CN118380620A - Electrolyte for titanium cerium flow battery and preparation method and application thereof - Google Patents
Electrolyte for titanium cerium flow battery and preparation method and application thereof Download PDFInfo
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- CN118380620A CN118380620A CN202410665486.4A CN202410665486A CN118380620A CN 118380620 A CN118380620 A CN 118380620A CN 202410665486 A CN202410665486 A CN 202410665486A CN 118380620 A CN118380620 A CN 118380620A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 171
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical compound [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 cerium ions Chemical class 0.000 claims abstract description 60
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 47
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- 150000005837 radical ions Chemical class 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 239000003929 acidic solution Substances 0.000 claims description 38
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 32
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 8
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- XPQVQIJYDXCEKC-UHFFFAOYSA-K cerium(3+);methanesulfonate Chemical compound [Ce+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O XPQVQIJYDXCEKC-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 238000003756 stirring Methods 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
- 150000002500 ions Chemical class 0.000 abstract description 18
- 230000035515 penetration Effects 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011530 conductive current collector Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000032895 transmembrane transport Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an electrolyte for a titanium cerium flow battery, a preparation method and application thereof, wherein the electrolyte comprises cerium ions, titanium ions, hydrogen ions and acid radical ions; the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition. The invention provides a novel electrolyte which can be used as an anode electrolyte of a titanium cerium flow battery and a cathode electrolyte of the titanium cerium flow battery, has the same components and can effectively avoid the mutual penetration of active ions. In addition, the electrolyte is high in concentration and easy to prepare, and the titanium-cerium flow battery prepared based on the electrolyte has the advantages of high energy density, high specific capacity, good cycle stability, long service life and the like.
Description
Technical Field
The invention belongs to the technical field of flow batteries, and particularly relates to an electrolyte for a titanium cerium flow battery, and a preparation method and application thereof.
Background
The flow battery is considered to be one of the most promising large-scale energy storage technologies due to the characteristics of safety, capacity and power decoupling, flexible large-scale setting and the like. The current developed and mature flow battery systems comprise all-vanadium flow batteries, zinc-bromine flow batteries, iron-chromium flow batteries and the like. However, the cost of the all-vanadium redox flow battery system is higher, the vanadium element is toxic, the problems of dendrite and hydrogen evolution of the zinc-bromine redox flow battery and the volatilization and corrosion of bromine are unavoidable, and the problems of chromium toxicity, lower activity, hydrogen evolution and the like of the iron-chromium redox flow battery also restrict the further development of the system. Therefore, there is a need for further development of a safe and environmentally friendly flow battery system.
Cerium, as a representative of high abundance rare earth elements, has variable valence properties while Ce 4+/3+ has an oxidation-reduction potential up to 1.61V. Titanium is also an extremely abundant element of the crust content, and TiO 2+/Ti3+ has a potential of 0.1V, which is higher than the theoretical hydrogen evolution potential. Therefore, if titanium is used as the negative electrode active element of the flow battery, no hydrogen evolution reaction theoretically occurs. If cerium and titanium are respectively used as active elements of the positive electrode and the negative electrode of the flow battery, the theoretical voltage can reach 1.51V, and the two elements are nontoxic and low in price, so that the titanium-cerium flow battery has the characteristics of safety, environmental protection, no toxicity and high voltage.
However, because the titanium cerium flow battery has different positive and negative active material elements, the permeation of the titanium cerium flow battery through the membrane can cause the mutual shuttling of active ions in a long-term circulation process, thereby causing the capacity attenuation of the battery and reducing the energy density of the battery.
