CN118173869A - TiO-containing material2/Ti3C2TxZinc ion battery electrolyte of composite material, preparation method and application thereof - Google Patents
TiO-containing material2/Ti3C2TxZinc ion battery electrolyte of composite material, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 66
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 12
- 229960001763 zinc sulfate Drugs 0.000 claims description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 4
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 11
- 230000006911 nucleation Effects 0.000 abstract description 10
- 238000010899 nucleation Methods 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 239000010936 titanium Substances 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002000 Electrolyte additive Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of water-based zinc ion batteries, in particular to a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material, a preparation method and application thereof, wherein Ti powder, tiC 2 powder and Al powder are mixed and sintered according to a certain proportion to obtain Ti 3AlC2 MAX, then Ti 3C2Tx MXene is obtained after etching, then Ti 3C2Tx MXene is oxidized in situ by a simple hydrothermal method to obtain a TiO 2/Ti3C2Tx composite material, and finally the composite material is added into the water-based zinc ion battery electrolyte according to a certain amount. According to the invention, the TiO 2/Ti3C2Tx composite material is added into the aqueous zinc ion battery electrolyte, so that the internal resistance of the battery is reduced, the hydrogen evolution side reaction of a zinc negative electrode is reduced, and meanwhile, the uniform nucleation and growth of zinc are promoted and the formation of zinc dendrites is inhibited by reducing the concentration gradient of zinc ions at the interface of the zinc negative electrode/electrolyte, so that the aqueous zinc ion battery with long cycle life under the condition of high current is obtained.
Description
Technical Field
The invention relates to the technical field of water-based zinc ion batteries, in particular to a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material, a preparation method and application thereof.
Background
With the massive consumption of energy by human beings, environmental pollution and energy crisis are increasingly advanced, and the demands of clean renewable energy are increasingly urgent in countries around the world. However, new energy sources such as solar energy and wind energy have significant randomness and volatility, making them difficult to use directly, requiring large energy storage systems to ensure their reliability and availability. The water system zinc ion battery has the advantages of high capacity, low cost, safety, environmental protection and the like, and is an energy storage system with development potential at the present stage. However, dendrite growth and side reactions of zinc cathodes can lead to reduced battery cycle life and capacity degradation, which hampers further development of aqueous zinc ion batteries. In order to prolong the cycle life of the water-based zinc ion battery, the protection of the negative electrode of the water-based zinc ion battery is of great significance.
In order to realize the negative electrode protection of the water-based zinc ion battery, the construction of an artificial interface layer is a common strategy, and the artificial interface layer can be formed by means of coating, interface in-situ adsorption and the like. The artificial interface layer can induce zinc to nucleate uniformly, and reduce side reaction. Ti 3C2Tx MXene is used as a two-dimensional transition metal carbon/carbon nitride, has (002) crystal face, excellent conductivity and hydrophilic functional groups, can form an artificial interface layer in situ on a negative electrode as an electrolyte additive, and induces zinc ions to deposit along the (002) crystal face, thus being an effective electrolyte additive material. However, due to the two-dimensional characteristics of the MXene, the MXene is easy to agglomerate, is not easy to uniformly adhere to a zinc cathode, and causes the defect of a protection effect, and the Ti 3C2Tx MXene needs to be modified to prepare an MXene-based cathode protection material which is not easy to collapse and accumulate, and increases zinc deposition active sites, so that the MXene-based cathode protection material has high-efficiency reactivity and conductivity.
The Chinese patent application CN202010248099.2 discloses a Ti 3C2Tx-TiO2 composite material, a preparation method and application thereof, and the preparation method of the Ti 3C2Tx-TiO2 composite material comprises the following steps: the Ti 3C2Tx_TiO2 composite material is prepared by an in-situ oxidation method through MXene and hydrogen peroxide. Chinese patent No. 202111317303.2 discloses a preparation method and application of N-TiO 2/Ti3C2Tx composite material. The preparation method of the N-TiO 2/Ti3C2Tx composite material comprises the following steps: the MXene hydrothermal method is used for obtaining a TiO 2/Ti3C2Tx composite material, and the TiO 2 N doping is carried out through urea so as to obtain an N-TiO 2/Ti3C2Tx composite material. The application scenes of the technical scheme are photocatalysis and lithium air batteries respectively. It should be noted that the particle sizes of TiO 2 obtained by oxidation in the two technical schemes are large.
