CN106876767B - A kind of positive electrolyte for all-vanadiumredox flow battery containing additive - Google Patents
A kind of positive electrolyte for all-vanadiumredox flow battery containing additive Download PDFInfo
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- CN106876767B CN106876767B CN201510927528.8A CN201510927528A CN106876767B CN 106876767 B CN106876767 B CN 106876767B CN 201510927528 A CN201510927528 A CN 201510927528A CN 106876767 B CN106876767 B CN 106876767B
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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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M2300/00—Electrolytes
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- 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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Abstract
The present invention relates to a kind of positive electrolyte for all-vanadiumredox flow battery containing additive, the additive is ammonium tungstate, ammonium molybdate, niobic acid ammonium, tantalic acid ammonium, ammonium paratungstate, ammonium paramolybdate, secondary niobic acid ammonium, ammonium metatungstate, metamolybdic acid ammonium, inclined niobic acid ammonium, ammonium dimolybdate, ammonium tetramolybdate, fluorine niobic acid ammonium one or two or more kinds: the concentration of the additive is 0.01mol/L~0.5mol/L.The salt that the present invention uses can effectively inhibit the capacity fade problem generated when battery is run under the high temperature conditions, realize the stable operation of battery as anolyte solution additive.Preparation process of the present invention is easy to operate, energy conservation and environmental protection, it is at low cost, can be realized the stable operation of electrolyte in the battery simultaneously.
Description
Technical field
The present invention relates to the application of the electrolyte stability of all-vanadium flow battery technical field of energy storage, in particular to one kind contains
The all-vanadium redox flow battery electrolyte of additive.
Background technique
It, can be again with continuous exhausted and people's environmental protection consciousness the continuous enhancing of fossil energy in worldwide
Raw energy source utilizing electricity generating techn increasingly has been favored by people.Renewable energy mainly includes wind energy, solar energy, biomass energy, sea
Ocean can wait, they are generally converted to electric energy use.And these renewable energy power generations are influenced tool by conditions such as region, meteorologies
There is apparent discontinuous, unstability.In order to smooth and stablize the power generation output of renewable energy and solve power generation with electricity consumption
Time difference contradiction improves power quality and electric network reliability, it is necessary to develop high-efficiency energy-storage technology.All-vanadium flow battery (VFB) due to
Rapidly with the mutually indepedent adjustable, response of power system capacity and power, securely and reliably, environmental-friendly, have extended cycle life, it is easy to maintain and
The outstanding advantages such as regeneration and become renewable energy power generation, power grid peak load shifting, in emergency and the scales energy storage such as stand-by station
One of most promising technology.
Electrolyte is the important component of all-vanadium flow battery, and concentration and volume directly determine the capacity of battery,
The stability of electrolyte directly influences the reliability and stability in VFB During Process of Long-term Operation.But actually in operational process,
Solubility and stability of the vanadium ion in supporting electrolyte are limited: the V (V) when temperature is higher than 40 DEG C, in anode electrolyte
It is easy that precipitating is precipitated.In practical applications it is generally necessary to be controlled and adjusted by temperature of the heat-exchanger rig to electrolyte.But
It is that heat management system would generally bring up to 20% additional energy to lose, while also will increase the cost of entire VFB system.
In addition, in anode electrolyte the lower solubility of pentavalent vanadium ion limit to a certain extent VFB system energy densities (<
25Wh kg-1) raising.Therefore, improve VFB anode electrolyte in pentavalent vanadium ion concentration and thermal stability for battery system
The high efficiency and stability of system are even more important.The problem of V (V) in electrolyte is precipitated, universal thinking is in electrolyte
It is middle to add a small amount of additive to stablize electrolyte, be stabilized it can at higher concentrations.Wherein draw into electrolyte
Entering complexing agent is a kind of effective means for improving anode electrolyte stability, and the pentavalent vanadium in heteropoly acid and anode electrolyte from
Son is expected to the longtime running stability for improving the stability of anode electrolyte and improving battery there are distinctive coordination.
Summary of the invention
Present invention aims at solving the above problems, a kind of all-vanadium flow battery anolyte containing additive is provided
Liquid, to achieve the purpose that all-vanadium flow battery efficient stable is run.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of positive electrolyte for all-vanadiumredox flow battery containing additive, the additive are ammonium tungstate, ammonium molybdate, niobic acid
Ammonium, tantalic acid ammonium, ammonium paratungstate, ammonium paramolybdate, secondary niobic acid ammonium, ammonium metatungstate, metamolybdic acid ammonium, inclined niobic acid ammonium, ammonium dimolybdate, four molybdenums
The one or two or more kinds of sour ammonium, fluorine niobic acid ammonium；The concentration of the additive is 0.01mol/L~0.5mol/L.The addition
The preferred concentration of agent is 0.01mol/L~0.05mol/L.
