CN107871881A - A kind of electrolyte for vanadium cell and preparation method thereof - Google Patents
A kind of electrolyte for vanadium cell and preparation method thereof Download PDFInfo
- Publication number
- CN107871881A CN107871881A CN201610851959.5A CN201610851959A CN107871881A CN 107871881 A CN107871881 A CN 107871881A CN 201610851959 A CN201610851959 A CN 201610851959A CN 107871881 A CN107871881 A CN 107871881A
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- electrolyte
- vanadium
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- liquid
- mother liquor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/186—Regeneration by electrochemical means by electrolytic decomposition of the electrolytic solution or the formed water product
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a kind of electrolyte for vanadium cell and preparation method thereof.The electrolyte is pyrovinic acid to be added into the obtained tetravalence of electrolysis and trivalent vanadium ion electrolyte obtains.Electrolyte proposed by the present invention significantly improves vanadium battery electrode reactivity and the energy efficiency of discharge and recharge.
Description
Technical field
The present invention relates to flow battery field, more particularly relate to that stability is good, high concentration redox all-vanadium flow electricity
The electrolyte in pond and preparation method thereof.
Background technology
The storage of electric energy is realized in mutual conversion between the vanadium ion that vanadium redox battery passes through different valence state
It is the battery system uniquely formed in electrochmical power source using same element with release, its advantage in avoiding positive and negative half electricity
Inhomogeneity active material interpenetrates caused cross pollution between pond, and different valence state vanadium ion is as battery positive and negative electrode
Active material, and storage both positive and negative polarity electrolyte is separated, self discharge during battery storage is eliminated, suitable for the secondary storage of scale
Energy.
More specifically, all-vanadium flow battery includes the separated positive and negative polarities of barrier film, and electrode is by active material and afflux
Body is formed；Anode electrolyte is made up of V 4+/V 5+ ion sulfuric acid solutions, and electrolyte liquid is by V 2+/V+3 ion sulfuric acid solutions
Composition.After battery charging, positive electrode material is V 5+ solions, and negative pole is V 2+ solions；After electric discharge, positive and negative polarities difference
For V 4+ and V+3 solions, inside battery passes through H+ ionic conductions.
The core of vanadium flow battery is that the concentration of electrolyte determines energy density, and the electrolyte of high concentration can realize battery
High-energy-density, but in actual use, the vanadium species of high-valence state can raise because of concentration, and temperature rise produces deposited phenomenon,
So that the concentration of electrolyte of vanadium redox battery can only be maintained at 1.8mol/L or so, its energy density can only reach 25Wh/kg.High concentration electric
It is that vanadium cell enters the critical problem that industrialization stage urgent need solves to solve the stability of liquid and excellent chemical property.
The content of the invention
It is an object of the invention to provide a kind of stability is good, chemical property is good, new electrolyte of vanadium redox battery and its system
Preparation Method.
A kind of preparation method of electrolyte for vanadium cell, includes the preparation of positive pole and electrolyte liquid, comprises the following steps：
1) mother liquor of anode electrolyte of vanadium battery, is prepared：The mixture of vanadic anhydride and sulfuric acid is inserted into the electrolysis of two Room
The cathode chamber of groove, the anode chamber of electrolytic cell add sulphuric acid electrolyte, tetravalent vanadium ion electrolyte, as vanadium cell anolyte are made
Liquid mother liquor；
2) vanadium redox battery negative pole electrolyte mother liquor, is prepared：The electrolysis system of step 1) is continued to be electrolysed, obtains trivalent vanadium ion
The mother liquor of electrolyte；Or obtained tetravalent vanadium ion electrolyte is respectively placed in the Room of both positive and negative polarity two of vanadium cell and charged, fill
Man Hou, anode chamber obtain the mother liquor of trivalent vanadium ion electrolyte；
3) tetravalence and trivalent electrolyte mother liquor for, obtaining step 1) and step 2) are separately added into pyrovinic acid, are prepared into
To vanadium cell positive pole and electrolyte liquid.