Disclosure of Invention
The invention aims to solve the problems that MXene is easy to agglomerate and is not easy to uniformly adhere to a zinc cathode, so that the defect of a protection effect is caused, and provides a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material, a preparation method and application thereof.
In order to achieve the above purpose, the invention discloses a preparation method of a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material, which comprises the following steps:
S1, placing Ti 3C2Tx MXene powder into water, stirring, performing ultrasonic treatment, transferring to a reaction kettle, performing hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished;
S2, centrifugally collecting the solution cooled in the step S1, wherein the obtained precipitate is the TiO 2/Ti3C2Tx composite material;
And S3, preparing zinc sulfate/zinc trifluoromethane sulfonate/zinc chloride/zinc acetate electrolyte, and adding the TiO 2/Ti3C2Tx composite material obtained in the step S2 to prepare the zinc ion battery electrolyte.
In the step S1, the amount of Ti 3C2Tx MXene powder is 1-5 mg.
In the step S1, the water is deionized water, and the volume is 20-30 mL.
In the step S1, the stirring time is 10-30 min, and the ultrasonic treatment time is 20-3 min.
In the step S1, the hydrothermal reaction conditions are as follows: reacting for 2-15 h at 120-180 ℃ with the temperature rising rate of 5-10 ℃/min.
In the step S2, the centrifugation condition is 10000rpm, and the centrifugation is performed for 1min.
In the step S3, the concentration of the zinc sulfate/zinc trifluoromethane sulfonate/zinc chloride/zinc acetate electrolyte is 2mol/L.
In the step S3, the concentration of the TiO 2/Ti3C2Tx composite material is 10-40 mg/L.
The invention also discloses a zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material prepared by the preparation method and application of the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material in zinc cathode protection of the zinc ion battery.
Ti 3C2Tx MXene is subjected to in-situ conversion by hydrothermal method to form a small-size TiO 2/Ti3C2Tx compound. The hydrothermal material has smaller size, can realize more uniform coverage, and can realize effective protection of the zinc cathode. Meanwhile, the derivative TiO 2 can form a heterojunction with Ti 3C2Tx MXene, which is favorable for uniform deposition of zinc, reduces generation of zinc dendrite and further improves the cycle performance of the water-based zinc ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. The TiO 2/Ti3C2Tx composite material prepared by the invention has rich zinc-philic functional groups, can promote desolvation in the zinc ion deposition process, and obviously reduces nucleation overpotential of zinc ions;
2. the TiO 2/Ti3C2Tx composite material prepared by the invention has rich hydrophilic functional groups, can improve the stability of the aqueous zinc ion battery electrolyte and prevent the hydrogen evolution side reaction;
3. The TiO 2/Ti3C2Tx composite material prepared by the method has very excellent conductivity, can reduce the internal resistance and polarization voltage of the water-based zinc ion battery, and improves the electrochemical performance of the water-based zinc ion battery;
4. The TiO 2/Ti3C2Tx composite material prepared by the method is negatively charged, so that the potential gradient and the zinc ion concentration gradient of the surface of a zinc cathode can be reduced, the uniform deposition of zinc ions is promoted, the generation of zinc dendrites is reduced, the timely replenishment of zinc ions in the deposition process is ensured, and the long-cycle performance of a water-based zinc ion battery under high current is improved;
5. The TiO 2/Ti3C2Tx composite material prepared by the method has a heterojunction structure, can promote uniform deposition of zinc ions, reduce generation of zinc dendrites, and improve the cycle performance of a water-based zinc ion battery;
6. According to the invention, through the process control of controlling the hydrothermal temperature and the hydrothermal time, the obtained TiO 2 has the particle size of about 10nm, and the smaller TiO 2 has the particle size which ensures a more uniform heterostructure, can promote the uniform deposition of zinc ions, and has more significance in the field of water-based zinc ion batteries.
