CN106395902B - A kind of method that anode electrolyte of vanadium battery using failure prepares vanadic anhydride - Google Patents
A kind of method that anode electrolyte of vanadium battery using failure prepares vanadic anhydride Download PDFInfo
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- CN106395902B CN106395902B CN201610994018.7A CN201610994018A CN106395902B CN 106395902 B CN106395902 B CN 106395902B CN 201610994018 A CN201610994018 A CN 201610994018A CN 106395902 B CN106395902 B CN 106395902B
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- Prior art keywords
- vanadium
- electrolyte
- failure
- vanadic anhydride
- anode electrolyte
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 54
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003792 electrolyte Substances 0.000 title claims abstract description 51
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a kind of method that anode electrolyte of vanadium battery using failure prepares vanadic anhydride.It the described method comprises the following steps：The anode electrolyte of vanadium battery of failure is passed through vanadium cell positive pole and carries out charging pre-oxidation, obtains the electrolyte of pentavalent vanadium ion；Concentration is evaporated to the electrolyte of pentavalent vanadium ion, then stood, forms the mixed liquor with the precipitation containing pentavalent vanadium；Filter mixed liquor, and filter cake is dried and ground, obtain vanadic anhydride powder.The method of the present invention not only realizes the recycling of V electrolyte, and caused purity of vanadium pentoxide is high, can continue for preparing electrolyte or for other purposes such as catalyst.
Description
Technical field
The present invention relates to vanadium battery field, more particularly, is related to a kind of anode electrolyte of vanadium battery system using failure
The method of standby vanadic anhydride.
Background technology
Vanadium cell full name vanadium oxide reduction flow battery, there is service life length, capacity is big, power is big, security performance is high
Etc. series of advantages.It is wide based on its unique advantage, the applicable field of vanadium energy storage system.It can be used as hospital, work
The emergency service facility in the place such as factory, military base and office block；Also can be real by being supplemented in gas station or changing electrolyte
" quickly recharging " of existing vehicle；It can be used as the power supply system of communication, radio repeater station, railway information instruction, military equipment etc.
System；Can be as the airborne power supply of the vehicles such as industrial truck, fork truck, delivery vehicle, bus, submarine；Apply also for side
Remote area home electric power system and solar energy, the supporting energy storage device of wind energy；It especially can be applied to extensive energy storage system
System and peak load regulation network.
When in sulfuric acid system, vanadium cell just extremely (VO2)SO4 -/VOSO4Right, the negative pole V of electricity3+/V2+Electricity is right, and battery fills
After electricity, positive electrode material V5+Solion, negative pole V2+Solion；After electric discharge, positive and negative electrode is respectively V4+And V3+Ion is molten
Liquid.V5+And V4+Ion is in an acidic solution respectively with VO2 +Ion and VO2+Ionic species is present.Electrolyte of vanadium redox battery is by vanadium electricity
After pond is recycled for a long time, vanadium ion concentration and sulfuric acid concentration severe overweight, vanadium ion valence state mismatch, or even produce precipitation etc.
Phenomenon, and then can not use.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is solve present in above-mentioned prior art
One or more problems.For example, an object of the present invention is to provide a kind of vanadium cell anolyte for recycling failure
The method of liquid.
To achieve these goals, a kind of anode electrolyte of vanadium battery using failure that provides of the invention prepares five oxygen
Change the method for two vanadium, the described method comprises the following steps：The anode electrolyte of vanadium battery of failure is passed through into vanadium cell positive pole to carry out
Charging pre-oxidation, obtains the electrolyte of pentavalent vanadium ion；Concentration is evaporated to the electrolyte of pentavalent vanadium ion, then stood,
Form the mixed liquor with the precipitation containing pentavalent vanadium；Filter mixed liquor, and filter cake is dried and ground, obtain vanadic anhydride powder
Body.
According to an implementation of the method that vanadic anhydride is prepared using the anode electrolyte of vanadium battery to fail of the present invention
, vanadium ion concentration can be 1.6mol/L in the anode electrolyte of vanadium battery of failure.
According to an implementation of the method that vanadic anhydride is prepared using the anode electrolyte of vanadium battery to fail of the present invention
Example, the electrolyte of the pentavalent vanadium ion is concentrated by evaporation to vanadium ion concentration and is more than 3.0mol/L.