It is that the mixture of the sulfuric acid solution by vanadic anhydride and 0.01-18.4mol/L inserts two in described step 1)
The cathode chamber of room electrolytic cell；0.01-6.0mol/L sulfuric acid is added in the anode chamber of electrolytic cell.
In obtained positive pole or electrolyte liquid：Vanadium ion concentration is 0.1-6mol/L；The concentration of sulfuric acid is 0.01-
6mol/L, the concentration of pyrovinic acid is in 0.01-12mol/L.
The mol ratio of sulfuric acid and pyrovinic acid is：1∶0.01-1∶6.
The electrolyte for vanadium cell of the present invention is prepared by the above method.
The V electrolyte being applicable in the present invention be in the prior art frequently with the systems of 2 SO of VOSO 4-H 4, can be with
Using normal concentration, such as VOSO 4 and V 2 (SO 4) 3 can be between 1.0-3.0mol/L, and the SO 4 of H 2 can be in 2-
Between 4mol/L.
The present invention introduces a kind of new supporting electrolyte pyrovinic acid creatively into above-mentioned V electrolyte.Can be by first
Base sulfonic acid is configured to 3mol/L as preferable concentration, and the vanadium concentration after reaction in system reaches 0.8-5.0M.The electrolyte can
To significantly improve the activity of electrolyte and invertibity.
Electrode suitable for the present invention can be PAN based graphite felt electrode.
The pyrovinic acid and the mol ratio of sulfuric acid that the present invention uses preferably 1-3: 1 scope.
It is an advantage of the present invention that the reagent (pyrovinic acid) chosen is formed while supporting electrolyte is served as with vanadium
Species in battery charge and discharge process stability and electro-chemical activity be improved, it is particularly reversible to electrolyte electrochemical to have
Larger raising, shows that the electrolyte has higher discharge voltage, larger improves vanadium cell in charge and discharge electric test
Energy efficiency.
Embodiment
A kind of preparation method of electrolyte for vanadium cell, includes the preparation of positive pole and electrolyte liquid, comprises the following steps：
1) mother liquor of anode electrolyte of vanadium battery, is prepared：The mixture of vanadic anhydride and sulfuric acid is inserted into the electrolysis of two Room
The cathode chamber of groove, the anode chamber of electrolytic cell add sulphuric acid electrolyte, tetravalent vanadium ion electrolyte, as vanadium cell anolyte are made
Liquid mother liquor；
2) vanadium redox battery negative pole electrolyte mother liquor, is prepared：The electrolysis system of step 1) is continued to be electrolysed, obtains trivalent vanadium ion
The mother liquor of electrolyte；Or obtained tetravalent vanadium ion electrolyte is respectively placed in the Room of both positive and negative polarity two of vanadium cell and charged, fill
Man Hou, anode chamber obtain the mother liquor of trivalent vanadium ion electrolyte；
3) tetravalence and trivalent electrolyte mother liquor for, obtaining step 1) and step 2) are separately added into pyrovinic acid, are prepared into
To vanadium cell positive pole and electrolyte liquid.
It is that the mixture of the sulfuric acid solution by vanadic anhydride and 0.01-18.4mol/L inserts two in described step 1)
The cathode chamber of room electrolytic cell；0.01-6.0mol/L sulfuric acid is added in the anode chamber of electrolytic cell.
In obtained positive pole or electrolyte liquid：Vanadium ion concentration is 0.1-6mol/L；The concentration of sulfuric acid is 0.01-
6mol/L, the concentration of pyrovinic acid is in 0.01-12mol/L.
The mol ratio of sulfuric acid and pyrovinic acid is：1∶0.01-1∶6.
The electrolyte for vanadium cell of the present invention is prepared by the above method.
The V electrolyte being applicable in the present invention be in the prior art frequently with the systems of 2 SO of VOSO 4-H 4, can be with
Using normal concentration, such as VOSO 4 and V 2 (SO 4) 3 can be between 1.0-3.0mol/L, and the SO 4 of H 2 can be in 2-
Between 4mol/L.
