CN114142077A - Method for preparing vanadium sulfide by using failure vanadium electrolyte - Google Patents
Method for preparing vanadium sulfide by using failure vanadium electrolyte Download PDFInfo
- Publication number
- CN114142077A CN114142077A CN202111441810.7A CN202111441810A CN114142077A CN 114142077 A CN114142077 A CN 114142077A CN 202111441810 A CN202111441810 A CN 202111441810A CN 114142077 A CN114142077 A CN 114142077A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- sulfide
- electrolyte
- failure
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- UDKXBPLHYDCWIG-UHFFFAOYSA-M [S-2].[S-2].[SH-].S.[V+5] Chemical compound [S-2].[S-2].[SH-].S.[V+5] UDKXBPLHYDCWIG-UHFFFAOYSA-M 0.000 claims description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 5
- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 claims description 5
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- IBJKCMMJJCJCLT-UHFFFAOYSA-M [S-2].[S-2].[SH-].[V+5] Chemical compound [S-2].[S-2].[SH-].[V+5] IBJKCMMJJCJCLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000003918 potentiometric titration Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M8/182—Regeneration by thermal means
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing vanadium sulfide by using a failure vanadium electrolyte, which comprises the steps of oxidizing low-valence vanadium ions in the failure vanadium electrolyte into pentavalent vanadium by using an electrolytic cell anode, adding a vector sulfur source and a reducing agent, and preparing a high-purity vanadium sulfide nano material through high-temperature high-pressure reaction; the method can recover and obtain various different vanadium sulfide products, can provide raw material support for future large-scale application of vanadium sulfide nano materials in the fields of energy storage elements, electronic ceramics, semiconductors and the like, and effectively expands the recycling way of the failure vanadium electrolyte; the sulfur source and the reducing agent adopted by the invention have wide sources, low price, environmental protection and cleanness, and the integral recovery process is simple, thereby being beneficial to realizing large-scale production.
Description
Technical Field
The invention relates to the technical field of vanadium battery production, in particular to a method for preparing vanadium sulfide by using a failure vanadium electrolyte.
Background
With the continuous development of social economy, the demand of industrial production or daily life for novel clean energy is continuously increased. The all-vanadium redox flow battery has the characteristics of low cost, high charging and discharging efficiency and deep discharging capability, has the advantages of safety, environmental protection and the like, and has been widely paid attention to and researched as a novel clean energy source for a long time. The electrolyte is used as the core part of the vanadium battery system, and is charged and discharged through the redox reaction of vanadium ions with different valence states on the surfaces of the positive electrode and the negative electrode; however, in the long-term circulation process, the capacity of the electrolyte is continuously attenuated, and the main reason is that the positive and negative vanadium ions are deviated to cause imbalance of valence states at two sides, so that the concentration of the vanadium ions is reduced, the acidity of the electrolyte is changed, and a series of problems such as crystallization, precipitation, viscosity increase, activity reduction and the like occur, and finally, the energy of the vanadium battery system is unbalanced and cannot be used continuously.
The recovery and treatment of the failure electrolyte are always a great problem troubling enterprises, the effective measures for the recovery and treatment of the failure electrolyte in the industry are few at present, and the method mainly focuses on two aspects, namely preparing a vanadium product by oxidizing low-valence vanadium in the electrolyte to pentavalent vanadium and then precipitating the vanadium product or directly precipitating the vanadium and calcining the vanadium product, and adding new electrolyte and distilled water into the failure electrolyte to obtain regenerated electrolyte. However, with the development of vanadium batteries, the existing technology for recovering the spent electrolyte cannot meet the large-scale electrolyte treatment requirement, and meanwhile, the problem of excess productivity caused by a single treatment method exists.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for preparing the vanadium sulfide by using the failed vanadium electrolyte is provided, and the recycling way of the failed vanadium electrolyte can be expanded.
