CN100511798C - All-vanadium redox flow battery electrolytic solution preparation method - Google Patents

All-vanadium redox flow battery electrolytic solution preparation method Download PDF

Info

Publication number
CN100511798C
CN100511798C CNB2007101883929A CN200710188392A CN100511798C CN 100511798 C CN100511798 C CN 100511798C CN B2007101883929 A CNB2007101883929 A CN B2007101883929A CN 200710188392 A CN200710188392 A CN 200710188392A CN 100511798 C CN100511798 C CN 100511798C
Authority
CN
China
Prior art keywords
vanadium
flow battery
electrolyte
valency
electrolytic solution
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.)
Expired - Fee Related
Application number
CNB2007101883929A
Other languages
Chinese (zh)
Other versions
CN101192674A (en
Inventor
崔旭梅
陈孝娥
刘国钦
王军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panzhihua University
Original Assignee
Panzhihua University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Panzhihua University filed Critical Panzhihua University
Priority to CNB2007101883929A priority Critical patent/CN100511798C/en
Publication of CN101192674A publication Critical patent/CN101192674A/en
Application granted granted Critical
Publication of CN100511798C publication Critical patent/CN100511798C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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

Landscapes

  • Fuel Cell (AREA)

Abstract

The invention relates to a method for preparing electrolyte for a flow battery with full vanadium oxidation reduction, which is characterized by the processes: mixing the three oxidation vanadium and the sulphuric acid with a specified volume of proportion of 1. 84, then calcining the mixture under 100 DEG C to 300DEG C in a pipe type electric stove to get vanadium compound in green color, at last dissolving the calcined product into the dilute sulfuric acid to get the vanadium electrolyte used in a vanadium battery in which 4 valence vanadium and 3 valence vanadium take 50 per cent of the total vanadium quantity. The electrolyte for a flow battery with whole vanadium oxidation reduction prepared by the method reduces the emission of SO2, simplifies the preparation work procedure and is beneficial for scale production and environment protection of the flow battery with full vanadium oxidation reduction.