The main component for being suitable for the invention electrolyte of vanadium redox battery is higher valence state (four, pentavalent) vanadium oxygen root-sulfuric acid body
System.Vanadium oxygen root (includes VO in the aqueous solution of anode electrolyte2+, VO2 +, V2O3 4+, VO2SO4 -Deng) concentration be 0.5~5mol/L,
Sulfate radical (contains SO4 2-And HSO4 -) concentration be 1~6mol/L.Vanadium oxygen root is preferred dense in the aqueous solution of the anode electrolyte
Degree is 1~3mol/L, and the preferred concentration of sulfate radical is 2~4mol/L.
Vanadium ion (includes V in the aqueous solution of corresponding electrolyte liquid2+, V3+-Deng) concentration be 0.5~5mol/L, sulphur
Acid group (contains SO4 2-And HSO4 -) concentration be 1~6mol/L.
Beneficial outcomes of the invention are as follows:
The anode electrolyte containing additive that the present invention uses can be obviously improved the coordination environment of pentavalent vanadium, improve just
The high high-temp stability of pole electrolyte, and capacity retention ratio of the battery in long-term cyclic process is effectively improved, realize electricity
The long-term stable operation in pond.Preparation process of the present invention is easy to operate, energy conservation and environmental protection, it is at low cost, can guarantee that battery can simultaneously
Chronically efficient stable is run.
Detailed description of the invention
Fig. 1 is the anode electrolyte of the additive containing ammonium paratungstate and the blank anode without any additive in embodiment 2
Charging and discharging curve comparison diagram when electrolyte assembled battery.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1:
1.8M pentavalent vanadium solution is prepared using electrolysis method, adds 1mM, 2mM and 5mM into 10mL pentavalent vanadium solution respectively
Ammonium paratungstate stirs evenly after being sufficiently mixed, and in the water-bath for being placed on 50 DEG C together with blank 1.8M pentavalent vanadium solution example
Heating, observes the state of solution, investigates influence of the ammonium paratungstate of Different adding amount to pentavalent vanadium thermal stability.
Influence situation table of the 1 different content ammonium paratungstate of table to electrolyte stability
The mechanism of action of additive is the emphasis of numerous research work, when pentavalent vanadium is in high temperature bath environment, blank
Pentavalent vanadium solution produces red V soon2O5Precipitating.And when the stabilization of the pentavalent vanadium of ammonium paratungstate with this condition is added
Between extend with the increase of additive amount, when additive amount be 5mM when, stablize time longest.Illustrate the addition of ammonium paratungstate for
The Precipitation of electrolyte has significant ground inhibiting effect, this is because the addition of a small amount of ammonium paratungstate, with five in electrolyte
Valence vanadium ion is complexed to form new state after, significantly reduce V2O5Evolution reaction, to realize electrolyte at high temperature
It is steady in a long-term to exist.The result has positive effect for the operation of electrolyte under high temperature, advantageously ensures that all-vanadium flow battery
Operation steady in a long-term in the high temperature environment.
Embodiment 2
To 60mL anode electrolyte (1.6M VOSO4+3M H2SO4) in be added 5mM ammonium paratungstate, stir simultaneously
And electrolyte to be measured is made after being completely dissolved.Respectively with electrolyte and blank electrolysis liquid (1.6M VOSO containing ammonium paratungstate4+3M
H2SO4) it is used as anode electrolyte, the 1.6M V of 60mL3++3M H2SO4As electrolyte liquid, two all-vanadium flow list electricity are assembled
Pond.Wherein, battery diaphragm is Nafion115 (Dupont), and film effective area is 48cm2, electrode is activated carbon-fiber felt, and bipolar plates are
Graphite plate, current density are 80mA cm-2.Monocell carries out constant current charge-discharge, blanking voltage 1.0- under the conditions of 50 DEG C
Thus 1.55V obtains battery capacity attenuation curve as shown in Figure 1.When battery reaches latter stage of charging, due to pentavalent in electrolyte
Vanadium ion is unstable and V is precipitated2O5, the blocking of the loss of active material and Carbon felt surface duct in electrolyte is caused, battery is caused
Capacity attenuation.As can be seen from Figure, compared with the battery that additive is not added, due to the phase between ammonium paratungstate and vanadium ion
Interaction not only improves significantly to the thermal stability of pentavalent vanadium, can also effectively inhibit latter stage of charging anode pentavalent
Vanadium Precipitation bring capacity attenuation.Therefore stability when ammonium paratungstate can be obviously improved electrolyte longtime running, mentions
The capacity retention ratio of high battery realizes that all-vanadium flow battery is more stably run.