According to an implementation of the method that vanadic anhydride is prepared using the anode electrolyte of vanadium battery to fail of the present invention
Example, the evaporation-concentration step include：The electrolyte of pentavalent vanadium ion is heated on electric furnace to being boiling for stirring.
According to an implementation of the method that vanadic anhydride is prepared using the anode electrolyte of vanadium battery to fail of the present invention
Example, the time of standing can be 24~48h.
Compared with prior art, the method that vanadic anhydride is prepared using the anode electrolyte of vanadium battery of failure, it is not only real
Showed the recycling of V electrolyte, and caused purity of vanadium pentoxide is high, can continue for prepare electrolyte or
Person is used for other purposes such as catalyst, has actual application value.
Embodiment
Hereinafter, it will be described in detail with reference to exemplary embodiment and the vanadium cell positive pole to fail utilized according to the present invention
The method that electrolyte prepares vanadic anhydride.
The present invention utilizes anode electrolyte of vanadium battery (also known as vanadium cell failure electrolyte, the failure electrolysis failed
Liquid, failure V electrolyte), failure electrolyte is mainly the mixed solution of tetravalence vanadium and pentavalent vanadium composition, is made wherein by charging
Tetravalent vanadium ion V4+It is changed into pentavalent vanadium ion V5+, reheating concentration is precipitated out the pentavalent vanadium in solution, stands one section
Filtering drying after time, you can obtain vanadic anhydride.
In one exemplary embodiment of the present invention, the anode electrolyte of vanadium battery using failure of the invention prepares five
The method of V 2 O comprises the following steps：
(1) tetravalent vanadium ion pre-oxidizes：By the anode electrolyte of vanadium battery of failure be passed through vanadium cell positive pole charge it is pre-
Oxidation, obtains the electrolyte of pentavalent vanadium ion.
Wherein, the concentration of vanadium ion can be 1.6mol/L in the electrolyte of failure.
(2) pentavalent vanadium ion precipitates：Concentration is evaporated to the electrolyte of pentavalent vanadium ion, then stood, formation has
The mixed liquor of the precipitation containing pentavalent vanadium.
In the present example embodiment, resulting solution (i.e. step (1) resulting solution) is taken out after battery is charged, in electric furnace
On be heated to seething with excitement and be stirred continuously, when vanadium ion concentration is concentrated by evaporation to more than 3.0mol/L, remove 24~48h of standing.
(3) preparation of vanadic anhydride：Solidliquid mixture (mixed liquor of the precipitation containing pentavalent vanadium) obtained by step (2) is entered
Row filtering, and vanadic anhydride powder will be obtained after filter cake drying grinding.
Above-mentioned example embodiment for a better understanding of the present invention, it is carried out further with reference to specific example
Explanation.
By the failure electrolyte charging pre-oxidation of vanadium cell positive pole, 10L pentavalents electrolyte (1 is prepared#Electrolyte) for future use,
Electrolyte needs low temperature to store.
Example 1
Measure 500ml 1#Electrolyte, it is 270ml to be concentrated by evaporation on electric furnace and continue stirring until liquor capacity；By gained
Solution remove stand 24h after filter, dry, obtain filter cake 43.69g, calculate vanadium yield be 60.01%, gained filter cake is ground
Mill, obtains vanadic anhydride powder.
Example 2
Measure 1000ml 1#Electrolyte, it is 530ml to be concentrated by evaporation on electric furnace and continue stirring until liquor capacity；By institute
Solution remove stand 48h after filter, dry, obtain filter cake 94.82g, calculate vanadium yield be 65.12%, by gained filter cake
Grinding, obtains vanadic anhydride powder.
Example 3
Measure 2000ml 1#Electrolyte, it is 800ml to be concentrated by evaporation on electric furnace and continue stirring until liquor capacity；By institute
Solution remove stand 96h after filter, dry, obtain filter cake 210.71g, calculate vanadium yield be 72.36%, by gained filter cake
Grinding, obtains vanadic anhydride powder.
In summary, it is of the invention using vanadium cell failure electrolyte prepare vanadic anhydride method have it is following excellent
Point：
(1) using the electrolyte that fails as raw material, resource reclaim recycling is realized.
