CN106099223A - A kind of original position recovers the method for battery capacity - Google Patents
A kind of original position recovers the method for battery capacity Download PDFInfo
- Publication number
- CN106099223A CN106099223A CN201610542653.1A CN201610542653A CN106099223A CN 106099223 A CN106099223 A CN 106099223A CN 201610542653 A CN201610542653 A CN 201610542653A CN 106099223 A CN106099223 A CN 106099223A
- Authority
- CN
- China
- Prior art keywords
- reducing agent
- vanadium
- battery capacity
- battery
- original position
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000007774 longterm Effects 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- -1 pyrosulfate Chemical compound 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to battery applications and energy recovers field, a kind of method recovering battery capacity in position.After using with long-term discharge and recharge, the anode electrolyte of vanadium battery of capacity attenuation is as raw material, add organic and inorganic or its complex reducing agent wherein, with the pentavalent vanadium ion generation reduction reaction in anode electrolyte, make pentavalent vanadium ion be reduced to tetravalent vanadium ion, recover battery capacity.The present invention passes through to add the organic-inorganic reducing agent of proper proportion, the problem of the capacity attenuation in solution battery operation in anode electrolyte, it is achieved battery electrolyte recycling and recovery.Present invention process method is simple, processing ease, raw material are easy to get, and effect is obvious.
Description
Technical field
The present invention relates to battery applications and energy recovers field, a kind of method recovering battery capacity in position.
Background technology
Vanadium oxide reduction flow battery, is called for short vanadium cell.It is a kind of novel electrochemical energy storage system, with traditional electric power storage
Pond is compared, have can quickly, the feature such as Large Copacity discharge and recharge, self-discharge rate be low and battery structure is simple, it is full oxidoreduction
Electricity to sulfuric acid solution, it is not only conducting medium, realizes the electroactive material of energy storage especially, is vanadium cell energy storage and energy
The core that amount converts.The operation principle of vanadium cell is that in charging process, positive pole Vanadium valence is oxidized to 5 valencys, negative pole vanadium valency from 4 valencys
State reverts to 2 valencys from 3 valencys.Electric discharge is the reversible process of said process, along with the increase of vanadium cell discharge and recharge number of times, side reaction
Constantly occurring, the vanadium ion in anode electrolyte is mainly 5 valencys, and the vanadium ion in electrolyte liquid is mainly trivalent, just causes
Electrolyte liquid valence state is unbalance, and battery cannot discharge and recharge.At present, also do not have not unbalance about process electrolyte of vanadium redox battery and recover it
The document of capacity.
Summary of the invention
It is an object of the invention to provide a kind of method recovering battery capacity, the capacity attenuation in solution battery operation
Problem, it is achieved battery electrolyte recycling and recovery.
The technical scheme is that
A kind of original position recover battery capacity method, with long-term discharge and recharge use after, the anode electrolyte of vanadium battery of capacity attenuation
For raw material, the pentavalent vanadium ion added wherein in organic and inorganic or its complex reducing agent, with anode electrolyte occurs reduction anti-
Should, make pentavalent vanadium ion be reduced to tetravalent vanadium ion, recover battery capacity；Wherein, pending anode electrolyte of vanadium battery vanadium is dense
Degree 0.1 ~ 3mol/L.
Described original position recovers the method for battery capacity, organic reducing agent include following one or more: carboxylic acids,
Aldehydes, alcohols, unsaturated hydro carbons；Inorganic reducing agent include following one or more: sulphite, pyrosulfate, sulfuration
Thing, metal, metal-oxide, the salt of multivalent state metal.
Described original position recovers the method for battery capacity, organic reducing agent be following one or more: formic acid, second
Acid, ethanedioic acid, formaldehyde, acetaldehyde, methanol, ethanol, glycerol, ethylene, propylene, 1,3-butadiene；Inorganic reducing agent is following one
Or two or more: sodium pyrosulfate, potassium pyrosulfate, sodium sulfite, potassium sulfite, ferrum, Vanadium sesquioxide, vanadium trichloride.