Comparative example 1
1.8M pentavalent vanadium solution is prepared using electrolysis method, adds 1mM, 2mM and 5mM into 10mL pentavalent vanadium solution respectively
Ammonium paratungstate or silico-tungstic acid stir evenly after being sufficiently mixed, and are placed on 50 DEG C together with blank 1.8M pentavalent vanadium solution example
Water-bath in heat, observe the state of solution, investigate influences of the different addition contents to pentavalent vanadium thermal stability.
Influence situation table of the 2 different content additive of table to electrolyte stability
From Table 2, it can be seen that compared with the electrolyte of the additive containing silico-tungstic acid, the electrolyte of the additive containing ammonium paratungstate
The stable time is longer, and ammonium paratungstate has better inhibiting effect to the Precipitation of electrolyte, is more advantageous to all-vanadium flow electricity
The longtime running in pond.
Claims (5)
1. a kind of application of additive in positive electrolyte for all-vanadiumredox flow battery, it is characterised in that: the additive is wolframic acid
Ammonium, ammonium molybdate, niobic acid ammonium, tantalic acid ammonium, ammonium paratungstate, ammonium paramolybdate, secondary niobic acid ammonium, ammonium metatungstate, metamolybdic acid ammonium, inclined niobic acid
One of ammonium, ammonium dimolybdate, ammonium tetramolybdate, fluorine niobic acid ammonium or two kinds or more；The additive is dense in anode electrolyte
Degree is the mol/L of 0.01 mol/L ~ 0.5；Cell operating temperature is 50 DEG C.
2. application according to claim 1, it is characterised in that: concentration of the additive in anode electrolyte is
0.02 mol/L~0.05 mol/L。
3. application according to claim 1, it is characterised in that: the total concentration of vanadium oxygen root in the aqueous solution of anode electrolyte
For 0.5 ~ 5 mol/L, the total concentration of sulfate radical is 1 ~ 6 mol/L.
4. the application according to claims 1 or 3, it is characterised in that: vanadium oxygen root in the aqueous solution of the anode electrolyte
Total concentration be 1 ~ 3 mol/L, sulfate radical total concentration be 2 ~ 4 mol/L.
5. application according to claim 1 or 3, it is characterised in that: vanadium oxygen root includes VO in the aqueous solution of anode electrolyte2 +, VO2 +, V2O3 4+, sulfate radical contains SO in the aqueous solution of anode electrolyte4 2-。
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| CN106876767B true CN106876767B (en) | 2019-09-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106299434A (en) * | 2016-11-11 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of electrolyte of vanadium redox battery containing inorganic molybdate and vanadium cell |
| CN108258292A (en) * | 2018-03-29 | 2018-07-06 | 四川大学 | A kind of positive electrolyte for all-vanadiumredox flow battery and its configuration method |
| CN110838592B (en) * | 2018-08-16 | 2021-06-29 | 江苏泛宇能源有限公司 | Preparation method of flow battery electrolyte |
| CN111180776A (en) * | 2018-11-13 | 2020-05-19 | 陕西华银科技股份有限公司 | Novel high-stability electrolyte and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103730674A (en) * | 2012-12-31 | 2014-04-16 | 刘军 | Low-temperature liquid phase fuel reformer for flow batteries |
| CN104332638A (en) * | 2014-10-20 | 2015-02-04 | 中国科学院金属研究所 | Preparation method of tungsten-based catalyst/nano carbon fiber composite electrode for full-vanadium flow battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103730674A (en) * | 2012-12-31 | 2014-04-16 | 刘军 | Low-temperature liquid phase fuel reformer for flow batteries |
| CN104332638A (en) * | 2014-10-20 | 2015-02-04 | 中国科学院金属研究所 | Preparation method of tungsten-based catalyst/nano carbon fiber composite electrode for full-vanadium flow battery |
Non-Patent Citations (1)
| Title |
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| 全钒液流电池电解液的研究;陈勇;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》;20150215(第2期);第30-42页 * |
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