CN109980259A - A kind of anode electrolyte of vanadium battery and preparation method thereof - Google Patents

A kind of anode electrolyte of vanadium battery and preparation method thereof Download PDF

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Publication number
CN109980259A
CN109980259A CN201711440025.3A CN201711440025A CN109980259A CN 109980259 A CN109980259 A CN 109980259A CN 201711440025 A CN201711440025 A CN 201711440025A CN 109980259 A CN109980259 A CN 109980259A
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China
Prior art keywords
electrolyte
vanadium
additive
sulfuric acid
preparation
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CN201711440025.3A
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Chinese (zh)
Inventor
倪翠
高丽珠
戴新国
梁超
朱灿
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Foxconn Kunshan Computer Connector Co Ltd
Foxconn Interconnect Technology Ltd
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Foxconn Kunshan Computer Connector Co Ltd
Foxconn Interconnect Technology Ltd
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Priority to CN201711440025.3A priority Critical patent/CN109980259A/en
Publication of CN109980259A publication Critical patent/CN109980259A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • 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
    • 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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  • 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)
  • Fuel Cell (AREA)

Abstract

The present invention provides a kind of electrolyte for vanadium cell, which includes vanadium ion, sulfuric acid and active additive, and the additive is organic acid salt compound, and concentration of the additive in the electrolyte is 0.01~0.1mol/L.The present invention also provides the methods for preparing the electrolyte.The addition of additive can improve vanadium redox flow battery electrolyte electro-chemical activity, not only increase the anode electrolyte of vanadium battery invertibity that tetravalence vanadium and pentavalent vanadium mutually convert in charge and discharge process, also increase vanadium cell in the running voltage and current efficiency that works.