The present invention introduces a kind of new supporting electrolyte pyrovinic acid creatively into above-mentioned V electrolyte.Can be by first
Base sulfonic acid is configured to 3mol/L as preferable concentration, and the vanadium concentration after reaction in system reaches 0.8-5.0M.The electrolyte can
To significantly improve the activity of electrolyte and invertibity.
Electrode suitable for the present invention can be PAN based graphite felt electrode.
The pyrovinic acid and the mol ratio of sulfuric acid that the present invention uses preferably 1-3: 1 scope.
Claims (7)
1. a kind of preparation method of electrolyte for vanadium cell, includes the preparation of positive pole and electrolyte liquid, it is characterised in that：Below
Step：
1) mother liquor of anode electrolyte of vanadium battery, is prepared：The mixture of vanadic anhydride and sulfuric acid is inserted into two Room electrolytic cells
Cathode chamber, the anode chamber of electrolytic cell add sulphuric acid electrolyte, and tetravalent vanadium ion electrolyte is made, and as anode electrolyte of vanadium battery is female
Liquid；
2) vanadium redox battery negative pole electrolyte mother liquor, is prepared：The electrolysis system of step 1) is continued to be electrolysed, obtains trivalent vanadium ion electrolysis
The mother liquor of liquid；Or obtained tetravalent vanadium ion electrolyte is respectively placed in the Room of both positive and negative polarity two of vanadium cell and charged, after being full of,
Anode chamber obtains the mother liquor of trivalent vanadium ion electrolyte；
3) tetravalence and trivalent electrolyte mother liquor for, obtaining step 1) and step 2) are separately added into pyrovinic acid, and vanadium is prepared
Anode and electrolyte liquid.
2. preparation method according to claim 1, it is characterised in that：Be in described step 1) by vanadic anhydride with
The mixture of 0.01-18.4mol/L sulfuric acid solution inserts the cathode chamber of two Room electrolytic cells.
3. preparation method according to claim 1, it is characterised in that：In described step 1), in the anode chamber of electrolytic cell
Add 0.01-6.0mol/L sulfuric acid.
4. preparation method according to claim 1, it is characterised in that：In obtained positive pole or electrolyte liquid, ion
Concentration is 0.1-6mol/L.
5. preparation method according to claim 1, it is characterised in that：In obtained positive pole or electrolyte liquid, sulfuric acid
Mol ratio with pyrovinic acid is 1: 0.01-1: 6.
6. preparation method according to claim 1, it is characterised in that：In obtained positive pole or electrolyte liquid, sulfuric acid
Concentration be 0.01-6mol/L, the concentration of pyrovinic acid is in 0.01-12mol/L.
A kind of 7. electrolyte for vanadium cell, it is characterised in that：It is to be prepared as any one method described in claim 1-6
Electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610851959.5A CN107871881A (en) | 2016-09-26 | 2016-09-26 | A kind of electrolyte for vanadium cell and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610851959.5A CN107871881A (en) | 2016-09-26 | 2016-09-26 | A kind of electrolyte for vanadium cell and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107871881A true CN107871881A (en) | 2018-04-03 |
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| CN201610851959.5A Pending CN107871881A (en) | 2016-09-26 | 2016-09-26 | A kind of electrolyte for vanadium cell and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113903964A (en) * | 2021-09-02 | 2022-01-07 | 香港科技大学 | Simple method for improving performance of vanadium battery and application |
| CN115020757A (en) * | 2022-06-09 | 2022-09-06 | 四川星明能源环保科技有限公司 | Electrodialysis-based method for removing organic matters in strong acid vanadium solution |
-
2016
- 2016-09-26 CN CN201610851959.5A patent/CN107871881A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113903964A (en) * | 2021-09-02 | 2022-01-07 | 香港科技大学 | Simple method for improving performance of vanadium battery and application |
| CN113903964B (en) * | 2021-09-02 | 2023-09-29 | 香港科技大学 | Simple method for improving performance of vanadium battery and application |
| CN115020757A (en) * | 2022-06-09 | 2022-09-06 | 四川星明能源环保科技有限公司 | Electrodialysis-based method for removing organic matters in strong acid vanadium solution |
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Application publication date: 20180403 |