Therefore, the problem of fast cycle performance decay due to the mutual permeation of the anode electrolyte and the cathode electrolyte in the titanium cerium flow battery is needed to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an electrolyte for a titanium cerium flow battery, and a preparation method and application thereof. The invention provides a novel electrolyte which can be used as an anode electrolyte of a titanium cerium flow battery and a cathode electrolyte of the titanium cerium flow battery, has the same components and can effectively avoid the mutual penetration of active ions. In addition, the electrolyte is high in concentration and easy to prepare, and the titanium-cerium flow battery prepared based on the electrolyte has the advantages of high energy density, high specific capacity, good cycle stability, long service life and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides an electrolyte for a titanium-cerium flow battery, the electrolyte comprising cerium ions, titanium ions, hydrogen ions and acid ions;
the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition.
The invention provides a novel electrolyte which can be used as an anode electrolyte of a titanium cerium flow battery and a cathode electrolyte of the titanium cerium flow battery, has the same components and can effectively avoid the mutual penetration of active ions. In addition, the electrolyte is high in concentration and easy to prepare, and the titanium-cerium flow battery prepared based on the electrolyte has the advantages of high energy density, high specific capacity, good cycle stability, long service life and the like.
As a preferable technical scheme of the invention, the electrolyte comprises the following components in terms of molar concentration:
In the present invention, the concentration of cerium ion is 0.1 to 2mol/L, and may be, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, or the like; the concentration of the titanium ion is 0.1 to 2mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, or the like; the concentration of the hydrogen ion is 0.2 to 8mol/L, for example, 0.2mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, or the like, and the concentration of the acid ion is 0.6 to 8mol/L, for example, 0.6mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, or the like. If the concentration of cerium ions or titanium ions is too low, the battery capacity is too low and the energy density is low; if the concentration of cerium ions or titanium ions is too high, the viscosity of the electrolyte is increased, the conductivity of the battery is reduced, the diffusion of active ions is not facilitated, and the concentration of cerium ions is too high, which may cause cerium precipitation and damage the stability of the electrolyte. If the concentration of hydrogen ions is too low, the conductivity of the electrolyte is lowered, and if the concentration of hydrogen ions is too high, trivalent cerium ions are likely to precipitate out, deteriorating the stability of the electrolyte.
As a preferable technical scheme of the invention, the electrolyte comprises the following components in terms of molar concentration:
In the present invention, the concentration of sulfate ion is 0.1 to 2mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, etc., and the concentration of titanium ion is 0.5 to 1.5mol/L, for example, 0.5mol/L, 0.75mol/L, 1mol/L, 1.25mol/L, 1.5mol/L, etc.
As a preferable embodiment of the present invention, the concentration of the hydrogen ion is 0.5 to 4mol/L, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, or the like.
In a second aspect, the present invention provides a method for preparing the electrolyte for a titanium cerium flow battery according to the first aspect, the method comprising the steps of:
and mixing a cerium source, a titanium source and an acidic solution to obtain the electrolyte for the titanium-cerium flow battery.
As a preferred embodiment of the present invention, the cerium source includes cerium salt and/or cerium hydroxide.
Preferably, the cerium salt comprises any one or a combination of at least two of cerium carbonate, cerium sulfate or cerium mesylate, preferably cerium carbonate.
Preferably, the cerium hydroxide is cerium hydroxide.
Preferably, the titanium source comprises a titanium salt and/or a titanium hydroxide.
Preferably, the titanium salt comprises any one or a combination of at least two of titanium tetrachloride, titanyl sulfate or titanyl methanesulfonate.
Preferably, the titanium hydroxide is tetra titanium hydroxide.
Preferably, the acidic solution comprises a sulfuric acid solution and/or a methanesulfonic acid solution, preferably a mixed solution of sulfuric acid solution and methanesulfonic acid solution.
Preferably, the mixing is accompanied by stirring.
As a preferred technical solution of the present invention, the mixing method includes the following steps:
(1) Mixing a cerium source with an acidic solution to obtain a first mixed solution with cerium ion concentration of 0.2-4 mol/L;
(2) Mixing a titanium source with the acidic solution to obtain a second mixed solution with the titanium ion concentration of 0.2-4 mol/L;
(3) Blending the first mixed liquid and the second mixed liquid.
