiment
The present invention is described further presently in connection with specific embodiment.
Embodiment 1
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 1.6mol/l；Institute
State ion liquid addictive and select inorganic molybdate, the inorganic molybdate is selected from sodium molybdate.
Embodiment 2
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 1.8mol/l；Its
In, for ion liquid addictive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:1.1；Wherein, inorganic molybdic acid
Salt is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:0.2:1.2.
Wherein, oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.2:1.
Embodiment 3
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 2mol/l；Ion
For liquid additive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:1.2.
Wherein, inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:
0.8:1.5。
Wherein, oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.3:1.3.
Embodiment 4
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 2.1mol/l；From
For sub- liquid additive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:1.3.
Wherein, inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:
0.8:1.6。
Wherein, oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.3:1.6.
Embodiment 5
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 2.5mol/l；Its
In, for ion liquid addictive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:1.4.
Wherein, inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:
1.1:1.6。
Wherein, oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.4:1.5.
Embodiment 6
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 2.8mol/l；Its
In, for ion liquid addictive from inorganic molybdate and the mixture of oxalates, its mass ratio is 1:1.5.
Wherein, inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:
1.2:1.8。
Wherein, oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.5:1.6.
Embodiment 7
A kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, the concentration of vanadium ion is 2.8mol/l；Its
In, ion liquid addictive selects the mixture of inorganic molybdate, phosphate and oxalates, and its mass ratio is 1:1.1:1.5.
Wherein, inorganic molybdate is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:
1.2:1.8。
Wherein, oxalates is selected from zinc oxalate, ferric oxalate, the mixture of calcium oxalate, and its mass ratio is 1:1.5:1.6.
The additive of the present invention can improve the solubility of electrolyte, suppress the hydrolysis of pentavalent vanadium ion, greatly improve just
The stability of pole electrolysis.
Present invention uses inorganic molybdate as anolyte solution additive, improves the stability of anode electrolyte,
The temperature range of operation of vanadium cell is widened.Preparation technology of the present invention is simple to operate, cost is low while is easily achieved vanadium cell
High-temperature stable is run.
It is complete by above-mentioned description, relevant staff using the above-mentioned desirable embodiment according to the present invention as enlightenment
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to determines its technical scope according to right.
Claims (8)
1. a kind of electrolyte of vanadium redox battery, including vanadium ion, sulfuric acid and ionic liquid composition, it is characterised in that：The ionic liquid
Additive selects at least one of inorganic molybdate, phosphate, oxalates,
The inorganic molybdate is selected from sodium molybdate, ammonium molybdate, potassium molybdate, lithium molybdate, magnesium molybdate, zinc molybdate, iron molybdate, molybdic acid
At least one of manganese, calcium molybdate；The oxalates is selected from sodium oxalate, ammonium oxalate, potassium oxalate, lithium oxalate, magnesium oxalate, oxalic acid
At least one of zinc, ferric oxalate, manganese oxalate, calcium oxalate；The phosphate is selected from sodium phosphate, ammonium phosphate, potassium phosphate, phosphoric acid
At least one of lithium, magnesium phosphate, trbasic zinc phosphate, ferric phosphate, manganese phosphate, calcium phosphate.
A kind of 2. electrolyte of vanadium redox battery according to claim 1, it is characterised in that：The concentration of the vanadium ion is 1.6-
2.8mol/l。
A kind of 3. electrolyte of vanadium redox battery according to claim 1, it is characterised in that：The ion liquid addictive selects nothing
The mixture of machine molybdate and oxalates, its mass ratio are 1:1.1-1.5.
A kind of 4. electrolyte of vanadium redox battery according to claim 3, it is characterised in that：The ion liquid addictive selects nothing
The mixture of machine molybdate and oxalates, its mass ratio are 1:1.2.
A kind of 5. electrolyte of vanadium redox battery according to any one of claim 3 or 4, it is characterised in that：The inorganic molybdic acid
Salt is selected from the mixture of sodium molybdate, lithium molybdate, magnesium molybdate and calcium molybdate, and its mass ratio is 1:0.2-1.2:1.2-1.8.
A kind of 6. electrolyte of vanadium redox battery according to claim 5, it is characterised in that：The inorganic molybdate is selected from molybdic acid
Sodium, lithium molybdate, the mixture of magnesium molybdate and calcium molybdate, its mass ratio are 1:0.8:1.5.
A kind of 7. electrolyte of vanadium redox battery according to claim 1, it is characterised in that：The oxalates is selected from zinc oxalate, grass
The mixture of sour iron, calcium oxalate, its mass ratio are 1:1.2-1.5:1-1.6.
A kind of 8. electrolyte of vanadium redox battery according to claim 7, it is characterised in that：The careless salt is selected from zinc oxalate, oxalic acid
Iron, the mass ratio of calcium oxalate are 1:1.3:1.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711036668.1A CN107658487A (en) | 2017-10-30 | 2017-10-30 | A kind of electrolyte of vanadium redox battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711036668.1A CN107658487A (en) | 2017-10-30 | 2017-10-30 | A kind of electrolyte of vanadium redox battery |
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| Publication Number | Publication Date |
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| CN107658487A true CN107658487A (en) | 2018-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201711036668.1A Pending CN107658487A (en) | 2017-10-30 | 2017-10-30 | A kind of electrolyte of vanadium redox battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878943A (en) * | 2018-06-15 | 2018-11-23 | 中国大唐集团科学技术研究院有限公司西北分公司 | A method of all-vanadium redox flow battery electrolyte is prepared using waste and old SCR catalyst |
| CN109888350A (en) * | 2019-01-18 | 2019-06-14 | 清华大学 | A kind of electrolyte of middle warm type all-vanadium flow battery |
-
2017
- 2017-10-30 CN CN201711036668.1A patent/CN107658487A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878943A (en) * | 2018-06-15 | 2018-11-23 | 中国大唐集团科学技术研究院有限公司西北分公司 | A method of all-vanadium redox flow battery electrolyte is prepared using waste and old SCR catalyst |
| CN109888350A (en) * | 2019-01-18 | 2019-06-14 | 清华大学 | A kind of electrolyte of middle warm type all-vanadium flow battery |
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Application publication date: 20180202 |