Description

A kind of preparation method of all-vanadium redox flow battery electrolytic solution
Technical field
The present invention relates to a kind of flow battery-vanadium redox battery, particularly relate to the preparation method of all-vanadium redox flow battery electrolytic solution.
Background technology
Because energy crisis and environmental protection pressure, traditional energy is changed to regenerative resource.Along with the application of wind energy and solar energy equal energy source, it is very necessary researching and developing inexpensive, high efficiency energy-storage system.In numerous energy-storage systems, redox flow batteries is because its unique advantage, thereby obtained development rapidly in recent years.Vanadium oxide reduction flow battery (vanadium redox flow battery wherein, VRB) be one of powerful outstanding environmental protection energy-storage battery of present growth momentum (its manufacturing, use and discarded process does not all produce harmful substance), it has special battery structure, but degree of depth high current density discharge; Charging rapidly; The specific energy height; Cheap; Application is very wide: as can be used as mansion, airport, programme-controlled exchange station stand-by power supply; Can be used as the supporting energy storage device of clean electric power generation systems such as solar energy; For ocean-going ship provides electric power and is used for peak load regulation network etc.Vanadium cell cost and lead-acid battery are close, and it also can prepare the MW class battery pack, and the large power long time provides electric energy, so vanadium cell has lithium ion battery, the incomparable superiority of effectiveness of Ni-MH battery in extensive energy storage field.The vanadium cell production technology is simple, price economy, and the electrical property excellence,, expensive fuel cell complicated with manufacturing compared, and no matter is aspect the extensive energy storage or the application prospect of electric powered motor power supply, all has more competitive strength.
The principle of vanadium redox battery is as far back as 1985, and researchers such as the Maria Skyllas-Kazacos proposition by University of New South Wales afterwards through technology transfer and development, obtains further investigation in Australia, Japan and Canada.At present, the all-vanadium flow battery technology of Canadian VRB PowerSystems company and SUMITOMO CHEMICAL electrician research and development enters the practicability stage.The vanadium redox battery research of China at the critical material of flow battery, comprises aspects such as amberplex, electrode material, high concentration electrolyte and engineering amplifying technique with respect to abroad, still is in the starting stage.
All-vanadium ionic liquid flow battery adopts and contains the active material of vanadium solution as positive and negative electrode, transforms the storage and the release of realization electric energy mutually by the vanadium ion of different valence state.Active material is that the preparation method of electrolyte is with V at present 2O 5Be dissolved in sulfuric acid, use liquid SO then 2Deng the reducing agent reduction, vanadium concentration is adjusted in the back that reacts completely, and adds additive, and last electrolysis obtains the V electrolyte that vanadium cell is used; Or use V 2O 5, simple substance S and H 2SO 4Calcining under certain conditions obtains the compound of vanadium, prepares the electrolyte of vanadium cell at last with this compound.Yet the time of first method electrolysis is longer, has influenced the preparation efficiency of electrolyte.In addition, SO in the two kinds of methods in front 2With the use meeting of simple substance S environment is caused great pollution, this and " the control pollution emission reduction " advocated at present are contrary
Therefore, vanadium redox battery presses for and new can reduce SO 2Discharging improves the preparation method of preparation efficiency simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of easy to makely, can reduce SO 2The preparation method of a kind of vanadium redox battery electrolyte of discharging.
The present invention is that the technical scheme that achieves the above object is: adopt the method preparation of calcining dissolving then to contain V (III) and V (IV) and M V (III)/ M TV=M V (IV)/ M TV=50% electrolyte for vanadium cell.Wherein V (III) and V (IV) represent 3 valency vanadium and 4 valency vanadium respectively, and M V (III), M V (IV), M TVThe molar concentration of representing 3 valency vanadium and 4 valency vanadium and total vanadium respectively.
The preparation method of this all-vanadium redox flow battery electrolytic solution: the vanadium trioxide and the concentrated sulfuric acid are mixed, material by weight, proportioning is 1:1.45～2.3, put into the temperature lower calcination 0.5～5 hour of 100～300 ℃ of electric furnace inherences again, at last calcined product is dissolved in the dilute sulfuric acid, obtains the vanadium cell V electrolyte.
Further, above-mentioned sulfuric acid is that proportion is 1.84 the concentrated sulfuric acid.
Also have, above-mentioned electric furnace is an electric tube furnace.
Advantage of the present invention and good effect show as:
Adopt the method for calcining dissolving to prepare all-vanadium redox flow battery electrolytic solution, the present invention has reduced SO in the electrolyte preparation process 2Discharging.V (III) and V (IV) ion concentration respectively account for 50% in the electrolyte simultaneously; this electrolyte can be used for the positive and negative electrode electrolyte of vanadium redox battery; simplify the assembling and the formation process of vanadium cell, can increase work efficiency, be of value to large-scale production and environmental protection.
Embodiment
Embodiment 1
Agents useful for same:
V 2O 3: metallurgical grade
H 2SO 4: analyze pure, d=1.84
With 11.5g vanadium trioxide and 17g proportion is to put into 100～300 ℃ of temperature ranges in stove inherence after 1.84 the concentrated sulfuric acid stirs to calcine 0.5～5 hour, obtains green calcined product.This product is dissolved in the sulfuric acid solution of 2mol/l, can obtains the solution of 4 valency vanadium and 3 valency vanadium ions.The concentration of vanadium ion in the methods analyst electrolyte of employing constant-current titration, 4 valency vanadium ion concentration: 3 valency vanadium ion concentration ≈ 1.Electrolyte is placed the vanadium that finds no crystalline state more than 100 days and is produced.
Embodiment 2
Agents useful for same:
V 2O 3: metallurgical grade
H 2SO 4: analyze pure, d=1.84
With 13g vanadium trioxide and 30g proportion is to put into 120～230 ℃ of temperature ranges in stove inherence after 1.84 the concentrated sulfuric acid stirs to calcine 0.5～5 hour, obtains green calcined product.This product is dissolved in the sulfuric acid solution of 2mol/l, can obtains the solution of 4 valency vanadium and 3 valency vanadium ions.The concentration of vanadium ion in the methods analyst electrolyte of employing constant-current titration, 4 valency vanadium ion concentration: 3 valency vanadium ion concentration ≈ 1.Electrolyte is placed the vanadium that finds no crystalline state more than 100 days and is produced.
Embodiment 3
Agents useful for same:
V 2O 3: metallurgical grade
H 2SO 4: analyze pure, d=1.84
With 4g vanadium trioxide and 8g proportion is to put into 130～240 ℃ of temperature ranges in stove inherence after 1.84 the concentrated sulfuric acid stirs to calcine 0.5～5 hour, obtains green calcined product.This product is dissolved in the sulfuric acid solution of 2mol/l, can obtains the solution of 4 valency vanadium and 3 valency vanadium ions.The concentration of vanadium ion in the methods analyst electrolyte of employing constant-current titration, 4 valency vanadium ion concentration: 3 valency vanadium ion concentration ≈ 1.Electrolyte is placed the vanadium that finds no crystalline state more than 100 days and is produced.

