CN114156514A - Flow battery electrolyte and application thereof - Google Patents
Flow battery electrolyte and application thereof Download PDFInfo
- Publication number
- CN114156514A CN114156514A CN202010937173.1A CN202010937173A CN114156514A CN 114156514 A CN114156514 A CN 114156514A CN 202010937173 A CN202010937173 A CN 202010937173A CN 114156514 A CN114156514 A CN 114156514A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- flow battery
- bromine
- concentration
- bromide
- 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.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 80
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 23
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 23
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- HQRTUZASZSPFOU-UHFFFAOYSA-N [Ti].[Br] Chemical compound [Ti].[Br] HQRTUZASZSPFOU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 12
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 6
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229960003178 choline chloride Drugs 0.000 claims abstract description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 14
- 239000003115 supporting electrolyte Substances 0.000 claims description 12
- 150000003608 titanium Chemical class 0.000 claims description 12
- -1 hydrogen ions Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 229940006460 bromide ion Drugs 0.000 claims description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 150000003842 bromide salts Chemical class 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 abstract description 19
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000002238 attenuated effect Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Fuel Cell (AREA)
Abstract
The application discloses a flow battery electrolyte and application thereof, wherein the electrolyte contains organic ammonium salt; the organic ammonium salt is at least one selected from 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and choline chloride. The novel complexing agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride or choline chloride introduced into the electrolyte can be complexed with bromine generated in the charging process under an acidic condition, so that the effects of inhibiting the diffusion and volatilization of bromine are achieved, the product after complexing is close to a homogeneous phase, a large amount of compact oil phase cannot be generated in the electrolyte, and the performance attenuation caused by insufficient contact between the electrolyte and an electrode due to the separation phase generated by the generated bromine complex and the electrolyte is avoided. The titanium-bromine flow battery containing the electrolyte is at 40mA/cm2The energy efficiency is over 80% under the current density of the high-voltage power supply, and the performance is not attenuated when the high-voltage power supply is stably operated for over 1000 circles.
Description
Technical Field
The application relates to a flow battery electrolyte and application thereof, and belongs to the field of flow batteries.
Background
The redox flow battery is considered as the most promising large-scale energy storage technology due to the advantages of independent and adjustable power density and energy density, long cycle life, high safety, low cost and the like. In view of the fact that the all-vanadium redox flow battery with the highest comprehensive performance and the most mature research technology still has higher cost and limited vanadium reserves, researchers are focusing on other new systems with energy storage potential.
Compared with an organic system, the inorganic system has higher competitiveness due to the advantages of good stability and high concentration of active substances, and a zinc bromine battery in the inorganic system is widely researched due to the advantages of low cost, high energy density and the like, but still has the problems of zinc dendrite, limited surface capacity, positive electrode bromine diffusion, non-uniformity of a bromine simple substance after being complexed with a complexing agent, battery performance attenuation and the like.
Disclosure of Invention
According to one aspect of the application, the liquid flow battery electrolyte is provided, wherein the hydroxyl-containing complexing agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride or choline chloride is in a nearly homogeneous phase with the electrolyte after being complexed with bromine, and the battery performance is improved.
The electrolyte contains organic ammonium salt;
the organic ammonium salt is at least one selected from 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and choline chloride.
Preferably, the organic ammonium salt is 3-chloro-2-hydroxypropyltrimethylammonium chloride.
Optionally, the electrolyte further comprises an active material;
the active material comprises hydrobromic acid or a bromide salt.
Alternatively, the concentration of the organic ammonium salt is 0.05 to 2.5 mol/L.
Specifically, the lower limit of the concentration of the organic ammonium salt may be independently selected from 0.05mol/L, 0.1mol/L, 0.5mol/L, 0.7mol/L, 1 mol/L; the upper concentration limit of the organic ammonium salt can be independently selected from 1.2mol/L, 1.5mol/L, 2mol/L, 2.1mol/L and 2.5 mol/L.
Alternatively, the bromide ion concentration is 0.1-5 mol/L;
preferably, the bromide ion concentration is 0.5 to 3 mol/L.
Specifically, the lower limit of the concentration of the bromide ions can be independently selected from 0.1mol/L, 0.5mol/L, 1mol/L, 1.4mol/L and 2 mol/L; the upper limit of the concentration of the bromide ion can be independently selected from 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L and 5 mol/L.
