CN109841885A - The method of high concentration electrolyte liquid stability when improving all-vanadium flow battery operation - Google Patents
The method of high concentration electrolyte liquid stability when improving all-vanadium flow battery operation Download PDFInfo
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- CN109841885A CN109841885A CN201711213861.8A CN201711213861A CN109841885A CN 109841885 A CN109841885 A CN 109841885A CN 201711213861 A CN201711213861 A CN 201711213861A CN 109841885 A CN109841885 A CN 109841885A
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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 the method for high concentration electrolyte liquid stability when improving all-vanadium flow battery operation, the soluble alkali materials are at least one of the ammonium hydroxide of mass concentration 20-35%, sodium hydroxide, potassium hydroxide, aluminium hydroxide, lithium hydroxide, rubidium hydroxide.The high concentration electrolyte liquid is the aqueous sulfuric acid of divalent and/or trivalent vanadium, and wherein vanadium ion concentration is 1.6-4mol/L, sulfuric acid concentration 0.5-3mol/L.The stabilizer for the raising high concentration electrolyte liquid stability that the present invention uses, can make the H in high concentration electrolyte liquid in a short time+Concentration is restored to normal level, and the stability of high concentration electrolyte liquid is improved；The raw materials used in the present invention is from a wealth of sources, cheap, and technological operation is simple, reaction speed is controllable, can guarantee battery simultaneously chronically efficient stable to run.
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.When vanadium ion concentration in electrolyte
Gao Shi, the trivalent vanadium ion in electrolyte liquid are easier to be precipitated under high proton concentration.Therefore, it is necessary to improve high concentration cathode
The stability of electrolyte, to improve the stability of system.
Summary of the invention
Present invention aims at solving the above problems, high concentration cathode when providing a kind of operation of raising all-vanadium flow battery
The method of electrolyte stability will lead to the increased H of cathode due to migration etc.+Concentration reduces, and improves all-vanadium flow electricity to reach
The purpose of pond high concentration electrolyte liquid stability.This method can reduce H in electrolyte liquid in a short time+Concentration makes
System stable operation.
The electrolyte liquid of all-vanadium flow battery under normal circumstances, H+Concentration is will not be changed, because of cathode
Reaction will not generate H+, H will not be consumed+.And there is H in anode reaction+It participates in,
Positive reaction equation is
Battery passes through the operation of certain time, as ion is mutually gone here and there, the generation of side reaction and ion are spread, positive H+Migration
To cathode, lead to the H of cathode+Concentration increases, and works as cathode H+Concentration increase when, the bad stability of cathode vanadium ion and be precipitated
Solid causes battery can not normal charge and discharge.The present invention is to solve the above problems, the technical solution used are as follows:
Operation, H is added in the alkaline matter for dissolving in all-vanadium redox flow battery electrolyte system and do not generate precipitating+Concentration
In raised high concentration electrolyte liquid, its H is reduced+Concentration, to achieve the purpose that improve electrolyte liquid stability.This hair
The bright high concentration electrolyte liquid is the aqueous sulfuric acid of divalent and/or trivalent vanadium, before battery operation, wherein vanadium ion concentration
It is 2-3mol/L, sulfuric acid concentration 1- for 1.6-4mol/L, sulfuric acid concentration 0.5-3mol/L, preferably vanadium ion concentration
2.5mol/L；After battery operation, H in electrolyte liquid+Concentration is higher than H+Initial concentration 0.8-4mol/L (preferably 0.8-2mol/L,
More preferable 0.8-1mol/L) when, soluble alkali materials are added thereto, make H+It is initial dense to being less than that concentration is down to initial concentration
Degree+0.8mol/L, battery continue to run.
Alkaline matter of the present invention is as high concentration electrolyte liquid stability when improving all-vanadium flow battery operation
Restorative, alkaline matter are ammonium hydroxide, sodium hydroxide, potassium hydroxide, aluminium hydroxide, lithium hydroxide, the hydrogen of mass concentration 20-35%
At least one of rubidium oxide.Ammonium hydroxide, sodium hydroxide, the potassium hydroxide of preferred mass concentration 20-35%.