In order to solve the technical problems, the invention adopts the technical scheme that: the method for preparing vanadium sulfide by using the failed vanadium electrolyte comprises the following steps:
step one, taking a certain amount of failure vanadium electrolyte, measuring the concentration of all vanadium ions in the failure vanadium electrolyte, then putting all failure vanadium electrolyte into an electrolytic cell anode for electrolysis, and stopping electrolysis after all vanadium electrolyte is reddish brown;
adding at least one of sodium sulfide, potassium sulfide, ammonium sulfide, elemental sulfur, thioacetamide or thiourea into the electrolyte, adding at least one of methanol, ethanol, propanol, butanol or ethylene glycol, stirring the solution to obtain a precursor solution, transferring the precursor solution into the inner liner of a polytetrafluoroethylene reaction kettle, and then putting the polytetrafluoroethylene reaction kettle into an oven for heating;
and step three, taking out the reaction kettle after heating, collecting a product generated by heating through suction filtration, obtaining black powder through centrifugal washing, putting the obtained black powder into a tubular furnace, introducing argon, and calcining to remove residual free acid in the product to obtain at least one of vanadium disulfide, vanadium tetrasulfide and vanadium trisulfide.
Further, the method comprises the following steps: in the first step, the concentration of all vanadium ions in the failure vanadium electrolyte is measured by adopting a potentiometric titration method.
Further, the method comprises the following steps: in the second step, according to V: the molar ratio of S is 1: 2-2.5, and taking at least one of sodium sulfide, potassium sulfide, ammonium sulfide, elemental sulfur, thioacetamide or thiourea.
Further, the method comprises the following steps: in the second step, the adding amount of at least one of methanol, ethanol, propanol, butanol or glycol is 10-20% of the volume of the used spent vanadium electrolyte in the first step.
Further, the method comprises the following steps: in the second step, magnetic stirring is adopted for 30-60 min, and the stirring speed is 150-300 r/min.
Further, the method comprises the following steps: in the second step, the heating temperature in the oven is 160-200 ℃, and the heating time is 24-48 h.
Further, the method comprises the following steps: and in the third step, distilled water and ethanol are alternately used for centrifugal washing, and the washing times are 4-8.
Further, the method comprises the following steps: in the third step, the calcining temperature of the tubular furnace is 300-550 ℃, and the calcining time is 2-3 h.
The invention has the beneficial effects that: according to the method, low-valence vanadium ions in the failure vanadium electrolyte are oxidized into pentavalent vanadium by using the anode of an electrolytic cell, and then a vector sulfur source and a vector reducing agent are added to prepare a high-purity vanadium sulfide nano material through high-temperature high-pressure reaction; the method can recover and obtain various different vanadium sulfide products, can provide raw material support for future large-scale application of vanadium sulfide nano materials in the fields of energy storage elements, electronic ceramics, semiconductors and the like, and effectively expands the recycling way of the failure vanadium electrolyte; the sulfur source and the reducing agent adopted by the invention have wide sources, low price, environmental protection and cleanness, and the integral recovery process is simple, thereby being beneficial to realizing large-scale production.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be further described with reference to the following examples.
The method for preparing vanadium sulfide by using the failed vanadium electrolyte comprises the following steps:
taking a certain amount of failure vanadium electrolyte, measuring the concentration of all vanadium ions in the failure vanadium electrolyte by adopting a potentiometric titration method, then putting all failure vanadium electrolyte into an electrolytic cell anode for electrolysis, and stopping electrolysis after all vanadium electrolyte turns into reddish brown;
step two, according to V: the molar ratio of S is 1: 2-2.5, adding at least one of sodium sulfide, potassium sulfide, ammonium sulfide, elemental sulfur, thioacetamide or thiourea into the electrolyte, adding at least one of methanol, ethanol, propanol, butanol or ethylene glycol which is 10-20% of the volume of the spent vanadium electrolyte used in the step one, stirring the solution for 30-60 min by adopting magnetic stirring at a rotating speed of 150-300 r/min to obtain a precursor solution, transferring the precursor solution into a lining of a polytetrafluoroethylene reaction kettle, and then heating the polytetrafluoroethylene reaction kettle in an oven at a temperature of 160-200 ℃ for 24-48 h;
and step three, taking out the reaction kettle after heating, collecting a product generated by heating through suction filtration, alternately performing centrifugal washing for 4-8 times by using distilled water and ethanol to obtain black powder, putting the obtained black powder into a tubular furnace, introducing argon, calcining for 2-3 hours at the calcining temperature of 300-550 ℃ to remove residual free acid in the product, and obtaining at least one of vanadium disulfide, vanadium tetrasulfide and vanadium trisulfide.