Preferably, the concentration ratio of the organic ammonium salt to the bromide ion in the electrolyte is 1: 1-1: 2.
Optionally, the electrolyte further comprises a supporting electrolyte;
the supporting electrolyte is acid;
preferably, the supporting electrolyte is selected from HCl, H2SO4、HNO3At least one of (1).
Optionally, the concentration of hydrogen ions in the electrolyte is 1-5 mol/L;
preferably, the concentration of hydrogen ions is 2 to 3 mol/L.
Specifically, the lower limit of the concentration of the hydrogen ions can be independently selected from 1mol/L, 1.5mol/L, 2.1mol/L, 2.5mol/L and 3 mol/L; the upper limit of the concentration of the hydrogen ions can be independently selected from 3.4mol/L, 3.8mol/L, 3.5mol/L, 4mol/L and 5 mol/L.
Optionally, the bromide-containing salt is at least one of potassium bromide, sodium bromide, and ammonium bromide.
Optionally, the electrolyte contains bromide salt as active material, and HCl and H as supporting electrolyte2SO4、HNO3At least one of (1).
In the present application, when the active material is hydrobromic acid, a supporting electrolyte may be added in order to ensure that the concentration of hydrogen ions is optimal, and if the concentration of hydrobromic acid is less than 1mol/L, the supporting electrolyte must be added.
According to still another aspect of the application, the application of the electrolyte of the flow battery is provided, and the electrolyte is applied to a single cell.
The single battery comprises a positive electrode, a negative electrode and a diaphragm for separating the positive electrode and the negative electrode, wherein a cavity between the positive electrode and the diaphragm is filled with positive electrolyte, and a cavity between the negative electrode and the diaphragm is filled with negative electrolyte;
the positive electrode electrolyte comprises at least one of the flow battery electrolytes described in any one of the above.
The specific composition structure of the flow battery in the application is conventional in the prior art, specifically, the single battery comprises a positive electrode, a negative electrode, a diaphragm for separating the positive electrode from the negative electrode, and a silica gel pad for sealing, and the positive electrode and the negative electrode of the single battery respectively comprise a metal end plate, a current collector, a flow frame, a corresponding positive electrode/negative electrode, and a corresponding filled positive electrolyte/negative electrolyte.
Optionally, in the titanium-bromine flow battery, the solvents of the positive electrolyte and the negative electrolyte are both water;
the active material in the negative electrode electrolyte is a tetravalent titanium salt.
Optionally, in the electrolyte of the negative electrode, the concentration of the tetravalent titanium salt is 0.1-3mol/L,
preferably, the concentration of the tetravalent titanium salt is 0.4 to 1.4 mol/L;
preferably, the tetravalent titanium salt is at least one of titanium sulfate, titanyl sulfate and titanium tetrachloride;
further preferably, the tetravalent titanium salt is titanium sulfate.
Specifically, the lower limit of the concentration of the tetravalent titanium salt may be independently selected from 0.1mol/L, 0.4mol/L, 1.0mol/L, 1.4mol/L, 1.8 mol/L; the upper concentration limit of the tetravalent titanium salt may be independently selected from 2.0mol/L, 2.2mol/L, 2.5mol/L, 2.7mol/L, 3.0 mol/L.
In the single cell of the present application, the composition of the positive electrode electrolyte and the negative electrode electrolyte may be the same or different. The same positive electrolyte and negative electrolyte means that the initial electrolytes are the same, the electrolytes are respectively changed into different substances at two electrodes after charging, the same initial components can reduce interpenetration, and the performance is improved. When the positive electrode electrolyte and the negative electrode electrolyte are different, other components may be added under the condition of having at least the components defined in the present application.
Optionally, the positive electrode and the negative electrode are independently selected from at least one of carbon felt, graphite felt and carbon cloth;
the diaphragm is a porous film;
preferably, the porous membrane has a thickness of 10 to 1000 μm, a porosity of 10 to 80%, and a pore diameter ranging from 0.5 to 10 nm.
The porous film of the present application contains at least one of polyolefin group materials. The cost is much lower than that of the common Nafion membrane, and the performance is more excellent.
According to yet another aspect of the present application, there is provided an acid bromine-based flow battery, which is a single cell or a stack of at least two single cells;
the single cell is selected from any one of the single cells described above.