The positive electrolyte for all-vanadiumredox flow battery is the aqueous sulfuric acid of tetravalence and/or pentavalent vanadium, and wherein vanadium ion is dense
Degree is 1.0-4mol/L, and sulfuric acid concentration 0.5-3mol/L, preferably vanadium ion concentration are 2-3mol/L, sulfuric acid concentration 1-2.5
mol/L。
According to theoretical value, after 1mol alkaline matter is neutralized, there is fixed power loss subnumber, if the stabilizer is more than required
Amount, will lead to H in electrolyte+Concentration is too low, and conductivity is too low, influences battery performance, if stabilizer additive amount is insufficient, bears
Pole vanadium ion is there are still risk is precipitated, to influence battery operation.Those skilled in the art can be by measuring cathode H+
Concentration, electrolyte volume and its selected stabilizer type determine that the additive amount of stabilizer, the additive amount of the alkaline matter are
OH-Molar concentration is equal to H in the electrolyte after battery operation+Molar concentration and initial electrolysis liquid H+Difference-the A, A of molar concentration be
0mol/L to 0.8mol/L.
Beneficial outcomes of the invention:
1) method that the present invention proposes high concentration electrolyte liquid stability when a kind of raising all-vanadium flow battery operation, energy
Enough H reduced in high concentration electrolyte liquid in a short time+Concentration improves the stability of high concentration electrolyte liquid；
2) addition of additive of the present invention forms electrolyte and influences without significant adverse, to battery performance and each portion of system
Part is also influenced without significant adverse.
3) present invention process is easy to operate, reaction speed is controllable, can guarantee battery simultaneously being capable of chronically efficient stable
Operation.
4) the raw materials used in the present invention is from a wealth of sources, cheap.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
Comparative example 1
Being formed with positive and negative anodes is vanadium ion concentration 2mol/L, and the electrolyte of sulfuric acid concentration 2mol/L carries out all-vanadium flow electricity
Pond experiment, positive and negative anodes electrolyte product are respectively 200mL, experimental result discovery, the circulation left and right cathode trivalent vanadium of battery operation 220
Solid is attached in carbon felt, and carbon felt is caused to be hardened, and flow of electrolyte decline, battery can not continue to run.Through detecting, cathode at this time
H+Concentration is 6.85mol/L.
Embodiment 1
Being formed with positive and negative anodes is vanadium ion concentration 2mol/L, and the electrolyte of sulfuric acid concentration 2mol/L carries out all-vanadium flow electricity
Pond experiment, positive and negative anodes electrolyte product are respectively 200mL, after battery operation 150 recycles, detect cathode H+Concentration is 6mol/
The ammonium hydroxide of appropriate mass concentration 28% is added, by H in L thereto+Concentration is down to 4.8mol/L, and battery continues to run, when battery is transported
After row to 400 circulations, cathode H is detected+Concentration is 5.4mol/L, experimental result discovery, still can be with after battery operation 400 recycles
It operates normally, and performance is without obvious decaying.Battery performance is as shown in table 1
Table 1 adds battery performance before and after stabilizer ammonium hydroxide
| Coulombic efficiency | Voltage efficiency | Energy efficiency | |
| Initially | 97% | 86% | 83% |
| After 150 circulations | 97% | 85% | 82% |
| After ammonium hydroxide is added | 97% | 85% | 82% |
Embodiment 2
Being formed with positive and negative anodes is vanadium ion concentration 2mol/L, and the electrolyte of sulfuric acid concentration 2mol/L carries out all-vanadium flow electricity
Pond experiment, positive and negative anodes electrolyte product are respectively 200mL, after battery operation 100 recycles, detect cathode H+Concentration is
Appropriate aluminium hydroxide is added in 5.7mol/L thereto, by H+Concentration is down to 4.2mol/L, and battery continues to run, and works as battery operation
To 450 circulations, cathode H is detected+Concentration is 5mol/L, and experimental result discovery still can be normal after battery operation 450 recycles
Operation, and performance is without obvious decaying.Battery performance is as shown in table 2
Table 2 adds battery performance before and after stabilizer aluminium hydroxide
| Coulombic efficiency | Voltage efficiency | Energy efficiency | |
| Initially | 97% | 87% | 84% |
| After 100 circulations | 97% | 86% | 83% |
| After aluminium hydroxide is added | 97% | 86% | 83% |
Embodiment 3
Being formed with positive and negative anodes is vanadium ion concentration 3mol/L, and the electrolyte of sulfuric acid concentration 1.8mol/L carries out all-vanadium flow
Cell Experimentation An, positive and negative anodes electrolyte product are respectively 200mL, after battery operation 70 recycles, detect cathode H+Concentration is