Described original position recovers the method for battery capacity, and reducing agent uses complex reducing agent or single reducing agent, and it is combined
In reducing agent, organic reducing agent is (1: 1) ~ (1: 4) with the mass ratio of inorganic reducing agent.
Described original position recovers the method for battery capacity, and during reaction is carried out, battery carries out discharge and recharge operation, needs
The anode electrolyte liquid stream circulation of battery.
Described original position recovers the method for battery capacity, the pentavalent vanadium amount of pending electrolyte and the molar ratio of reducing agent
For (2: 1) ~ (1: 3).
Advantages of the present invention: 1, the present invention is by adding the organic-inorganic reduction of proper proportion in anode electrolyte
Agent, can solve the recovery regeneration issues after battery capacity declines, it is not necessary to extras, and the method using electronation, often
Pressure is carried out, and technique is simple, processing ease, and raw material is easy to get, and can substantially recover the capacity of battery, once recovers reaction and can recover
Battery capacity is to the 85% of its initial capacity.2, chemical levels of the present invention is few, reduces secondary pollution dangerous, and does not use two
Sulfur oxide, the toxic gas such as hydrogen sulfide, environmental pollution is little.3, the present invention consumes energy low, saves the energy, and electrolyte after treatment
Character is stable.4, of the present invention organic and inorganic or its complex reducing agent, its main component is environmentally friendly thing
Matter, will not produce adverse effect to environment, meet the feature of the environmental protection of vanadium cell, and consumption is low, to cost control not
Can affect greatly.
Detailed description of the invention
Embodiment 1
With lose 95% capacity anode electrolyte of vanadium battery as raw material, wherein in anode electrolyte, pentavalent vanadium ion is
1.34mol/L, tetravalent vanadium ion is 0.06mol/L, and anode electrolyte volume is 110ml.During electrolyte flow, just
Pole fluid reservoir adds ethanedioic acid 9 grams.After reacting 16 hours, capacity resuming to the 85.3% of former capacity.Electrolysis after recovery
Liquid is through charge-discharge test, coulombic efficiency 92.5%, energy efficiency 79%, voltage efficiency 73%.
Embodiment 2
With lose 50% capacity anode electrolyte of vanadium battery as raw material, wherein in anode electrolyte, pentavalent vanadium ion is
0.6mol/L, tetravalent vanadium ion is 0.6mol/L, and anode electrolyte volume is 110ml.During electrolyte flow, at positive pole
Add storage tank and enter ethanedioic acid 5 grams.After reacting 9 hours, capacity resuming to the 87.1% of former capacity.Electrolyte warp after recovery
Charge-discharge test, coulombic efficiency 93%, energy efficiency 77%, voltage efficiency 71.1%.
Claims (7)
1. the method recovering in situ battery capacity, it is characterised in that after using with long-term discharge and recharge, the vanadium electricity of capacity attenuation
Pond anode electrolyte is raw material, add wherein pentavalent vanadium in organic and inorganic or its complex reducing agent, with anode electrolyte from
There is reduction reaction in son, makes pentavalent vanadium ion be reduced to tetravalent vanadium ion, recover battery capacity；Wherein, pending vanadium cell is just
Pole electrolyte vanadium concentration 0.1 ~ 3mol/L.
2. according to described in claim 1 original position recover battery capacity method, it is characterised in that organic reducing agent include with
Descend one or more: carboxylic acids, aldehydes, alcohols, unsaturated hydro carbons；Inorganic reducing agent include following one or both with
Upper: sulphite, pyrosulfate, sulfide, metal, metal-oxide, the salt of multivalent state metal.
3. the method recovering battery capacity according to the original position described in claim 2, it is characterised in that organic reducing agent is following
One or more: formic acid, acetic acid, ethanedioic acid, formaldehyde, acetaldehyde, methanol, ethanol, glycerol, ethylene, propylene, 1,3-fourth two
Alkene；Inorganic reducing agent be following one or more: sodium pyrosulfate, potassium pyrosulfate, sodium sulfite, potassium sulfite, ferrum, three oxygen
Change two vanadium, vanadium trichloride.