Example 1
Taking 100ml of failure vanadium electrolyte, measuring the concentration of all vanadium in the failure vanadium electrolyte to be 1.55mol/L by using a potential titrator, putting the failure vanadium electrolyte into the anode of an electrolytic cell for electrolysis, and stopping electrolysis after the failure vanadium electrolyte is completely reddish brown; adding 0.31mol of thioacetamide into the failure vanadium electrolyte, adding 10ml of ethylene glycol, magnetically stirring the electrolyte for 20min at the rotating speed of 150r/min to obtain a precursor solution, transferring the precursor solution into a polytetrafluoroethylene reaction kettle lining with a corresponding size, and placing the precursor solution into an oven to be heated to 160 ℃ for reaction for 24 h; and (3) taking out the reaction kettle after the reaction is finished, collecting the generated product in a suction filtration mode, alternately centrifuging and washing for 6 times by using distilled water and ethanol to obtain a powder product, putting the powder product into a tubular furnace, introducing argon, and calcining for 2 hours at 400 ℃. And (3) performing XRD test on the finally generated sample, wherein the diffraction peak of the finally generated sample is basically consistent with that of a standard VS2PDF card, and the generated product can be determined to be vanadium disulfide.
Example 2
Taking 200ml of failure vanadium electrolyte, measuring the concentration of all vanadium in the failure vanadium electrolyte to be 1.60mol/L by using a potential titrator, putting the failure vanadium electrolyte into the anode of an electrolytic cell for electrolysis, and stopping electrolysis when the failure vanadium electrolyte is completely changed into reddish brown; adding 0.69mol of thioacetamide into the electrolyte, adding 30ml of ethylene glycol, magnetically stirring the electrolyte for 30min at the rotating speed of 200r/min to obtain a precursor solution, transferring the precursor solution into a polytetrafluoroethylene reaction kettle lining with a corresponding size, and placing the precursor solution into an oven to be heated to 180 ℃ for reaction for 30 h; and (3) taking out the reaction kettle after the reaction is finished, collecting the generated product in a suction filtration mode, alternately centrifuging and washing for 7 times by using distilled water and ethanol to obtain a powder product, putting the powder product into a tubular furnace, introducing argon, and calcining for 2.5 hours at 450 ℃. And (3) carrying out XRD test on the finally generated sample, wherein most diffraction peaks are basically consistent with standard VS2PDF cards, and a small part of diffraction peaks correspond to standard VS4PDF cards, so that the generated product can be determined to be the composite material of vanadium disulfide and vanadium tetrasulfide.
Example 3
Taking a failed vanadium electrolyte with the volume of 300ml, measuring the total vanadium concentration in the failed vanadium electrolyte to be 1.65mol/L by using a potential titrator, putting the failed vanadium electrolyte into the anode of an electrolytic cell for electrolysis, and stopping electrolysis when the failed vanadium electrolyte is completely changed into reddish brown; adding 1.24mol of thioacetamide into the electrolyte, adding 60ml of ethylene glycol, magnetically stirring the electrolyte for 40min at the rotating speed of 250r/min to obtain a precursor solution, transferring the precursor solution into a polytetrafluoroethylene reaction kettle lining with a corresponding size, and placing the precursor solution into an oven to be heated to 200 ℃ for reaction for 36 h; and (3) taking out the reaction kettle after the reaction is finished, collecting the generated product in a suction filtration mode, alternately centrifuging and washing for 8 times by using distilled water and ethanol to obtain a powder product, putting the powder product into a tubular furnace, introducing argon, and calcining for 3 hours at 500 ℃. And (3) carrying out XRD test on the finally generated sample, wherein most diffraction peaks are basically consistent with standard VS4PDF cards, and a small part of diffraction peaks correspond to standard V2S3PDF cards, so that the generated product can be determined to be the composite material of vanadium tetrasulfide and vanadium trisulfide.
Claims (8)
1. The method for preparing vanadium sulfide by using the failure vanadium electrolyte is characterized by comprising the following steps: the method comprises the following steps:
step one, taking a certain amount of failure vanadium electrolyte, measuring the concentration of all vanadium ions in the failure vanadium electrolyte, then putting all failure vanadium electrolyte into an electrolytic cell anode for electrolysis, and stopping electrolysis after all vanadium electrolyte is reddish brown;
adding at least one of sodium sulfide, potassium sulfide, ammonium sulfide, elemental sulfur, thioacetamide or thiourea into the electrolyte, adding at least one of methanol, ethanol, propanol, butanol or ethylene glycol, stirring the solution to obtain a precursor solution, transferring the precursor solution into the inner liner of a polytetrafluoroethylene reaction kettle, and then putting the polytetrafluoroethylene reaction kettle into an oven for heating;
and step three, taking out the reaction kettle after heating, collecting a product generated by heating through suction filtration, obtaining black powder through centrifugal washing, putting the obtained black powder into a tubular furnace, introducing argon, and calcining to remove residual free acid in the product to obtain at least one of vanadium disulfide, vanadium tetrasulfide and vanadium trisulfide.
2. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: in the first step, the concentration of all vanadium ions in the failure vanadium electrolyte is measured by adopting a potentiometric titration method.
3. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: in the second step, according to V: the molar ratio of S is 1: 2-2.5, and taking at least one of sodium sulfide, potassium sulfide, ammonium sulfide, elemental sulfur, thioacetamide or thiourea.
4. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: in the second step, the adding amount of at least one of methanol, ethanol, propanol, butanol or glycol is 10-20% of the volume of the used spent vanadium electrolyte in the first step.
5. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: in the second step, magnetic stirring is adopted for 30-60 min, and the stirring speed is 150-300 r/min.
6. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: in the second step, the heating temperature in the oven is 160-200 ℃, and the heating time is 24-48 h.
7. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: and in the third step, distilled water and ethanol are alternately used for centrifugal washing, and the washing times are 4-8.
8. The method of preparing vanadium sulfide using spent vanadium electrolyte according to claim 1, wherein: in the third step, the calcining temperature of the tubular furnace is 300-550 ℃, and the calcining time is 2-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111441810.7A CN114142077B (en) | 2021-11-30 | 2021-11-30 | Method for preparing vanadium sulfide by utilizing failure vanadium electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111441810.7A CN114142077B (en) | 2021-11-30 | 2021-11-30 | Method for preparing vanadium sulfide by utilizing failure vanadium electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114142077A true CN114142077A (en) | 2022-03-04 |
| CN114142077B CN114142077B (en) | 2023-10-27 |
Family
ID=80389942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111441810.7A Active CN114142077B (en) | 2021-11-30 | 2021-11-30 | Method for preparing vanadium sulfide by utilizing failure vanadium electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114142077B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728560A (en) * | 2009-04-10 | 2010-06-09 | 承德万利通实业集团有限公司 | Method for preparing vanadium redox battery negative pole electrolyte |
| 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 |
| 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 |
| CN103035963A (en) * | 2012-12-14 | 2013-04-10 | 中国科学院金属研究所 | Method for restoring battery capacity in situ |
| US20150050570A1 (en) * | 2011-10-14 | 2015-02-19 | Imergy Power Systems Inc. | Production of vanadium electrolyte for a vanadium flow cell |
| US20160197369A1 (en) * | 2012-07-25 | 2016-07-07 | Showa Denko K.K. | Membrane electrode assembly and fuel cell comprising the same |
| CN106340657A (en) * | 2016-11-11 | 2017-01-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium electrolytic solution |
| CA2962794A1 (en) * | 2016-04-01 | 2017-10-01 | Kourosh Khaje | Method for producing electrolyte for vanadium redox batteries from oil sands waste |
| CN107910578A (en) * | 2017-10-26 | 2018-04-13 | 成都先进金属材料产业技术研究院有限公司 | The minimizing technology of nickel ion in a kind of V electrolyte |
| CN108352553A (en) * | 2015-10-20 | 2018-07-31 | Le系统株式会社 | The manufacturing method of the V electrolyte of redox flow batteries |
| CN108777316A (en) * | 2018-06-05 | 2018-11-09 | 长沙有色冶金设计研究院有限公司 | A kind of production technology and system of electrolyte of vanadium redox battery |
| CN110729474A (en) * | 2019-10-24 | 2020-01-24 | 成都先进金属材料产业技术研究院有限公司 | NaV preparation by using failure vanadium battery electrolyte6O15Method for preparing sodium ion battery electrode material |
-
2021
- 2021-11-30 CN CN202111441810.7A patent/CN114142077B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728560A (en) * | 2009-04-10 | 2010-06-09 | 承德万利通实业集团有限公司 | Method for preparing vanadium redox battery negative pole electrolyte |
| US20150050570A1 (en) * | 2011-10-14 | 2015-02-19 | Imergy Power Systems Inc. | Production of vanadium electrolyte for a vanadium flow cell |
| US20160197369A1 (en) * | 2012-07-25 | 2016-07-07 | Showa Denko K.K. | Membrane electrode assembly and fuel cell comprising the same |
| 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 |