Appropriate rubidium hydroxide is added in 5.5mol/L thereto, by H+Concentration is down to 4mol/L, and battery continues to run, when battery operation extremely
After 200 circulations, cathode H is detected+Concentration is 4.8mol/L, and experimental result discovery still can be normal after battery operation 200 recycles
Operation, and performance is without obvious decaying.Battery performance is as shown in table 3
Table 3 adds battery performance before and after stabilizer rubidium hydroxide
| Coulombic efficiency | Voltage efficiency | Energy efficiency | |
| Initially | 98% | 86% | 84% |
| After 70 circulations | 98% | 85% | 83% |
| After rubidium hydroxide is added | 98% | 84% | 82% |
Claims (4)
1. the method for high concentration electrolyte liquid stability when improving all-vanadium flow battery operation, it is characterised in that: described highly concentrated
Electrolyte liquid is spent for divalent and/or the aqueous sulfuric acid of trivalent vanadium, and before battery operation, wherein vanadium ion concentration is 1.6-
4mol/L, sulfuric acid concentration 0.5-3mol/L, preferably vanadium ion concentration are 2-3mol/L, sulfuric acid concentration 1-2.5mol/L, electricity
After the operation of pond, H in electrolyte liquid+Concentration is higher than H+Initial concentration 0.8-4mol/L (preferably 0.8-2mol/L, more preferable 0.8-
When 1mol/L), soluble alkali materials are added thereto, make H+Concentration is down to initial concentration to less than initial concentration+0.8mol/
L, battery continue to run.
2. according to the method described in claim 1, it is characterized by: the soluble alkali materials are mass concentration 20-35%
Ammonium hydroxide, sodium hydroxide, potassium hydroxide, aluminium hydroxide, lithium hydroxide, at least one of rubidium hydroxide；The water soluble alkali
Property substance is preferably at least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide of mass concentration 20-35%.
3. method according to claim 1 or 2, it is characterised in that: the positive electrolyte for all-vanadiumredox flow battery is tetravalence
And/or the aqueous sulfuric acid of pentavalent vanadium, wherein vanadium ion concentration be 1.6-4mol/L, sulfuric acid concentration 0.5-3mol/L, preferably
Vanadium ion concentration is 2-3mol/L, sulfuric acid concentration 1-2.5mol/L.
4. method according to claim 1 or 2, it is characterised in that: in cell operation, detect H in electrolyte liquid+
When concentration increases, soluble alkali materials are added into electrolyte liquid, the additive amount of the alkaline matter is OH-Molar concentration
Equal to H in the electrolyte after battery operation+Molar concentration and initial electrolysis liquid H+Difference-the A of molar concentration, A arrive for 0mol/L
0.8mol/L。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711213861.8A CN109841885B (en) | 2017-11-28 | 2017-11-28 | Method for improving stability of high-concentration negative electrolyte during operation of all-vanadium redox flow battery |
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| CN201711213861.8A CN109841885B (en) | 2017-11-28 | 2017-11-28 | Method for improving stability of high-concentration negative electrolyte during operation of all-vanadium redox flow battery |
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| CN109841885B CN109841885B (en) | 2021-06-29 |
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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 |
| CN118336060A (en) * | 2024-04-10 | 2024-07-12 | 山西国润储能科技有限公司 | All-vanadium redox flow battery electrolyte and preparation method thereof |
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| JP2000281345A (en) * | 1999-03-31 | 2000-10-10 | Shinko Kagaku Kogyo Kk | Tetravalent vanadium compound and production of solution containing the same |
| CN101572319A (en) * | 2009-06-18 | 2009-11-04 | 湖南维邦新能源有限公司 | Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte |
| CN104716335A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Electrode for liquid flow batteries, preparation and application |
| CN105702995A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Method for restoring capacity of all-vanadium redox flow battery |
| CN106997958A (en) * | 2016-01-22 | 2017-08-01 | 大连融科储能技术发展有限公司 | A kind of method for eliminating all-vanadium redox flow battery electrolyte impurity effect |
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2017
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| JP2000281345A (en) * | 1999-03-31 | 2000-10-10 | Shinko Kagaku Kogyo Kk | Tetravalent vanadium compound and production of solution containing the same |
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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 |
| CN118336060A (en) * | 2024-04-10 | 2024-07-12 | 山西国润储能科技有限公司 | All-vanadium redox flow battery electrolyte and preparation method thereof |
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| CN109841885B (en) | 2021-06-29 |
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