Description

A kind of anode electrolyte of vanadium battery and preparation method thereof
[technical field]
The present invention relates to battery electrolyte field more particularly to a kind of vanadium flow battery anode electrolyte and its preparation sides Method.
[background technique]
The energy of vanadium flow battery derives from the sulfuric acid solution containing different valence state vanadium ion, and the energy of battery work is close Degree and operational efficiency depend not only on the concentration of vanadium ion, and and vanadium ion electrode surface electrochemical reaction activity closely It is related.Again since the principle and reaction power of vanadium cell work are mainly in positive and negative anodes electrolyte between four kinds of valence state vanadium ions Invertibity conversion, this is also that vanadium cell is able to efficient, stable operation key.Therefore, the invertibity of vanadium ion electrochemical reaction Prepared by the research and development of vanadium cell most important, people also improve V electrolyte electro-chemical activity and stability in continuous explore Scheme, it is desirable to the performance of vanadium cell work operation is improved from the active angle of vanadium ion electrochemical reaction is improved.
Currently, especially main two kinds of the reversible method of cyclic voltammetric of V electrolyte electrochemical reaction activity are improved, one It kind is to make some activity modifyings to electrode from the angle of reaction electrode to improve the activity that vanadium ion is reacted in electrode surface with this With invertibity, another kind is directly to add some catalyst, activating agent etc. in the solution to improve the electrochemistry of vanadium ion reaction Activity.For the former, although the activity and invertibity of vanadium ion electrochemical reaction can be improved, enforcement difficulty is higher, and And more stringent requirements are proposed to materials such as electrode, shells, to improve cost.
Another kind improves vanadium ion stability and the reversible method of electrochemical reaction is exactly to be added to fit in V electrolyte Measure active additive.Studies have shown that although some additives such as urea, glycerol, pyridine, ammonium oxalate and EDTA etc. can make V5+Surely Qualitative increase, but the invertibity of anode electrolyte reaction can not be improved.By cyclic voltammetry, addition organic acid is had studied The vanadium ion electrolyte of salt, amino acids and glucose substance.Studies have shown that the addition of amino acid and glucose compounds Can be improved anode electrolyte reaction invertibity, but due to the intersolubility of the organic additive of addition and V electrolyte compared with Difference, therefore the resistance of electrolyte is increased to a certain extent.And the presence of acylate, it can not only increase anode electrolyte The invertibity of redox reaction can also increase the electric current of reaction and improve the conductivity of solution.
About the research of this respect, inorganic or organic additive is generallyd use to change and improve the performance of electrolyte, document Report, organic compounds majority is not readily dissolved in aqueous solution, therefore the addition of organic matter increases the resistance of V electrolyte, simultaneously The organic solvents such as ethyl alcohol need to be introduced to improve solubility of additive, affect the activity and electrochemistry of electrolyte to a certain extent Invertibity.Therefore, the additive used in the prior art, which can't be fully solved, improves V electrolyte stability and activity problems, And avoid the problem that valence state mismatches Accumulation Phenomenon.
Therefore, all-vanadium ionic liquid flow battery is there is an urgent need to find a kind of new suitable additive, to form new electricity Solve formula of liquid system, the long-term running stability of Lai Tigao electrolyte, so as to improve the invertibity of vanadium ion redox reaction So as to improve the Current Voltage efficiency of electrolyte reaction, to guarantee battery long-time steady operation.
[summary of the invention]
It is an object of the invention to solve electrolyte reactivity and vanadium ion electrochemical reaction circulation in vanadium flow battery Invertibity problem.
The purpose of the present invention is achieved through the following technical solutions: a kind of electrolyte for vanadium cell, including vanadium ion, sulfuric acid And active additive, the additive are organic acid salt compound, concentration of the additive in the electrolyte is 0.01~0.1mol/L.
Further, the additive is sodium tartrate.
The purpose of the present invention is also achieved through the following technical solutions: a kind of preparation method of electrolyte for vanadium cell, should Method is the following steps are included: step 1: vanadic anhydride is mixed with sulfuric acid solution, in oxalic acid reduction and heating under conditions of system The sulfuric acid solution of vanadium is obtained, wherein the concentration of vanadium ion is 1.5~2.0mol/L；Step 2: the vanadium is added in the additive In sulfuric acid solution be made the electrolyte containing active additive, concentration of the additive in the electrolyte be 0.01~ 0.1mol/L。
Further, the heating temperature in the first step is 65 DEG C.
Further, the additive is sodium tartrate.
Compared with prior art, the invention has the following beneficial effects: the present invention passes through addition wine from the angle of electrolyte Stone acid sodium this active constituent improves reactivity and invertibity.The present invention is implemented simply, and additive amount is few, and effect is bright It is aobvious, vanadium ion reaction redox reversible is not only improved, also improves the voltage and current efficiency of reaction to a certain extent.
[Detailed description of the invention]
Fig. 1 is vanadium ion (V4+,V5+) cyclic voltammetry curve of the electrolyte when being free of additive.
Fig. 2 is vanadium ion (V4+,V5+) cyclic voltammetry curve of electrolyte when containing 0.05mol/L sodium tartrate.
[specific embodiment]
In order to make the content of the present invention more clearly understood, with reference to the accompanying drawing, the present invention is made further It is described in detail.For improving the invertibity of vanadium redox flow battery electrolyte, a variety of methods can be used.It both can be from modified electrode Angle does activity modifying appropriate to electrode surface, to improve vanadium ion in the electro-chemical activity of electrode surface, especially improves it Invertibity；It can also start with from the angle of electrolyte, i.e., active additive, such as amino acids, sulfuric acid are added in the electrolytic solution Salt, glucose and acylate substance change and improve the reversible of vanadium ion redox reaction in electrolyte with this Property.During test, one or more reliable active additives can be chosen so that the new electrolyte formed is made.Addition Agent is not only able to improve the redox reversible of vanadium ion in electrolyte, can also improve the electric current and voltage efficiency of reaction, To maintain V electrolyte stable and high effective operation in battery charge and discharge process.
For vanadium redox flow battery electrolyte problem poorly reversible in electrode reaction, the present invention is added using activity is added The mode of agent improves the cyclic voltammetric invertibity of its electrolyte, and the energy density of electrolyte is improved with this.The present invention by The mode of additive sodium tartrate is added in vanadium liquid stream anode electrolyte to improve the reciprocal characteristics of electrolyte electrochemical reaction. Meanwhile the ameliorative way is the angle based on electrolyte, rather than the angle of electrode modification, it implements and is relatively easy to.Specifically, The present invention provides a kind of electrolyte for vanadium cell, including vanadium ion, sulfuric acid and active additive, and the additive is acylate Class compound sodium tartrate, concentration of the additive in the electrolyte are 0.01~0.1mol/L.
The present invention also provides a kind of preparation methods for preparing above-mentioned electrolyte for vanadium cell, and the method includes following steps Rapid: the first step mixes vanadic anhydride with sulfuric acid solution, and the sulfuric acid that vanadium is made under conditions of oxalic acid restores and heats is molten Liquid, wherein heating temperature is 65 DEG C, and the concentration of vanadium ion is 1.5~2.0mol/L, and the additive is sodium tartrate；Second The additive is added in the vanadium sulfuric acid solution and the electrolyte containing active additive is made by step, and the additive is in institute Stating the concentration in electrolyte is 0.01~0.1mol/L.
In the preferred embodiment, step 1: weighing V first2O5 72.8g,H2C2O4.2H2O 75.6g is in 500mL beaker In, addition 3mol/L sulfuric acid is supporting electrolyte, and the stirring and dissolving at 65 DEG C obtains 1.6mol/L tetravalence vanadium solution；Step 2: It is spare to weigh each 300mL of solution obtained in two parts of first steps；Step 3: three mouthfuls of electrolysis are added in a solution in second step Chi Zhong, installs three electrodes, that is, is separately connected working electrode, to electrode and reference electrode, applies current potential -0.6V~1.4V, into Row cyclic voltammetry scan obtains scanning curve and sees Fig. 1；It is put into second step step 4: weighing additive sodium tartrate described in 6g Another solution in dissolution electrolyte of the invention is made, the amount of substance concentration of the additive in the electrolytic solution is 0.05mol/L repeats the Electrochemical Scanning of third step, obtains curve such as Fig. 2.
Therefore, Fig. 1 is that cyclic voltammetric of the vanadium flow battery anode electrolyte on graphite electrode is bent when additive not being added Line chart, Fig. 2 are the cyclic voltammetry curve figure of electrolyte when additive 0.05mol/L sodium tartrate is added；Comparison diagram 1 and Fig. 2 Curve can be seen that be added sodium tartrate after, espespecially invertibity significantly improves the Cyclic voltamogram of electrolyte, i.e., its electricity Solving the cyclic voltammetric property of liquid irreversible becomes the polar-symmetric reciprocal characteristics of yin-yang from original.The additive sodium tartrate exists Can not only improve that anode electrolyte of vanadium battery tetravalence vanadium and pentavalent vanadium in charge and discharge process mutually convert in electrolyte can Inverse property, can also increase the electric conductivity of electrolyte, to improve vanadium cell in the running voltage and current efficiency that works.
Improve vanadium ion redox reversible compared to from modified electrode angle, the present invention passes through from the angle of electrolyte Active constituent is added to improve reactivity and invertibity.This method is implemented simply, and additive amount is few, and effect is obvious, not only Vanadium ion reaction redox reversible is improved, also improves the voltage and current efficiency of reaction to a certain extent.
The foregoing is merely some embodiments of the invention, the embodiment being not all of, ordinary skill people Any equivalent variation that member takes technical solution of the present invention by reading description of the invention, is right of the invention It is required that being covered.