Optionally, the acid bromine-based flow battery is a titanium bromine flow battery.
Specifically, the application provides a titanium-bromine flow battery, which comprises a galvanic pile formed by connecting one or more than two single cells in series, a positive electrolyte and a negative electrolyte storage tank, wherein the positive electrolyte is hydrobromic acid or a bromide ion-containing salt solution, a supporting electrolyte and an additive for inhibiting bromine diffusion and volatilization, the negative electrolyte is a tetravalent titanium salt solution and the supporting electrolyte, and the solvent is water.
The positive and negative electrolytes enter the positive and negative electrodes from the positive and negative electrolyte storage tanks through pipelines by a pump. Positive electrode active material Br during charging-Oxidation reaction to produce Br2And polybromide, negative active material TiO2+Reduction reaction is carried out to generate Ti3+(ii) a At the time of discharge, positive electrode Br2Reduction reaction with polybromide to produce Br-Negative electrode Ti3+Oxidation reaction to produce TiO2+。
The beneficial effects that this application can produce include:
1) according to the flow battery electrolyte provided by the application, a novel complexing agent 3-chloro-2-hydroxypropyl trimethyl ammonium Chloride (CHA) or choline Chloride (CHO) is introduced, and can be complexed with bromine generated in a charging process under an acidic condition, so that the diffusion and volatilization of bromine are inhibited; compared with the traditional complexing of 1-methyl-1-ethyl pyrrolidine bromide (MEP), the product after complexing is close to a homogeneous phase, and a large amount of compact oil phase can not be generated in the electrolyte, so that the performance attenuation caused by insufficient contact between the electrolyte and an electrode due to the generated bromine complex and the separation phase generated by the electrolyte is avoided.
2) The novel complexing agent adopted in the flow battery electrolyte is industrially used for the cation etherifying agent, the production capacity is large, the cost is greatly lower than MEP, and the battery cost is reduced.
3) When the flow battery electrolyte provided by the application is used for an acid bromine-based flow battery, not only can the diffusion and volatilization of bromine be inhibited, but also the solubility in water exceeds 3mol/L without being limited by surface capacity under the condition that titanium is used as a negative electrode active substance, so that the theoretical energy density of the battery is up to 72.36 wh/L; in addition, the titanium has abundant reserves in the earth crust, low cost and high electrochemical activity, thereby greatly reducing the cost of the battery and improving the performance of the battery.
4) The titanium-bromine flow battery assembled by adopting the flow battery electrolyte provided by the application is at 40mA/cm2The energy efficiency is over 80% under the current density, the performance attenuation is avoided when the stable operation is over 1000 circles, and the circulation stability is obviously superior to that of the flow battery adopting the conventional well-known MEP bromine complexing agent.
5) The acidic bromine-based flow battery assembled by the method uses the porous membrane as the diaphragm, not only has lower cost than Nafion, but also obtains higher performance due to high ion conductivity.
Drawings
FIG. 1 shows the Ti-Br flow battery obtained in example 2, using 1.0M HBr +1.0M Ti (SO)4)2+2M HCl +0.5M CHA as electrolyte, 40mA/cm2Battery performance at 70% electrolyte utilization at current density, where plot a is a plot of battery efficiency and plot b is a plot of charge and discharge capacity;
FIG. 2 is a graph of the titanium bromine flow batteries obtained in example 2 and comparative example 1 at 40mA/cm2A plot of cell performance at 70% electrolyte utilization at current density;
FIG. 3 is a graph comparing the charge and discharge capacities of the titanium bromine flow batteries obtained in example 2, example 5, comparative example 1 and comparative example 4;
FIG. 4 is a graph comparing the energy efficiency of the titanium bromine flow batteries obtained in example 2, example 5, comparative example 1 and comparative example 4;
FIG. 5 is a graph comparing the coulombic efficiencies of the titanium-bromine flow batteries obtained in example 2, example 5, comparative example 1, and comparative example 4;
fig. 6 is a graph comparing the voltage efficiency of the titanium bromine flow batteries obtained in example 2, example 5, comparative example 1 and comparative example 4.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The battery performance test adopts an Arbin 2000 charging and discharging instrument.
Example 1
Assembling the titanium bromine flow battery:
the positive electrolyte and the negative electrolyte have the same composition and are respectively 0.1mol/L hydrobromic acid and 0.1mol/L Ti (SO)4)20.1mol/L of 3-chloro-2-hydroxypropyl trimethyl ammonium Chloride (CHA) and 2mol/L of HCl.