As a preferred technical solution of the present invention, the mixing method includes the following steps:
adding a cerium source into part of the acidic solution for dissolution, cooling to room temperature, and then adding a titanium source and the other part of the acidic solution for mixing; or alternatively
The titanium source is added to a portion of the acidic solution for dissolution, cooled to room temperature, and then the cerium source and another portion of the acidic solution are added for mixing.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
Mixing a cerium source, a titanium source, a methanesulfonic acid solution and a sulfuric acid solution to obtain an electrolyte for the titanium-cerium flow battery;
wherein, the mode of mixing is a mode one or a mode two, and the specific steps of the mode one comprise:
Mixing a methanesulfonic acid solution and a sulfuric acid solution to obtain an acidic solution;
Adding a cerium source into part of the acidic solution for dissolution, cooling to room temperature, then adding a titanium source and the other part of the acidic solution, fixing the volume and uniformly mixing; or alternatively
Adding a titanium source into part of the acidic solution for dissolution, cooling to room temperature, then adding a cerium source and the other part of the acidic solution, fixing the volume and uniformly mixing;
the specific steps of the second mode include:
(a) Mixing a cerium source, a methanesulfonic acid solution and a sulfuric acid solution to obtain a first mixed solution with cerium ion concentration of 0.2-4 mol/L;
(b) Mixing a titanium source, a methanesulfonic acid solution and a sulfuric acid solution to obtain a second mixed solution with the titanium ion concentration of 0.2-4 mol/L;
(c) Blending the first mixed liquor of step (a) and the second mixed liquor of step (b).
In a third aspect, the invention provides a titanium cerium flow battery, which comprises a positive electrolyte and a negative electrolyte, wherein the positive electrolyte and the negative electrolyte are both the electrolytes in the first aspect.
The anode and the cathode of the titanium cerium flow battery independently comprise any one of nickel mesh, carbon felt, graphite felt or carbon cloth.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a novel electrolyte which can be used as an anode electrolyte of a titanium cerium flow battery and a cathode electrolyte of the titanium cerium flow battery, has the same components, balances the concentration of active substances at two sides of the battery, can effectively avoid the mutual penetration of active ions, reduces the transmembrane transport of the active substances, reduces the capacity attenuation and prolongs the cycle life of the battery.
(2) The electrolyte provided by the invention has the advantages of high concentration, easiness in preparation, good reversibility, high single cell voltage, simple electrolyte composition and the like.
(3) The titanium-cerium flow battery prepared based on the electrolyte provided by the invention has the advantages of high energy density, high specific capacity, good cycle stability, long service life and the like, and the energy efficiency can reach 82.49% within 100 circles under the current density of 30mA/cm 2.
(4) The preparation method of the electrolyte provided by the invention has the advantages of simple process, low cost, safety and environmental protection.
Drawings
Fig. 1 is an energy efficiency graph of cerium-titanium flow batteries prepared in example 1, example 2 and comparative example 1 according to the present invention at a current density of 30mA/cm 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The room temperature hereinafter means 25 ℃.
Example 1
The embodiment provides an electrolyte for a titanium-cerium flow battery, which comprises cerium ions, titanium ions, hydrogen ions, sulfate ions and methanesulfonate ions;
the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition;
the electrolyte comprises the following components in terms of molar concentration:
The embodiment also provides a preparation method of the electrolyte, which comprises the following steps:
(1) Adding methanesulfonic acid with a certain mass into 20mL of deionized water to prepare methanesulfonic acid solution, and then adding sulfuric acid solution to obtain acidic solution;
(2) Adding a certain mass of cerium carbonate into a part of the acidic solution for dissolution, cooling to room temperature, adding a certain mass of titanyl sulfate and another part of the acidic solution, adding deionized water to a constant volume of 50mL, and fully and uniformly mixing to obtain the electrolyte.