4. the method recovering battery capacity according to the original position described in claim 2 or 3, it is characterised in that reducing agent uses multiple
Closing reducing agent or single reducing agent, in its complex reducing agent, organic reducing agent is (1: 1) with the mass ratio of inorganic reducing agent
~ (1: 4).
5. the method recovering battery capacity according to the original position described in claim 1, it is characterised in that carry out process in reaction
In, battery carries out discharge and recharge operation, needs the anode electrolyte liquid stream of battery to circulate.
6. the method recovering battery capacity according to the original position described in claim 1, it is characterised in that the five of pending electrolyte
Valency vanadium amount is (2: 1) ~ (1: 3) with the molar ratio of reducing agent.
7. the method recovering battery capacity according to the original position described in claim 1, it is characterised in that the reduction reaction time is 8-
48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610542653.1A CN106099223A (en) | 2016-07-11 | 2016-07-11 | A kind of original position recovers the method for battery capacity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610542653.1A CN106099223A (en) | 2016-07-11 | 2016-07-11 | A kind of original position recovers the method for battery capacity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106099223A true CN106099223A (en) | 2016-11-09 |
Family
ID=57219713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610542653.1A Pending CN106099223A (en) | 2016-07-11 | 2016-07-11 | A kind of original position recovers the method for battery capacity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106099223A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111261889A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | A kind of on-line recovery method of positive electrolyte of zinc-iron flow battery |
-
2016
- 2016-07-11 CN CN201610542653.1A patent/CN106099223A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111261889A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | A kind of on-line recovery method of positive electrolyte of zinc-iron flow battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103035963B (en) | A kind of original position recovers the method for battery capacity | |
| CN104716374B (en) | Neutral zinc iron double fluid flow battery | |
| JP7035181B2 (en) | Zinc-iodide flow battery | |
| CN112786938B (en) | Acid-base Hybrid High Voltage Aqueous Zinc Batteries and Zinc Flow Batteries with Dual Dissolution Deposition Reactions | |
| CN105680082A (en) | Long-lifetime zinc-bromine flow battery structure and electrolyte | |
| CN106532079B (en) | A kind of recycling and reusing method of vanadium redox flow battery electrolyte | |
| WO2018103518A1 (en) | Neutral zinc-iron flow battery | |
| CN102227029B (en) | High-concentration vanadium electrolyte and preparation method thereof | |
| CN104979577A (en) | Vanadium/chloride electrolyte and redox flow battery using vanadium/chloride electrolyte | |
| CN106532093A (en) | Quinone metal redox couple flow cell system | |
| CN102983340B (en) | Method for removing copper ions from copper-containing vanadium liquid | |
| CN102694143A (en) | Air/vanadium redox flow battery | |
| CN102544563B (en) | A zinc deposition type liquid flow energy storage battery system and its operation mode | |
| CN201514973U (en) | A flow battery | |
| CN107565151B (en) | Regeneration method of electrode activity of all-vanadium redox flow battery | |
| CN109273786A (en) | Utilize the method for sulfuric acid system vanadium cell failure anode electrolyte regeneration V electrolyte | |
| CN103456977B (en) | Improve the method for operation efficiency of all-vanadium redox flow battery | |
| CN108134120A (en) | A kind of zinc-bromine flow battery method for restoring performance | |
| CN105679985A (en) | Quinone polyhalogenide flow cell | |
| CN109449470A (en) | Utilize the method for sulfuric acid system vanadium cell failure electrolyte liquid regeneration V electrolyte | |
| CN108123159B (en) | A method for improving the stability of the negative electrode electrolyte of an all-vanadium redox flow battery | |
| CN106099223A (en) | A kind of original position recovers the method for battery capacity | |
| CN109360997A (en) | The regeneration method of sulfuric acid system failure V electrolyte | |
| CN106876814B (en) | All-vanadium redox flow battery capacity recovery method | |
| CN104638289A (en) | Electrochemical preparation device of low valence vanadium electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161109 |