Assembling single cells:
the structure of the monocell comprises end plates, a graphite plate current collector, 6 multiplied by 8cm carbon felts as positive and negative electrodes, a Daramic 900-micron polyethylene film as a porous film, a liquid flow frame, a silica gel pad, positive and negative electrolyte storage tanks, pumps and pipelines.
Other examples assembled batteries having only the electrolyte composition different from that of example 1 are shown in table 1.
The performance of the batteries obtained in all the examples is tested, and the test conditions of the performance of the batteries are as follows: the flow rate of electrolyte (positive and negative electrolyte) in the battery is 50ml/min, and the charging current is 40-80mA/cm2The charge cut-off voltage was 1.4V, the discharge cut-off voltage was 0.1V, and the charge capacity was 20 Ah/L. The average values of coulombic efficiency CE, voltage efficiency VE, and energy efficiency EE were measured 100 cycles before the charge-discharge cycle, and the results are shown in table 1.
TABLE 1 Battery Performance of different examples and comparative examples
As can be seen from the performance data of examples 1-4, when CHA was used as a complexing agent for bromine, the hydrogen ion concentration was adjusted from 2.0mol/L to 3.4mol/L by the supporting electrolyte at 40mA/cm2Under the current density, the high performance that the energy efficiency exceeds 80 percent and the coulombic efficiency exceeds 95 percent can be realized.
In example 5, CHO was used as an additive, and the concentration of hydrogen ions was 40mA/cm at 3mol/L2Under the current density, the high performance that the energy efficiency exceeds 80 percent and the coulombic efficiency exceeds 93 percent can be realized.
It can be seen from examples 2, 6 and 7 that the amount of additive also affects the bromine complexing effect. In examples 6 and 7, when the additive concentration: when the concentrations of the bromide ions are 1:1 and 2:1 respectively, the coulombic efficiency can reach more than 97%, and the voltage efficiency is slightly lower than that of the embodiment 2 when the concentration ratio of the bromide ions to the bromide ions is 1:2, but the energy efficiency can be finally achieved to exceed 75%. Therefore, the additive concentration is preferably: the bromide ion concentration was 1: 2.
FIG. 1 shows the Ti-Br flow battery obtained in example 2, using 1.0M HBr +1.0M Ti (SO)4)2+2M HCl +0.5M CHA as electrolyte, 40mA/cm2Under the current density, the battery performance diagram at the electrolyte utilization rate of 70 percent shows that the battery can stably run for 1000 circles without capacity and efficiency attenuation, and the energy efficiency can reach 80 percent.
FIG. 2 is a graph showing the discharge capacity of the titanium-bromine flow batteries obtained in example 2 and comparative example 1, and it can be seen that 40mA/cm is present2At a current density of 70% of the electrolyte utilization rate, the battery (example 2) added with the complexing agent (i.e., the additive is CHA) can achieve 1000-cycle discharge capacity without significant attenuation, and the coulombic efficiency is only 72.13% and the energy efficiency is only 66.89% in a system without the complexing agent (comparative example 1). The battery discharge capacity decays severely.
FIGS. 3-6 are 1.0M HBr +1.0M Ti (SO) respectively4)2And+ 2M HCl is an initial electrolyte, and when CHA, MEP and CHO are complexing agents, the performances of the battery are compared. It can be seen that the discharge capacity, energy efficiency and coulombic efficiency are higher and the performance is most stable without fading when CHA is used as the complexing agent, and the initial performance similar to that of CHA when MEP is used as the complexing agent but with the same effect as that of CHAThe cycle is carried out, and the discharge capacity, the energy efficiency and the coulomb efficiency are attenuated continuously; when CHO is used as a complexing agent, although the initial performance is slightly lower than MEP, the performance is stable, and obvious attenuation can not occur; without complexing agents, the performance decay is severe. Meanwhile, when the CHA and the CHO are complexing agents, the voltage efficiency of the battery is equivalent to that of a battery which takes the MEP as the complexing agent and does not have the complexing agent, and the battery has good performance.