The embodiment also provides a titanium cerium flow battery, the structure of which comprises an anode end plate, an insulating gasket, a conductive current collector, a flow frame, an anode electrode, an ion exchange membrane, a cathode electrode, a flow frame, a conductive current collector, an insulating gasket and a cathode end plate;
Wherein, the positive electrode and the negative electrode are both 3cm multiplied by 3cm carbon felt, and are heat treated for 4 hours at 500 ℃ before use;
The titanium cerium flow battery is assembled and then connected with the anode and cathode liquid storage tanks through the silica gel hose, the electrolyte is the anode electrolyte and the cathode electrolyte of the titanium cerium flow battery, the anode electrolyte and the cathode electrolyte are respectively stored in the anode liquid storage tank and the cathode liquid storage tank, and the anode electrolyte and the cathode electrolyte circularly flow between the battery and the liquid storage tank through the peristaltic pump.
Example 2
The embodiment provides an electrolyte for a titanium-cerium flow battery, which comprises cerium ions, titanium ions, hydrogen ions, sulfate ions and methanesulfonate ions;
the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition;
the electrolyte comprises the following components in terms of molar concentration:
The embodiment also provides a preparation method of the electrolyte, which comprises the following steps:
(1) Adding methanesulfonic acid with a certain mass into 20mL of deionized water to prepare methanesulfonic acid solution, and then adding sulfuric acid solution to obtain acidic solution;
(2) Adding a certain mass of cerium carbonate into a part of the acidic solution for dissolution, cooling to room temperature, adding a certain mass of titanyl sulfate and another part of the acidic solution, adding deionized water to a constant volume of 50mL, and fully and uniformly mixing to obtain the electrolyte.
The embodiment also provides a titanium cerium flow battery, the structure of which comprises an anode end plate, an insulating gasket, a conductive current collector, a flow frame, an anode electrode, an ion exchange membrane, a cathode electrode, a flow frame, a conductive current collector, an insulating gasket and a cathode end plate;
Wherein, the positive electrode and the negative electrode are both 3cm multiplied by 3cm carbon felt, and are heat treated for 4 hours at 500 ℃ before use;
The titanium cerium flow battery is assembled and then connected with the anode and cathode liquid storage tanks through the silica gel hose, the electrolyte is the anode electrolyte and the cathode electrolyte of the titanium cerium flow battery, the anode electrolyte and the cathode electrolyte are respectively stored in the anode liquid storage tank and the cathode liquid storage tank, and the anode electrolyte and the cathode electrolyte circularly flow between the battery and the liquid storage tank through the peristaltic pump.
Example 3
The embodiment provides an electrolyte for a titanium-cerium flow battery, which comprises cerium ions, titanium ions, hydrogen ions, sulfate ions and methanesulfonate ions;
the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition;
the electrolyte comprises the following components in terms of molar concentration:
The embodiment also provides a preparation method of the electrolyte, which comprises the following steps:
(1) Adding methanesulfonic acid with a certain mass into 20mL of deionized water to prepare methanesulfonic acid solution, and then adding sulfuric acid solution to obtain acidic solution;
(2) Adding a certain mass of cerium carbonate into a part of the acidic solution for dissolution, cooling to room temperature, adding a certain mass of titanyl sulfate and another part of the acidic solution, adding deionized water to a constant volume of 50mL, and fully and uniformly mixing to obtain the electrolyte.
The embodiment also provides a titanium cerium flow battery, the structure of which comprises an anode end plate, an insulating gasket, a conductive current collector, a flow frame, an anode electrode, an ion exchange membrane, a cathode electrode, a flow frame, a conductive current collector, an insulating gasket and a cathode end plate;
Wherein, the positive electrode and the negative electrode are both 3cm multiplied by 3cm carbon felt, and are heat treated for 4 hours at 500 ℃ before use;
The titanium cerium flow battery is assembled and then connected with the anode and cathode liquid storage tanks through the silica gel hose, the electrolyte is the anode electrolyte and the cathode electrolyte of the titanium cerium flow battery, the anode electrolyte and the cathode electrolyte are respectively stored in the anode liquid storage tank and the cathode liquid storage tank, and the anode electrolyte and the cathode electrolyte circularly flow between the battery and the liquid storage tank through the peristaltic pump.