| 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 |
| CN103035963A (en) * | 2012-12-14 | 2013-04-10 | 中国科学院金属研究所 | Method for restoring battery capacity in situ |
| CN108352553A (en) * | 2015-10-20 | 2018-07-31 | Le系统株式会社 | The manufacturing method of the V electrolyte of redox flow batteries |
| CA2962794A1 (en) * | 2016-04-01 | 2017-10-01 | Kourosh Khaje | Method for producing electrolyte for vanadium redox batteries from oil sands waste |
| CN106340657A (en) * | 2016-11-11 | 2017-01-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium electrolytic solution |
| CN107910578A (en) * | 2017-10-26 | 2018-04-13 | 成都先进金属材料产业技术研究院有限公司 | The minimizing technology of nickel ion in a kind of V electrolyte |
| CN108777316A (en) * | 2018-06-05 | 2018-11-09 | 长沙有色冶金设计研究院有限公司 | A kind of production technology and system of electrolyte of vanadium redox battery |
| CN110729474A (en) * | 2019-10-24 | 2020-01-24 | 成都先进金属材料产业技术研究院有限公司 | NaV preparation by using failure vanadium battery electrolyte6O15Method for preparing sodium ion battery electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114142077B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103280610A (en) | Method for recovering waste lithium iron phosphate battery positive pieces | |
| CN106929664A (en) | A kind of method that lithium is reclaimed from waste and old ternary lithium ion battery | |
| CN103280611B (en) | A kind of lithium iron phosphate battery negative electrode waste paper recovery method | |
| CN104319412A (en) | Method for preparing high-purity and high-concentration vanadium electrolyte | |
| CN113912033A (en) | Method for recycling anode and cathode mixed powder of waste lithium iron phosphate battery with pre-positioned lithium extraction | |
| CN116216674A (en) | Method for obtaining battery-grade lithium phosphate from waste lithium iron phosphate battery anode material | |
| CN114142077B (en) | Method for preparing vanadium sulfide by utilizing failure vanadium electrolyte | |
| CN105907995A (en) | Method for separating and recovering cobalt and manganese in low-cobalt and high-manganese waste by virtue of sulphide salt and oxidizing agent | |
| CN112158818B (en) | Method for preparing modified iron phosphate from modified iron phosphate and steel pickling waste liquid and application | |
| CN116259811B (en) | Method for preparing vanadium electrolyte from sodium vanadate solution | |
| CN104064795A (en) | Preparation method of high-purity vanadyl sulfate electrolyte | |
| CN103343230B (en) | Valuable metal leaching process and device for waste lithium ion batteries | |
| CN114318009A (en) | Method for recovering lithium from lithium iron phosphate | |
| CN106395910A (en) | Method for preparation of battery grade high-purity manganese sulfate from industrial grade manganese sulfate | |
| CN109818029A (en) | The preparation method of all-vanadium flow battery V electrolyte | |
| CN109461924A (en) | A kind of method that lithium recycles NCA presoma processed | |
| CN116130692B (en) | Recycling method of waste vanadium battery electrolyte | |
| CN108975399B (en) | Method for preparing vanadyl sulfate | |
| CN104064800A (en) | Preparation method of vanadyl sulfate electrolyte | |
| CN105428681A (en) | Remelting type reduction preparation method for vanadyl sulfate electrolyte | |
| CN105428686A (en) | Method for reducing preparation of vanadyl sulfate electrolyte through hydrazine hydrate/oxalic acid | |
| CN115566239A (en) | Method for preparing vanadium battery electrolyte from vanadium-containing solution and vanadium battery electrolyte | |
| CN115305354A (en) | Method for recycling precious metal nickel cobalt manganese lithium from waste ternary lithium battery | |
| CN117585718A (en) | Method for recycling vanadium pentoxide in vanadium electrolyte | |
| CN110867592A (en) | Treatment method of failure vanadium electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20220304 Assignee: SICHUAN PAN YAN TECHNOLOGY Co.,Ltd. Assignor: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Contract record no.: X2024980001678 Denomination of invention: Method for preparing vanadium sulfide using expired vanadium electrolyte Granted publication date: 20231027 License type: Common License Record date: 20240131 |
|
| EE01 | Entry into force of recordation of patent licensing contract |