Tests on the battery obtained in the comparative example 2-3 show that the battery cannot run for a long time when the hydrogen ion concentration is lower than 0.2mol/L, and experiments show that the product of the additive and bromine generated after charging is solid, so that a pipeline is blocked after the battery runs for less than 10 circles, and the battery cannot run normally.
The battery obtained in comparative example 4 was tested to find that 40mA/cm was used as a complexing agent in the case of using a commonly used MEP as a complexing agent2At the current density, the coulombic efficiency is 89.23%, the energy efficiency is 76.46%, the battery performance is lower than that of the CHA system at the same concentration, and the cycling stability of the battery is not as good as that of the battery obtained in the application.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The flow battery electrolyte is characterized by comprising an organic ammonium salt;
the organic ammonium salt is at least one selected from 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and choline chloride.
2. The flow battery electrolyte as recited in claim 1, further comprising an active material;
the active material comprises hydrobromic acid or a bromide salt;
preferably, the concentration of the organic ammonium salt in the electrolyte is 0.05-2.5 mol/L;
preferably, the concentration of bromide ions in the electrolyte is 0.1-5 mol/L;
further preferably, the bromide ion concentration is 0.5 to 3 mol/L.
3. The flow battery electrolyte of claim 2,
the electrolyte also comprises a supporting electrolyte;
the supporting electrolyte is an acid;
preferably, the supporting electrolyte is selected from HCl, H2SO4、HNO3At least one of;
preferably, the concentration of hydrogen ions in the electrolyte is 1-5 mol/L;
further preferably, the concentration of hydrogen ions is 2 to 3 mol/L.
4. A flow battery electrolyte as recited in any one of claims 1-3, wherein the bromide-containing salt is at least one of potassium bromide, sodium bromide, and ammonium bromide.
5. The single cell is characterized by comprising a positive electrode, a negative electrode and a diaphragm for separating the positive electrode from the negative electrode, wherein a cavity between the positive electrode and the diaphragm is filled with a positive electrolyte, and a cavity between the negative electrode and the diaphragm is filled with a negative electrolyte;
the positive electrolyte comprises at least one of the electrolytes of the flow battery of any one of claims 1-4.
6. The cell as claimed in claim 5, wherein the solvent of the positive electrolyte and the negative electrolyte is water;
the active substance in the negative electrode electrolyte is tetravalent titanium salt.
7. The cell as claimed in claim 5, wherein the concentration of the tetravalent titanium salt in the negative electrode electrolyte is 0.1 to 3mol/L,
preferably, the concentration of the tetravalent titanium salt is 0.4-1.4 mol/L;
preferably, the tetravalent titanium salt is at least one of titanium sulfate, titanyl sulfate and titanium tetrachloride.
8. The cell as claimed in claim 5, wherein the positive electrode and the negative electrode are independently selected from at least one of carbon felt, graphite felt, carbon cloth;
the diaphragm is a porous membrane;
preferably, the porous membrane has a thickness of 10 to 1000 μm, a porosity of 10 to 80%, and a pore diameter ranging from 0.5 to 10 nm.
9. The acid bromine-based flow battery is characterized in that the acid bromine-based flow battery is a single battery or a galvanic pile formed by at least two single batteries;
the cell is selected from the cell according to any one of claims 5 to 8.