Example 4
The embodiment provides an electrolyte for a titanium-cerium flow battery, which comprises cerium ions, titanium ions, hydrogen ions, sulfate ions and methanesulfonate ions;
the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition;
the electrolyte comprises the following components in terms of molar concentration:
The embodiment also provides a preparation method of the electrolyte, which comprises the following steps:
(1) Adding methanesulfonic acid with a certain mass into 20mL of deionized water to prepare methanesulfonic acid solution, and then adding sulfuric acid solution to obtain acidic solution;
(2) Adding a certain mass of cerium carbonate into a part of the acidic solution for dissolution, cooling to room temperature, adding a certain mass of titanyl sulfate and another part of the acidic solution, adding deionized water to a constant volume of 50mL, and fully and uniformly mixing to obtain the electrolyte.
The embodiment also provides a titanium cerium flow battery, the structure of which comprises an anode end plate, an insulating gasket, a conductive current collector, a flow frame, an anode electrode, an ion exchange membrane, a cathode electrode, a flow frame, a conductive current collector, an insulating gasket and a cathode end plate;
Wherein, the positive electrode and the negative electrode are both 3cm multiplied by 3cm carbon felt, and are heat treated for 4 hours at 500 ℃ before use;
The titanium cerium flow battery is assembled and then connected with the anode and cathode liquid storage tanks through the silica gel hose, the electrolyte is the anode electrolyte and the cathode electrolyte of the titanium cerium flow battery, the anode electrolyte and the cathode electrolyte are respectively stored in the anode liquid storage tank and the cathode liquid storage tank, and the anode electrolyte and the cathode electrolyte circularly flow between the battery and the liquid storage tank through the peristaltic pump.
Example 5
This example differs from example 1 in that the preparation method comprises the following steps:
(a) Mixing cerium carbonate, methanesulfonic acid solution and sulfuric acid solution with certain mass to prepare a first mixed solution with cerium ion concentration of 1.0 mol/L;
(b) Mixing a certain mass of titanyl sulfate, methanesulfonic acid solution and sulfuric acid solution to obtain a second mixed solution with titanium ion concentration of 1.0 mol/L;
(c) Blending the first mixed solution in the step (a) and the second mixed solution in the step (b) to obtain the electrolyte.
The remaining parameters remain the same as in example 1.
Example 6
This example differs from example 1 in that the concentration of cerium ions and titanium ions in the electrolyte is 0.05mol/L.
The remaining preparation methods and parameters remain the same as in example 1.
Example 7
The difference between this example and example 1 is that the concentration of cerium ion and titanium ion in the electrolyte is 2mol/L.
The remaining preparation methods and parameters remain the same as in example 1.
Example 8
This example differs from example 1 in that the concentration of hydrogen ions in the electrolyte is 0.1mol/L.
The remaining preparation methods and parameters remain the same as in example 1.
Example 9
This example differs from example 1 in that the concentration of hydrogen ions in the electrolyte is 5mol/L.
The remaining preparation methods and parameters remain the same as in example 1.
Example 10
This example differs from example 1 in that the electrolyte contains no sulfate ion and the concentration of methanesulfonate ion is 4.5mol/L.
The remaining preparation methods and parameters remain the same as in example 1.
Example 11
This example differs from example 1 in that the electrolyte does not contain methanesulfonate ions and the concentration of sulfate ions is 2.25mol/L.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 1
The difference between this comparative example and example 1 is that the positive electrode electrolyte in the titanium-cerium flow battery contains no titanium ions, the concentration of cerium ions in the positive electrode electrolyte is 1mol/L, the negative electrode electrolyte contains no cerium ions, and the concentration of titanium ions in the negative electrode electrolyte is 1mol/L, namely the preparation step of the positive electrode electrolyte comprises:
mixing cerium carbonate, methanesulfonic acid solution and sulfuric acid solution with certain mass to obtain positive electrode electrolyte;
The preparation method of the negative electrode electrolyte comprises the following steps:
mixing a certain mass of titanyl sulfate, methanesulfonic acid solution and sulfuric acid solution to obtain the negative electrode electrolyte.
The remaining preparation methods and parameters remain the same as in example 1.
Fig. 1 shows energy efficiency diagrams of the cerium-titanium flow batteries prepared in example 1, example 2 and comparative example 1 at a current density of 30mA/cm 2, and it is clear from the diagrams that the cycling stability of comparative example 1 is poor because of the diffusion of active ions and the capacity fading is fast. The cycle performance of example 1 is highest, the stability is also best, and the energy efficiency in 100 circles can reach 82.49%. In example 2, the solution viscosity was increased, the conductivity was decreased, and the overall energy efficiency was lowered after the concentration was increased, but the total cyclic stability was improved because the active ion permeation was lowered with the same positive and negative electrolyte components.
Performance testing
The titanium cerium flow batteries prepared in the above examples and comparative examples were tested for average coulombic efficiency, average voltage efficiency, and average energy efficiency at a current density of 30mA/cm 2.
The test results are shown in tables 1 and 2.
TABLE 1
TABLE 2
Analysis:
As can be seen from tables 1 and 2, the invention provides a novel electrolyte which can be used as the positive electrode electrolyte of the titanium cerium flow battery and the negative electrode electrolyte of the titanium cerium flow battery, has the same components, and can effectively avoid the mutual penetration of active ions. In addition, the electrolyte is high in concentration and easy to prepare, and the titanium-cerium flow battery prepared based on the electrolyte has the advantages of high energy density, high specific capacity, good cycle stability, long service life and the like.
As can be seen from the change of the test temperature, the increase of the temperature can accelerate the ion diffusion and reduce the viscosity of the electrolyte, thereby improving the ion transmission rate of the electrolyte and the electrochemical activity of the electrode.
As is clear from examples 1,2 and 6 to 7, if the concentration of cerium ions and titanium ions is too low, the battery charge depth is high, which tends to cause battery polarization, resulting in deterioration of cycle performance; if the concentration of cerium ions and titanium ions is too high, the viscosity of the high-concentration mixed electrolyte is rapidly increased, so that the transmission and diffusion of active ions are blocked, and the polarization is increased, and therefore, the high-concentration mixed electrolyte is unfavorable for improving the electrochemical performance of the battery.
As is clear from examples 1 and 8 to 9, if the concentration of hydrogen ions is too low, the conductivity of the electrolyte is lowered; if the concentration of hydrogen ions is too high, trivalent cerium ions are likely to precipitate out, deteriorating the stability of the electrolyte.
As is clear from examples 1 and 10-11, if the electrolyte contains no sulfate ion, the viscosity of the methanesulfonic acid system is higher, which is unfavorable for ion diffusion, resulting in deterioration of average voltage efficiency and average energy efficiency; if the electrolyte does not contain methanesulfonate ions, cerium in a sulfuric acid system is easy to precipitate out, so that the electrolyte is unstable and the cycle performance is poor.
As is clear from example 1 and comparative example 1, if the positive electrode electrolyte and the negative electrode electrolyte in the titanium-cerium flow battery do not contain titanium ions, the battery prepared based on the above is deteriorated in performance because titanium and cerium active ions are ion-permeated due to concentration differences during circulation, so that the concentration of the positive and negative active ions is continuously reduced, resulting in polarization.
In summary, the above examples and comparative examples and data demonstrate that the electrolyte provided by the present invention can effectively avoid the problem of rapid degradation of electrochemical performance of a battery caused by concentration decrease due to active ion permeation.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. An electrolyte for a titanium-cerium flow battery is characterized by comprising cerium ions, titanium ions, hydrogen ions and acid radical ions;
the electrolyte is positive electrolyte or negative electrolyte, and the positive electrolyte and the negative electrolyte have the same composition.
2. The electrolyte of claim 1, wherein the electrolyte comprises the following components in molar concentration:
3. Electrolyte according to claim 1 or 2, characterized in that it comprises the following components in molar concentration:
4. the electrolyte according to any one of claims 1 to 3, wherein the concentration of hydrogen ions is 0.5 to 4mol/L.
5. A method for preparing the electrolyte for the titanium cerium flow battery as claimed in any one of claims 1 to 4, wherein the preparation method comprises the following steps:
and mixing a cerium source, a titanium source and an acidic solution to obtain the electrolyte for the titanium-cerium flow battery.
6. The method of claim 5, wherein the cerium source comprises a cerium salt and/or a cerium hydroxide;
preferably, the cerium salt comprises any one or a combination of at least two of cerium carbonate, cerium sulfate or cerium mesylate, preferably cerium carbonate;
preferably, the cerium hydroxide is cerium hydroxide;
Preferably, the titanium source comprises a titanium salt and/or a titanium hydroxide;
preferably, the titanium salt comprises any one or a combination of at least two of titanium tetrachloride, titanyl sulfate or titanyl methanesulfonate;
Preferably, the titanium hydroxide is tetra titanium hydroxide;
preferably, the acidic solution comprises a sulfuric acid solution and/or a methanesulfonic acid solution, preferably a mixed solution of sulfuric acid solution and methanesulfonic acid solution;
Preferably, the mixing is accompanied by stirring.
7. The method of claim 5 or 6, wherein the mixing comprises the steps of:
(1) Mixing a cerium source with an acidic solution to obtain a first mixed solution with cerium ion concentration of 0.2-4 mol/L;
(2) Mixing a titanium source with the acidic solution to obtain a second mixed solution with the titanium ion concentration of 0.2-4 mol/L;
(3) Blending the first mixed liquid and the second mixed liquid.
8. The method of claim 5 or 6, wherein the mixing comprises the steps of:
adding a cerium source into part of the acidic solution for dissolution, cooling to room temperature, and then adding a titanium source and the other part of the acidic solution for mixing; or alternatively
The titanium source is added to a portion of the acidic solution for dissolution, cooled to room temperature, and then the cerium source and another portion of the acidic solution are added for mixing.
9. The preparation method according to any one of claims 5 to 8, characterized in that the preparation method comprises the steps of:
Mixing a cerium source, a titanium source, a methanesulfonic acid solution and a sulfuric acid solution to obtain an electrolyte for the titanium-cerium flow battery;
wherein, the mode of mixing is a mode one or a mode two, and the specific steps of the mode one comprise:
Mixing a methanesulfonic acid solution and a sulfuric acid solution to obtain an acidic solution;
Adding a cerium source into part of the acidic solution for dissolution, cooling to room temperature, then adding a titanium source and the other part of the acidic solution, fixing the volume and uniformly mixing; or alternatively
Adding a titanium source into part of the acidic solution for dissolution, cooling to room temperature, then adding a cerium source and the other part of the acidic solution, fixing the volume and uniformly mixing;
the specific steps of the second mode include:
(a) Mixing a cerium source, a methanesulfonic acid solution and a sulfuric acid solution to obtain a first mixed solution with cerium ion concentration of 0.2-4 mol/L;
(b) Mixing a titanium source, a methanesulfonic acid solution and a sulfuric acid solution to obtain a second mixed solution with the titanium ion concentration of 0.2-4 mol/L;
(c) Blending the first mixed liquor of step (a) and the second mixed liquor of step (b).
10. A titanium cerium flow battery, characterized in that the titanium cerium flow battery comprises a positive electrode electrolyte and a negative electrode electrolyte, wherein the positive electrode electrolyte and the negative electrode electrolyte are the electrolyte as claimed in any one of claims 1 to 4.
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