Claims (2)

1. the preparation method of an all-vanadium redox flow battery electrolytic solution, it is characterized in that: with vanadium trioxide and proportion is that 1.84 the concentrated sulfuric acid mixes, material by weight, proportioning is 1:1.45～2.3, put into the temperature lower calcination 0.5～5 hour of 100～300 ℃ of electric furnace inherences again, at last calcined product is dissolved in the dilute sulfuric acid of 2mol/l, obtain the vanadium cell V electrolyte, contain V (III) and V (IV) in the described electrolyte for vanadium cell, and MV (III)/MTV=MV (IV)/MTV=50%, wherein V (III) and V (IV) represent 3 valency vanadium and 4 valency vanadium respectively, and MV (III), MV (IV), MTV represents the molar concentration of 3 valency vanadium and 4 valency vanadium and total vanadium respectively.
2. the preparation method of a kind of all-vanadium redox flow battery electrolytic solution according to claim 1 is characterized in that described electric furnace is an electric tube furnace.
CNB2007101883929A 2007-11-21 2007-11-21 All-vanadium redox flow battery electrolytic solution preparation method Expired - Fee Related CN100511798C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007101883929A CN100511798C (en) 2007-11-21 2007-11-21 All-vanadium redox flow battery electrolytic solution preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007101883929A CN100511798C (en) 2007-11-21 2007-11-21 All-vanadium redox flow battery electrolytic solution preparation method

Publications (2)

Publication Number Publication Date
CN101192674A CN101192674A (en) 2008-06-04
CN100511798C true CN100511798C (en) 2009-07-08

Family

ID=39487507

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007101883929A Expired - Fee Related CN100511798C (en) 2007-11-21 2007-11-21 All-vanadium redox flow battery electrolytic solution preparation method

Country Status (1)

Country Link
CN (1) CN100511798C (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101834302B (en) * 2009-07-03 2012-09-05 中南大学 All-vanadium redox flow battery electrolyte, preparation method thereof and all-vanadium redox flow battery
CN102074719A (en) * 2010-12-09 2011-05-25 攀枝花学院 Method for preparing electrolyte for all-vanadium redox flow battery
CN102569863B (en) * 2012-02-06 2013-12-18 四川省达州钢铁集团有限责任公司 Preparation method of electrolyte used in all-vanadium redox flow battery
CN111200150B (en) * 2018-11-19 2021-10-26 大连融科储能技术发展有限公司 All-vanadium redox flow battery electrolyte formula and process for maintaining high performance of electrolyte

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1598063A (en) * 2003-09-18 2005-03-23 攀枝花钢铁有限责任公司钢铁研究院 Process for electrolyzing preparing electrolyte of full vanadium ion flow battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1598063A (en) * 2003-09-18 2005-03-23 攀枝花钢铁有限责任公司钢铁研究院 Process for electrolyzing preparing electrolyte of full vanadium ion flow battery

Also Published As

Publication number Publication date
CN101192674A (en) 2008-06-04

Similar Documents

Publication Publication Date Title
CN101562256B (en) Preparation method of electrolyte used for all vanadium redox flow batteries
CN105070901B (en) A kind of preparation method of zinc lithium manganese aqueous systems secondary cell
CN103401010B (en) Method for preparing electrolytes of all-vanadium flow battery
CN105006585A (en) Preparation method of electrolyte for all-vanadium redox-flow battery
CN102263263B (en) Zinc and fluorine doped carbon coating lithium manganese phosphate positive electrode material and preparation method thereof
CN102079516A (en) Preparation method of sheet-form iron phosphate crystal
CN102244246B (en) Preparation method of lithium iron phosphate/carbon composite material
CN102881933B (en) Electrolyte of all-vanadium flow battery
CN102110837A (en) Preparation method of electrolyte for vanadium redox battery (VRB)
CN102354762A (en) Method for manufacturing high-purity vanadium battery electrolyte
CN104269572A (en) Preparation method of vanadium redox flow battery electrolyte optimized by compound stabilizer
CN102074682A (en) Method for preparing high-temperature lithium manganate material for lithium ion power battery
CN108418202B (en) Renewable energy-based circulating power generation system
CN104393256A (en) Preparation method of lithium iron phosphate. lithium vanadium phosphate/carbon in-situ composite positive pole material
CN102881931A (en) Phosphorus-containing all-vanadium redox flow battery anode electrolyte
CN105206832A (en) Sintering preparation method for zinc anode material
CN100511798C (en) All-vanadium redox flow battery electrolytic solution preparation method
CN102185146B (en) Rare-earth doped manganese-lithium phosphate anode material and preparation method thereof
CN101901937B (en) Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof
CN101800339B (en) Method for preparing vanadium cell electrolyte
CN104835962A (en) Low-cost flow battery anode electrolyte and preparation method thereof
CN102881932B (en) Vanadium redox flow battery electrolyte containing manganese
CN105304895A (en) Lithium-containing metal oxide lithium electricity nanoelectrode materials and preparation method thereof
CN115992357A (en) Preparation method of electrolyte of all-vanadium redox flow battery
CN116443941A (en) Preparation and application of in-situ carbon-coated sodium ferric sulfate positive electrode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090708

Termination date: 20181121

CF01 Termination of patent right due to non-payment of annual fee