Drawings
FIG. 1 is an XRD pattern of an aqueous zinc-ion battery electrolyte additive material prepared in example 3 of the present invention;
FIG. 2 is a TEM image of the aqueous zinc-ion battery electrolyte additive material prepared in example 3 of the present invention;
FIG. 3 is a cycle performance test of example 3 and comparative example 1 of the present invention in zinc-titanium half cells;
FIG. 4 is a Tafel test (Tafel) performed on zinc electrodes in inventive example 3 and comparative example 1; ;
FIG. 5 is a hydrogen evolution reaction test of zinc electrode in inventive example 3 and comparative example 1;
FIG. 6 is an oxygen evolution reaction test of zinc electrode in inventive example 3 and comparative example 1;
FIG. 7 is an electrochemical impedance test (EIS) performed on a standard symmetrical cell composed of example 3 and comparative example 1 according to the present invention;
FIG. 8 is a nucleation overpotential test at 10mA cm -2 current density for a standard symmetrical cell composed of example 3 and comparative example 1 of the present invention;
FIG. 9 is a graph showing the cycle time of a standard symmetrical cell of example 3 and comparative example 1 of the present invention at a current density of 10mA cm -2;
FIG. 10 is an optical view of the in-situ deposition of zinc electrodes for 1h in example 3 of the present invention;
FIG. 11 is an optical view of in situ deposition of zinc electrodes in comparative example 1 of the present invention for 1 h;
FIG. 12 is a cycle stability test of zinc electrode and titanium foil supported MnO 2 at a current density of 10A g -1 for aqueous zinc ion full cells with electrolyte composition criteria of example 3 and comparative example 1;
Fig. 13 is a graph showing the nucleation overpotential test for standard symmetrical batteries of examples 1,2, 3 and 4 according to the present invention at a current density of 20mA cm -2.
Detailed Description
The above and further technical features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
A preparation method of a zinc ion battery electrolyte containing TiO 2/Ti3C2Tx composite material comprises the following steps:
Accurately weighing 1mg of Ti 3C2Tx Mxene, dissolving in 30mL of deionized water, stirring for 30min, performing ultrasonic treatment for 20min, transferring the solution into a 50mL reaction kettle, performing hydrothermal reaction at 120 ℃, stopping heating when the reaction time reaches 6h, and naturally cooling the reaction kettle to room temperature. The obtained solution was centrifuged at 10000r/min for 5min and repeated three times. And freeze-drying the precipitate to obtain the TiO 2/Ti3C2Tx composite material.
Weighing each component according to the concentration of zinc sulfate of 2mol/L and TiO 2/Ti3C2Tx mg/L, and dissolving the components in water to obtain the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material.
Example 2
A preparation method of a zinc ion battery electrolyte containing TiO 2/Ti3C2Tx composite material comprises the following steps:
Accurately weighing 1mg of Ti 3C2Tx Mxene, dissolving in 30mL of deionized water, stirring for 30min, performing ultrasonic treatment for 20min, transferring the solution into a 50mL reaction kettle, performing hydrothermal reaction at 120 ℃, stopping heating when the reaction time reaches 6h, and naturally cooling the reaction kettle to room temperature. The obtained solution was centrifuged at 10000r/min for 5min and repeated three times. And freeze-drying the precipitate to obtain the TiO 2/Ti3C2Tx composite material.
Weighing each component according to the concentration of zinc sulfate of 2mol/L and TiO 2/Ti3C2Tx mg/L, and dissolving the components in water to obtain the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material.
Example 3
A preparation method of a zinc ion battery electrolyte containing TiO 2/Ti3C2Tx composite material comprises the following steps:
Accurately weighing 1mg of Ti 3C2Tx Mxene, dissolving in 30mL of deionized water, stirring for 30min, performing ultrasonic treatment for 20min, transferring the solution into a 50mL reaction kettle, performing hydrothermal reaction at 120 ℃, stopping heating when the reaction time reaches 6h, and naturally cooling the reaction kettle to room temperature. The obtained solution was centrifuged at 10000r/min for 5min and repeated three times. And freeze-drying the precipitate to obtain the TiO 2/Ti3C2Tx composite material.
Weighing each component according to the concentration of zinc sulfate of 2mol/L and TiO 2/Ti3C2Tx mg/L, and dissolving the components in water to obtain the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material.