10. The acid bromine-based flow battery of claim 9 wherein the acid bromine-based flow battery is a titanium bromine flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010937173.1A CN114156514B (en) | 2020-09-08 | 2020-09-08 | Electrolyte of flow battery and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010937173.1A CN114156514B (en) | 2020-09-08 | 2020-09-08 | Electrolyte of flow battery and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114156514A true CN114156514A (en) | 2022-03-08 |
| CN114156514B CN114156514B (en) | 2023-11-21 |
Family
ID=80462081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010937173.1A Active CN114156514B (en) | 2020-09-08 | 2020-09-08 | Electrolyte of flow battery and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114156514B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115051006A (en) * | 2022-06-27 | 2022-09-13 | 辽宁大学 | Neutral water system all-quinone organic flow battery couple and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600338A (en) * | 2013-11-01 | 2015-05-06 | 上海空间电源研究所 | Zinc-bromine flow battery electrolyte additive and production method thereof |
| US20150318568A1 (en) * | 2014-04-30 | 2015-11-05 | Ftorion, Inc. | High Specific Energy Aqueous Flow Battery |
| US20170237129A1 (en) * | 2014-08-20 | 2017-08-17 | Albemarle Corporation | Quaternary Ammonium Halides With Ether Functional Groups For Use As Battery Electrolytes |
| US20180079721A1 (en) * | 2015-04-01 | 2018-03-22 | Fundación Centro De Investigación Cooperativa De Energías Alternativas Cic Energigune Fundazioa | Organic electrolyte compounds for redox-flow batteries |
| US20180190991A1 (en) * | 2015-07-09 | 2018-07-05 | Sumitomo Electric Industries, Ltd. | Electrode for redox flow battery and redox flow battery system |
| KR20190008470A (en) * | 2017-07-14 | 2019-01-24 | 동국대학교 산학협력단 | An electrolyte for hybrid flow cell including bromine complex agent |
-
2020
- 2020-09-08 CN CN202010937173.1A patent/CN114156514B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600338A (en) * | 2013-11-01 | 2015-05-06 | 上海空间电源研究所 | Zinc-bromine flow battery electrolyte additive and production method thereof |
| US20150318568A1 (en) * | 2014-04-30 | 2015-11-05 | Ftorion, Inc. | High Specific Energy Aqueous Flow Battery |
| US20170237129A1 (en) * | 2014-08-20 | 2017-08-17 | Albemarle Corporation | Quaternary Ammonium Halides With Ether Functional Groups For Use As Battery Electrolytes |
| US20180079721A1 (en) * | 2015-04-01 | 2018-03-22 | Fundación Centro De Investigación Cooperativa De Energías Alternativas Cic Energigune Fundazioa | Organic electrolyte compounds for redox-flow batteries |
| US20180190991A1 (en) * | 2015-07-09 | 2018-07-05 | Sumitomo Electric Industries, Ltd. | Electrode for redox flow battery and redox flow battery system |
| KR20190008470A (en) * | 2017-07-14 | 2019-01-24 | 동국대학교 산학협력단 | An electrolyte for hybrid flow cell including bromine complex agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115051006A (en) * | 2022-06-27 | 2022-09-13 | 辽宁大学 | Neutral water system all-quinone organic flow battery couple and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114156514B (en) | 2023-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112490515B (en) | Neutral zinc-manganese secondary battery and electrolyte | |
| CN111244518B (en) | Water system neutral organic flow battery | |
| WO2016078491A1 (en) | Zinc-bromine flow battery having extended service life | |
| WO2018103518A1 (en) | Neutral zinc-iron flow battery | |
| CN113437340B (en) | Positive electrode electrolyte for zinc-manganese flow battery | |
| Zhu et al. | A high-performance aqueous iron–hydrogen gas battery | |
| CN114614038A (en) | Zinc-bromine flow battery electrolyte and application thereof in zinc-bromine flow battery | |
| CN114156514B (en) | Electrolyte of flow battery and application thereof | |
| CN113036156B (en) | Gel electrolyte and zinc-bromine or zinc-iodine single flow battery | |
| JP6247778B2 (en) | Quinone polyhalide flow battery | |
| CN111326778B (en) | Neutral lithium-bromine flow battery | |
| WO2023082842A1 (en) | Alkaline negative electrode electrolyte and alkaline zinc-iron flow battery assembled by same | |
| CN110556560A (en) | Catechol positive electrode electrolyte and application thereof in flow battery | |
| CN114447385B (en) | Double-membrane aqueous organic flow battery with positive and negative electrolyte with different pH values | |
| CN110071317A (en) | A kind of tin bromine flow battery | |
| CN113903964B (en) | Simple method for improving performance of vanadium battery and application | |
| WO2023103312A1 (en) | Amine-bromine two-electron electrolyte of flow battery and use thereof, and flow battery | |
| CN220914274U (en) | Zinc bromine flow battery structure capable of inhibiting self-discharge | |
| WO2023103313A1 (en) | Aqueous iodine-based battery based on multi-electron transfer | |
| CN117613335A (en) | Separated flow battery energy storage system and charging and discharging method thereof | |
| CN116207315A (en) | Double-electron transfer halogen flow battery electrolyte and application thereof | |
| CN116264300A (en) | Cadmium-bromine-manganese single flow battery | |
| CN118099492A (en) | Zinc-bromine double-flow battery | |
| CN116137340A (en) | Acid lead bromine flow battery | |
| Khan et al. | 12 Redox Flow Battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |