CN109768309A - A kind of application of electrolyte liquid in all-vanadium flow battery - Google Patents
A kind of application of electrolyte liquid in all-vanadium flow battery Download PDFInfo
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- CN109768309A CN109768309A CN201711094326.5A CN201711094326A CN109768309A CN 109768309 A CN109768309 A CN 109768309A CN 201711094326 A CN201711094326 A CN 201711094326A CN 109768309 A CN109768309 A CN 109768309A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of application of electrolyte liquid in all-vanadium flow battery, the electrolyte liquid contains the one or two or more kinds of the potassium of pyrophosphoric acid, phosphate, dihydric phosphate, phosphoric acid hydrogen disalt, polyphosphate or pyrophosphate, sodium, ammonium salt；The electrolyte liquid is the aqueous solution containing vanadium oxygen root and sulfate radical, and vanadium concentration is 1-5mol/L in all-vanadium flow battery electrolyte liquid, and concentration of the phosphorous substance in electrolyte liquid is 10‑3Mmol/L~1mol/L.The stabilizer for the electrolyte liquid that the present invention uses can effectively improve stability of the electrolyte liquid under high proton concentration, realize the stable operation of battery, and can improve the concentration of vanadium ion in electrolyte, improve battery energy density.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 a kind of application of electrolyte in all-vanadium flow battery.
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.
The critical material of all-vanadium flow battery mainly includes pole dual-pole board, film and electrolyte.All-vanadium flow battery is crucial
The research of material, especially research in terms of improving the stability of critical material, durability and reducing just seem outstanding
It is important.Electrolyte is the important component of all-vanadium flow battery, its concentration and volume directly determine the capacity of battery.
Therefore, the stability of electrolyte directly influences the stability of all-vanadium flow battery.Electricity is supported used by all-vanadium flow battery
Solution matter is the aqueous solution of sulfuric acid, and trivalent vanadium ion is easy to be precipitated under high proton concentration, and battery capacity is not only caused to reduce, and
And it is easy blocking battery and pipeline, affect stability of the battery in During Process of Long-term Operation.Therefore, it is necessary to improve trivalent vanadium
Stability be stabilized electrolyte also can under higher proton concentration, to improve the stability of system.
Summary of the invention
Present invention aims at solving the above problems, provides a kind of electrolyte liquid and is applied in all-vanadium flow battery,
To achieve the purpose that improve all-vanadium flow battery stability.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of application of electrolyte liquid in all-vanadium flow battery, the electrolyte liquid contain pyrophosphoric acid, phosphate,
The one or two or more kinds of dihydric phosphate, phosphoric acid hydrogen disalt, the potassium of polyphosphate or pyrophosphate, sodium, ammonium salt；It is described negative
Pole electrolyte is the aqueous solution containing vanadium oxygen root and sulfate radical, and vanadium concentration is 1-5mol/ in all-vanadium flow battery electrolyte liquid
L, SO4 2-Molar concentration be 4-8mol/L, H+Concentration is 6-12mol/L, and the phosphorous substance is dense in electrolyte liquid
Degree is 10-3Mmol/L~1mol/L.
SO in the all-vanadium flow battery electrolyte liquid4 2-Molar concentration be 6-8mol/L；H+Concentration is 8-12mol/
L。
Concentration of the phosphorous substance in electrolyte liquid is 0.01mmol/L~0.5mol/L.All-vanadium flow battery
Electrolyte liquid is using temperature in -20 DEG C -60 DEG C, preferably 0-50 DEG C.
Vanadium concentration is 1-5mol/L, SO in the all-vanadium flow battery electrolyte liquid4 2-Molar concentration be 2-8mol/
L, H+Concentration is 2-10mol/L.The electrolyte is in all-vanadium flow battery；The all-vanadium flow battery is with metal class electrode
Or carbon class electrode is used as anode and negative electrode material, using ion-conductive membranes as battery diaphragm.
Beneficial outcomes of the invention:
1) present invention proposes stabilizer of the phosphorous substance of one kind as all-vanadium flow battery electrolyte liquid, inhibits trivalent
Precipitation of the vanadium under high proton concentration；
2) stability of trivalent vanadium can be improved in the addition of additive of the present invention, thus can be improved in electrolyte liquid vanadium from
The effect of sub- concentration, finally improves battery energy density.Electrolyte liquid
3) 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 be chronically high simultaneously
Imitate stable operation.
Detailed description of the invention
Fig. 1 is the battery performance that electrolyte liquid is free of stabilizer in embodiment 4.
Fig. 2 is the battery performance of electrolyte liquid phosphoric acid stabilizer in embodiment 4.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Embodiment 1
2.2mol/L trivalent vanadium solution is prepared using electrolysis method, wherein sulfuric acid concentration is 4mol/L, respectively to 10mL trivalent
Different stabilizers is added in vanadium solution, stabilizer type and content are as shown in table 1, stirred evenly after being sufficiently mixed, and with sky
White 2mol/L trivalent vanadium solution example is stood together, observes the state of solution, investigates different stabilizers to trivalent vanadium thermal stability
Influence.
Experimental result is as shown in table 1.As can be seen from Table 1, when being added without any stabilizer, the stabilization time of trivalent vanadium
Less than 2 days, be added disodium hydrogen phosphate, potassium polyphosphate, sodium pyrophosphate when, the stabilization time of trivalent vanadium extend to respectively 15 days,
25 days and 18 days, illustrate that phosphoric acid, disodium hydrogen phosphate, potassium polyphosphate, sodium pyrophosphate can more effectively improve the stabilization of trivalent vanadium
Property, especially guarantee its stability under high proton concentration.Secondly, when the content of disodium hydrogen phosphate is 1.5mol/L, it is steady
It fixes time and is obviously shortened (1.5 days), solid precipitation is arranged at solution bottom, and in addition when temperature is subzero 25 degree, the stable time is
0.5 day, the temperature of the dosage and electrolyte that illustrate solution stabilizer had larger impact to electrolyte stability.
Table 1
| Stabilizer type | Temperature | Stabiliser content | Stablize the time |
| Blank | Room temperature | < 2 days | |
| Disodium hydrogen phosphate | Room temperature | 0.05mol/L | > 15 days |
| Potassium polyphosphate | Room temperature | 0.01mol/L | > 25 days |
| Sodium pyrophosphate | Room temperature | 0.1mol/L | > 18 days |
| Disodium hydrogen phosphate | Room temperature | 1.5mol/L | < 1.5 days |
| Disodium hydrogen phosphate | Subzero 25 degree | 0.05mol/L | < 0.5 day |
Note: stablizing the time is the time of solid precipitate occur in solution.
Embodiment 2
Being formed with positive and negative anodes is vanadium ion concentration 2.2mol/L, and the electrolyte of sulfuric acid concentration 4mol/L carries out all-vanadium flow
Cell Experimentation An, electrode are carbon felt, current density 100mA/cm2.Electrolyte liquid is free of stabilizer, B group battery in A group battery
Middle potassium polyphosphate of the electrolyte liquid containing 0.01mol/L carries out charge and discharge as stabilizer, with constant current mode, carries out simultaneously
Experiment.Experimental result discovery, the battery operation 20 without stabilizer recycle left and right cathode trivalent vanadium solid and are attached in carbon felt, lead
Carbon felt is caused to be hardened, flow of electrolyte decline, battery can not continue to run, and the battery operation 300 of the stabilizer containing potassium polyphosphate
Circulation, cathode are precipitated without obvious solid, illustrate that potassium polyphosphate can effectively improve the stability of trivalent vanadium.
Embodiment 3
Being formed with positive and negative anodes is vanadium ion concentration 2.2mol/L, and the electrolyte of sulfuric acid concentration 4mol/L carries out all-vanadium flow
Cell Experimentation An, electrode are carbon felt, current density 100mA/cm2.Wherein electrolyte liquid disodium hydrogen phosphate containing 0.05mol/L is steady
Determine agent.Experimental result discovery, the battery operation of phosphoric acid disodium hydrogen stabilizer be more than 200 circulation, dismantle battery find cathode without
Obvious solid is precipitated, and illustrates that the stabilizer can effectively improve the stability of trivalent vanadium.
Embodiment 4
Using electrode as carbon felt, current density 100mA/cm2Condition carry out all-vanadium flow battery experiment, A group battery
Vanadium ion concentration is 1.5mol/L in positive and negative anodes electrolyte, and is free of stabilizer, vanadium ion in the positive and negative anodes electrolyte of B group battery
Concentration is 2mol/L, and containing the pyrophosphoric acid of 0.1mol/L in electrolyte liquid, carries out charge and discharge with constant current mode, carry out simultaneously
Experiment.A group battery performance as shown in Figure 1, B group battery performance as shown in Fig. 2, as a result, it has been found that, phosphorous acid additive it is cell performance
It can be better than the performance of blank battery, illustrate that the comprehensive performance of the high concentration electrolyte is higher than 1.5mol/L electrolyte.