Example 4
A preparation method of a zinc ion battery electrolyte containing TiO 2/Ti3C2Tx composite material comprises the following steps:
Accurately weighing 1mg of Ti 3C2Tx Mxene, dissolving in 30mL of deionized water, stirring for 30min, performing ultrasonic treatment for 20min, transferring the solution into a 50mL reaction kettle, performing hydrothermal reaction at 120 ℃, stopping heating when the reaction time reaches 6h, and naturally cooling the reaction kettle to room temperature. The obtained solution was centrifuged at 10000r/min for 5min and repeated three times. And freeze-drying the precipitate to obtain the TiO 2/Ti3C2Tx composite material.
Weighing each component according to the concentration of zinc sulfate of 2mol/L and TiO 2/Ti3C2Tx of 10mg/L, and dissolving the components in water to obtain the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material.
Example 5
A preparation method of a zinc ion battery electrolyte containing TiO 2/Ti3C2Tx composite material comprises the following steps:
Accurately weighing 1mg of Ti 3C2Tx Mxene, dissolving in 30mL of deionized water, stirring for 30min, performing ultrasonic treatment for 20min, transferring the solution into a 50mL reaction kettle, performing hydrothermal reaction at 180 ℃, stopping heating when the reaction is performed for 6h, and naturally cooling the reaction kettle to room temperature. The obtained solution was centrifuged at 10000r/min for 5min and repeated three times. And freeze-drying the precipitate to obtain the TiO 2/Ti3C2Tx composite material.
Weighing each component according to the concentration of zinc sulfate of 2mol/L and TiO 2/Ti3C2Tx mg/L, and dissolving the components in water to obtain the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material.
Comparative example 1
In order to compare the effect of the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material and the additive-free electrolyte on inhibiting zinc dendrite, the additive-free aqueous electrolyte is prepared, the specific composition of the electrolyte is water and electrolyte, the electrolyte consists of zinc salt, and the zinc salt is zinc sulfate, and the preparation method comprises the following steps: the zinc sulfate solution is dissolved in water according to the concentration of 2mol/L, and the zinc sulfate solution is marked as no-additive electrolyte.
FIG. 1 shows the XRD pattern of the TiO 2/Ti3C2Tx composite prepared in example 3 of the present invention, from which it can be seen that there is a main peak between 5 and 10 degrees, which corresponds to Ti 3C2Tx MXene, and a peak between 20 and 30 degrees, which represents the in situ formation of TiO 2 oxide in Ti 3C2Tx MXene after hydrothermal treatment.
Fig. 2 is a TEM image of the TiO 2/Ti3C2Tx composite prepared in example 3 of the present invention, and it can be seen from the TEM image that the prepared material has a smaller size, and the size is 10 to 20nm. The size of the lattice fringes of the black dots in the figure corresponds to the (101) crystal plane in the TiO 2, further demonstrating the formation of TiO 2.
Fig. 3 is a cycle performance test of the assembled zinc-titanium half cell of example 3 and comparative example 1 of the present invention. As can be seen from fig. 3, the assembled half cell of example 3 has a higher coulombic efficiency at a current density of 1mA cm -2, indicating that it is capable of promoting the deposition and stripping of zinc ions under limited zinc conditions.
Fig. 4, 5 and 6 are respectively tafel test chart, hydrogen evolution reaction test chart and oxygen evolution reaction test chart of the present invention in example 3 and comparative example 1, wherein example 3 has a more positive corrosion potential, a higher hydrogen evolution reaction and oxygen evolution reaction overpotential, which indicates that it can effectively inhibit side reactions occurring in the aqueous zinc ion battery and improve the cycle stability of the aqueous zinc ion battery.
Fig. 7 is a graph of electrochemical impedance testing for a standard symmetrical cell assembled from example 3 and comparative example 1 according to the present invention, wherein the standard symmetrical cell assembled from example 3 has an impedance of about 140 Ω, which is significantly less than the standard symmetrical cell assembled from comparative example 1, indicating more excellent electrochemical performance.
Fig. 8 is a comparison of the nucleation overpotential of the assembled standard symmetrical cell of example 3 of the present invention with that of comparative example 1 at a current density of 10mA cm -2, wherein the assembled standard symmetrical cell of example 3 has a nucleation overpotential of 75mV, significantly less than that of comparative example 1, indicating that it can promote uniform nucleation of zinc ions and inhibit dendrite formation.
Fig. 9 is a graph of cycle time at a current density of 10mA cm -2 for an assembled standard symmetrical cell of example 3 and comparative example 1 of the present invention. As can be seen from the graph, the standard symmetrical battery assembled in example 3 can be cycled for more than 1300h under the current density, and the cycle number is more than 26000, which is far more than the standard symmetrical battery assembled in comparative example 1, so that the cycle performance of the aqueous zinc ion battery under the condition of high current can be effectively improved in example 3.
Fig. 10 and 11 are optical observations of in-situ deposition of zinc electrodes in example 3 and comparative example 1, respectively, for 1 h. As can be seen from the figure, the zinc electrode surface in example 3 was uniformly deposited without significant dendrite formation, while the comparative example 1 surface appeared from non-uniform dendrites, further demonstrating that example 3 was able to inhibit zinc dendrite growth.
Fig. 12 is a graph of the cyclic stability test of the aqueous zinc ion full cell of the electrolyte composition standard of example 3 and comparative example 1 at a current density of 10A g -1 for the zinc electrode and titanium foil supported MnO 2. As can be seen from the graph, after 1500 cycles, the aqueous zinc ion battery assembled in example 3 still has a capacity retention rate of 70.2%, which is far higher than that of 17.9% of comparative example 1, indicating that example 3 can improve the cycle performance of the aqueous zinc ion battery under high current.
Fig. 13 is a chart showing nucleation overpotential test of a standard symmetrical battery composed of the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 under the current density of 20mA cm -2, wherein the embodiment 3 has the lowest nucleation overpotential, which shows that the test can promote the uniform nucleation process of zinc ions, reduce the generation of zinc dendrites and improve the cycle performance of the water-based zinc ion battery.
The foregoing description of the preferred embodiment of the invention is merely illustrative of the invention and is not intended to be limiting. It will be appreciated by persons skilled in the art that many variations, modifications, and even equivalents may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the zinc ion battery electrolyte containing the TiO 2/Ti3C2Tx composite material is characterized by comprising the following steps:
S1, placing Ti 3C2Tx MXene powder into water, stirring, performing ultrasonic treatment, transferring to a reaction kettle, performing hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished;
S2, centrifugally collecting the solution cooled in the step S1, wherein the obtained precipitate is the TiO 2/Ti3C2Tx composite material;
And S3, preparing zinc sulfate/zinc trifluoromethane sulfonate/zinc chloride/zinc acetate electrolyte, and adding the TiO 2/Ti3C2Tx composite material obtained in the step S2 to prepare the zinc ion battery electrolyte.
2. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material according to claim 1, wherein in the step S1, the amount of Ti 3C2Tx MXene powder is 1-5 mg.
3. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material according to claim 1, wherein in the step S1, water is deionized water, and the volume is 20-30 mL.
4. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material according to claim 1, wherein in the step S1, the stirring time is 10-30 min, and the ultrasonic treatment time is 20-3 min.
5. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite according to claim 1, wherein in the step S1, the hydrothermal reaction conditions are as follows: reacting for 2-15 h at 120-180 ℃ with the temperature rising rate of 5-10 ℃/min.
6. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material according to claim 1, wherein in the step S2, the centrifugation condition is 10000rpm, and the centrifugation is performed for 1min.
7. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material according to claim 1, wherein in the step S3, the concentration of the zinc sulfate/zinc trifluoromethane sulfonate/zinc chloride/zinc acetate electrolyte is 2mol/L.
8. The method for preparing a zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite material according to claim 1, wherein in the step S3, the concentration of the TiO 2/Ti3C2Tx composite material is 10-40 mg/L.
9. A zinc ion battery electrolyte containing a TiO 2/Ti3C2Tx composite produced by the production method according to any one of claims 1 to 8.
10. Use of the electrolyte for zinc ion batteries containing TiO 2/Ti3C2Tx composite according to claim 9 in the protection of zinc anodes for zinc ion batteries.
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