Claims (5)

1. a kind of electrolyte for vanadium cell, including vanadium ion, sulfuric acid and active additive, it is characterised in that: the additive is Organic acid salt compound, concentration of the additive in the electrolyte are 0.01~0.1mol/L.
2. electrolyte as described in claim 1, it is characterised in that: the additive is sodium tartrate.
3. a kind of preparation method of electrolyte described in claim 1-2, it is characterised in that: the described method comprises the following steps:
Step 1: vanadic anhydride is mixed with sulfuric acid solution, the sulfuric acid that vanadium is made under conditions of oxalic acid restores and heats is molten Liquid, wherein the concentration of vanadium ion is 1.5~2.0mol/L；
The electrolyte containing active additive is made step 2: the additive is added in the vanadium sulfuric acid solution, it is described to add Adding concentration of the agent in the electrolyte is 0.01~0.1mol/L.
4. the preparation method of electrolyte as claimed in claim 3, it is characterised in that: the heating temperature in the first step is 65 ℃。
5. the preparation method of electrolyte as claimed in claim 3, it is characterised in that: the additive is sodium tartrate.
CN201711440025.3A 2017-12-27 2017-12-27 A kind of anode electrolyte of vanadium battery and preparation method thereof Pending CN109980259A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103066312A (en) * 2012-12-21 2013-04-24 攀钢集团攀枝花钢铁研究院有限公司 Preparation method for electrolyte used for vanadium flow cell
CN104269572A (en) * 2014-10-13 2015-01-07 四川长虹电源有限责任公司 Preparation method of vanadium redox flow battery electrolyte optimized by compound stabilizer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103066312A (en) * 2012-12-21 2013-04-24 攀钢集团攀枝花钢铁研究院有限公司 Preparation method for electrolyte used for vanadium flow cell
CN104269572A (en) * 2014-10-13 2015-01-07 四川长虹电源有限责任公司 Preparation method of vanadium redox flow battery electrolyte optimized by compound stabilizer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杨亚东等: ""化学还原法制备钒电池电解液中还原剂选择及性能"", 《化学进展》 *
钱程等: ""添加剂对钒液流电池正极液的影响"", 《化学工业与工程》 *

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Application publication date: 20190705