Embodiment 5
Being formed with positive and negative anodes is vanadium ion concentration 2.2mol/L, and the electrolyte of sulfuric acid concentration 4mol/L carries out all-vanadium flow
Cell Experimentation An, electrode are carbon felt, current density 100mA/cm2.Electrolyte liquid pyrophosphoric acid containing 0.05mol/L in A group battery
Stable sodium agent, positive and negative anodes electrolyte contains 0.05mol/L sodium pyrophosphate stabilizer in B group battery, is filled with constant current mode
Electric discharge, while being tested.Two groups of battery performances are as shown in table 2.As can be seen from the table, two groups of battery performances are without obvious poor
It is different, illustrate that positive and negative anodes two sides contain additive of the same race, battery performance is had no significant effect.
Table 2
| Coulombic efficiency | Voltage efficiency | Energy efficiency | |
| A group | 98.6% | 87.8% | 86.6% |
| B group | 98.5% | 87.8% | 86.5% |
Claims (6)
1. a kind of application of electrolyte liquid in all-vanadium flow battery, it is characterised in that: contain in the electrolyte liquid
Phosphorus substance, phosphorus containg substances are in pyrophosphoric acid, phosphate, dihydric phosphate, phosphoric acid hydrogen disalt, polyphosphate or pyrophosphate
One of one or two or more kinds of potassium, sodium, ammonium salt or two kinds or more；The electrolyte liquid is to contain vanadium oxygen root and sulfuric acid
The aqueous solution of root, vanadium concentration is 1-5mol/L, SO in all-vanadium flow battery electrolyte liquid4 2-Molar concentration be 4-8mol/L,
H+Concentration is 6-12mol/L, and concentration of the phosphorus containg substances in electrolyte liquid is 10-3Mmol/L~1mol/L.
2. application according to claim 1, it is characterised in that: SO in the all-vanadium flow battery electrolyte liquid4 2-Rub
Your concentration is 6-8mol/L；H+Concentration is 8-12mol/L.
3. application according to claim 1, it is characterised in that: concentration of the phosphorus containg substances in electrolyte liquid is
0.01mmol/L~0.5mol/L.
4. application according to claim 1, it is characterised in that: all-vanadium flow battery electrolyte liquid is using temperature -20
DEG C -60 DEG C, preferably 0-50 DEG C.
5. application according to claim 1, it is characterised in that: the electrolyte is in all-vanadium flow battery；It is described complete
Vanadium flow battery using metal class electrode or carbon class electrode as anode and negative electrode material, using ion-conductive membranes as battery every
Film.
6. application according to claim 1, it is characterised in that: vanadium concentration is 1-5mol/L, SO in anode electrolyte4 2-'s
Molar concentration is 2-8mol/L, H+Concentration is 2-10mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911704A (en) * | 2019-11-26 | 2020-03-24 | 中国科学院金属研究所 | Iron-chromium flow battery electrolyte and application thereof |
| CN112216856A (en) * | 2020-09-17 | 2021-01-12 | 大连博融新材料有限公司 | Hydrochloric acid electrolyte stable at high temperature, preparation method and application thereof |
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| CN102110836A (en) * | 2011-01-26 | 2011-06-29 | 上海林洋储能科技有限公司 | High-reliability vanadium ion electrolyte |
| CN103490086A (en) * | 2013-09-03 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of vanadium electrolyte |
| JP2014235946A (en) * | 2013-06-04 | 2014-12-15 | 旭化成イーマテリアルズ株式会社 | Electrolyte and redox flow battery |
| CN106384835A (en) * | 2016-11-11 | 2017-02-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Stabilizing agent for electrolyte of all-vanadium redox flow battery and preparation method thereof |
-
2017
- 2017-11-09 CN CN201711094326.5A patent/CN109768309A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102110836A (en) * | 2011-01-26 | 2011-06-29 | 上海林洋储能科技有限公司 | High-reliability vanadium ion electrolyte |
| JP2014235946A (en) * | 2013-06-04 | 2014-12-15 | 旭化成イーマテリアルズ株式会社 | Electrolyte and redox flow battery |
| CN103490086A (en) * | 2013-09-03 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of vanadium electrolyte |
| CN106384835A (en) * | 2016-11-11 | 2017-02-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Stabilizing agent for electrolyte of all-vanadium redox flow battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911704A (en) * | 2019-11-26 | 2020-03-24 | 中国科学院金属研究所 | Iron-chromium flow battery electrolyte and application thereof |
| CN112216856A (en) * | 2020-09-17 | 2021-01-12 | 大连博融新材料有限公司 | Hydrochloric acid electrolyte stable at high temperature, preparation method and application thereof |
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