(2) during vanadic anhydride is prepared as raw material using the electrolyte that fails, it is not necessary to extra addition precipitation
Step, process is simple, cost is low, application easy to spread.
(3) purity of vanadium pentoxide prepared by is high, and vanadium recovery is higher, and technique is suitable to industrialized production.
Although above by describing the present invention with reference to exemplary embodiment, those skilled in the art should be clear
Chu, in the case where not departing from the spirit and scope that claim is limited, the exemplary embodiment of the present invention can be carried out each
Kind modifications and changes.
Claims (3)
1. a kind of method that anode electrolyte of vanadium battery using failure prepares vanadic anhydride, it is characterised in that methods described
Comprise the following steps：
The anode electrolyte of vanadium battery of failure is passed through vanadium cell positive pole and carries out charging pre-oxidation, obtains the electrolysis of pentavalent vanadium ion
Liquid；
The electrolyte of pentavalent vanadium ion is heated to seething with excitement and is stirred continuously, when vanadium ion concentration is concentrated by evaporation to being more than
3.0mol/L, then stand, form the mixed liquor with the precipitation containing pentavalent vanadium；
Filter mixed liquor, and filter cake is dried and ground, obtain vanadic anhydride powder.
2. the method that the anode electrolyte of vanadium battery according to claim 1 using failure prepares vanadic anhydride, it is special
Sign is that vanadium ion concentration is 1.6mol/L in the anode electrolyte of vanadium battery of the failure.
3. the method that the anode electrolyte of vanadium battery according to claim 1 using failure prepares vanadic anhydride, it is special
Sign is that the time of standing is 24~48h.
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| CN201610994018.7A CN106395902B (en) | 2016-11-11 | 2016-11-11 | A kind of method that anode electrolyte of vanadium battery using failure prepares vanadic anhydride |
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| CN201610994018.7A CN106395902B (en) | 2016-11-11 | 2016-11-11 | A kind of method that anode electrolyte of vanadium battery using failure prepares vanadic anhydride |
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| CN106395902B true CN106395902B (en) | 2018-01-26 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109301300B (en) * | 2018-09-27 | 2021-07-06 | 成都先进金属材料产业技术研究院有限公司 | Method for adjusting vanadium valence state in vanadium battery electrolyte |
| CN109721101A (en) * | 2019-01-02 | 2019-05-07 | 成都先进金属材料产业技术研究院有限公司 | Vanadium cell failure electrolyte prepares V2O5The method of nano-powder |
| CN112408477A (en) * | 2020-11-30 | 2021-02-26 | 鞍钢集团北京研究院有限公司 | Method for preparing vanadium dioxide from failure vanadium battery positive electrolyte |
| CN114031114A (en) * | 2021-11-12 | 2022-02-11 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing bismuth vanadate powder by using failure electrolyte of vanadium battery |
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|---|---|---|---|---|
| CN102983346A (en) * | 2012-12-04 | 2013-03-20 | 中国科学院金属研究所 | Method for preparing vanadyl sulfate from electrolyte for failure vanadium cell |
| CN102983379A (en) * | 2012-12-04 | 2013-03-20 | 中国科学院金属研究所 | Method for preparing vanadium pentoxide from ineffective electrolyte for vanadium battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983346A (en) * | 2012-12-04 | 2013-03-20 | 中国科学院金属研究所 | Method for preparing vanadyl sulfate from electrolyte for failure vanadium cell |
| CN102983379A (en) * | 2012-12-04 | 2013-03-20 | 中国科学院金属研究所 | Method for preparing vanadium pentoxide from ineffective electrolyte for vanadium battery |
Non-Patent Citations (1)
| Title |
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| "含钒溶胶絮沉行为研究";徐滔;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150115(第01期);第41页第1段、第42页第3段以及第43页第3段 * |
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Application publication date: 20170215 Assignee: SICHUAN PAN YAN TECHNOLOGY Co.,Ltd. Assignor: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Contract record no.: X2024980003062 Denomination of invention: A Method for Preparing Vanadium Pentoxide by Utilizing Defective Cathode Electrolyte of Vanadium Batteries Granted publication date: 20180126 License type: Exclusive License Record date: 20240322 |
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