CN114132957A - Preparation method of two-phase zinc metatitanate negative electrode material - Google Patents
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Abstract
The invention discloses a preparation method of a double-phase zinc metatitanate negative electrode material, and belongs to the technical field of lithium ion batteries. The method comprises the following specific steps: dissolving zinc acetate, zinc citrate, zinc gluconate, tetrabutyl titanate and isopropyl titanate in an alcohol solution, and marking as a solution A; reacting NH4F、NH4Br, urea and N, N-dimethylformamide were dissolved in ethylene glycol, and polyvinylpyrrolidone was added, and the solution B was recorded. And mixing the solution A and the solution B, stirring to form a uniform solution, transferring the uniform solution into a polytetrafluoroethylene reaction kettle, and reacting for 22-26 h. Cooling to room temperature, centrifugally washing and drying. Then putting the precursor into a muffle furnace to be burnt for 2-4h, cooling to room temperature, and grinding to obtain the biphase ZnTiO3And (3) compounding the negative electrode material. The anode material has uniform and consistent particles, good dispersibility, high crystallinity and stable porous structure,therefore, the reversible capacity of the wide potential window is considerable, the rate capability is excellent, and the cycle life is stable.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a titanate negative electrode material of a lithium ion battery, in particular to a preparation method of a double-phase zinc metatitanate negative electrode material.
Background
The traditional fossil energy is facing the crisis of shortage and even exhaustion, and brings huge pressure to environmental protection, and the novel industrialization development direction of circular economy and low-carbon economy can promote the rapid development of the new energy automobile industry. The lithium ion power battery is used as a new-generation environment-friendly and high-energy battery and has become a mainstream product of the power battery for the new energy automobile at present. Although the protection circuit of the lithium ion battery is mature, for the power battery, the selection of the cathode material is very critical to really ensure the safety.
Most of the negative electrode materials of the current commercial lithium ion batteries are lithium intercalation type carbon materials, the oxidation-reduction potential of the carbon materials is close to that of metal lithium, and when the batteries are overcharged, the metal lithium can generate dendrite on the surface of the carbon negative electrode, so that the dendrite penetrates through a diaphragm to cause short circuit and thermal runaway of the batteries. The titanate-based material has higher lithium intercalation potential, can effectively avoid the precipitation of metal lithium, has a certain oxygen absorption function at high temperature, has obvious safety characteristic, and is considered as an ideal choice for replacing a carbon material as a lithium ion battery cathode material. Wherein Li4Ti5O12The titanium anode material is a successfully commercialized titanium anode material, and has the biggest advantages of basically no change in volume in the lithium removal/insertion process, good cycle performance, difficult formation of lithium dendrite in the charging and discharging process and high safety. However, Li is constrained by relatively low lithium ion diffusion rates, low electrical conductivity, and low theoretical capacity4Ti5O12More extensive application; therefore, it is necessary to develop a reliable new titanate negative electrode material with higher capacity. Titanium-based ternary metal oxides are one of the most promising anode materials for titanate anode materials because of their advantages of multiple redox reactions, excellent chemical and electrical properties, high transport capacity and tunable electrical conductivity. Wherein ZnTiO3Has higher theoretical capacity and obvious price advantage compared with other metal oxides containing lithium, but ZnTiO3The defects of the method are that the electronic conductivity and the ionic conductivity of the material are low, so that the capacity is quickly attenuated and the rate performance is poor during heavy-current charging and discharging.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the preparation method of the double-phase zinc metatitanate cathode material, which has the advantages of wide raw material source, simple and convenient operation, good controllability and high reproducibility, and the obtained material has smaller particles, uniform particle size distribution and high crystallinity, thereby improving the electrochemical performance of the material while reducing the preparation cost of the material.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving a zinc source and a titanium source in an alcohol solution, and uniformly stirring to obtain a solution A; dissolving ammonium salt and amide in ethylene glycol, uniformly stirring, then adding polyvinylpyrrolidone, uniformly stirring, and marking as a solution B;
(2) mixing the solution A and the solution B, stirring to form a uniform solution, transferring the uniform solution into a reaction kettle, and reacting at the temperature of 60-80 ℃ for 22-26 h;
(3) after the reaction is finished, cooling to room temperature, centrifuging, washing and drying to obtain a precursor;
(4) the precursor is put at 500-700 ℃ for burning for 2-4h and cooled to room temperature to obtain the biphase ZnTiO3And (3) a negative electrode material.
Further, in the step (1), the molar ratio of the zinc source to the titanium source is 1:1, and the mass-to-volume ratio (mol: L) of the zinc source/titanium source to the alcohol solution in the solution A is 1: 5.
Further, in the step (1), the molar ratio of ammonium salt to amide is 1:1.5, and the volume ratio (mol: L) of the total amount of ammonium salt and amide in the solution B to the ethylene glycol is 1: 1; the mass volume ratio (mol: L) of polyvinylpyrrolidone to ethylene glycol was 0.0006: 1.
Further, the solution A and the solution B in the step (2) are mixed according to the ratio of the total amount of the zinc source and the titanium source to the total amount of the ammonium salt and the amide which is 2: 5.
Further, the stirring time of the solution A in the step (1) is 2-3h, the stirring time of the solution B after adding the ethylene glycol is 1-2h, and the stirring time of the solution B after adding the polyvinylpyrrolidone is 2-3 h; the stirring time after the mixing in the step (2) is 20-24 h.
Further, the zinc source in the step (1) is a zinc source with a molar ratio of 7: 2: 1 a mixture of zinc acetate, zinc citrate and zinc gluconate; the titanium source was a mixture of tetrabutyl titanate and isopropyl titanate in a molar ratio of 3: 2.
Further, the alcohol solution in the step (1) is a mixed solution of absolute ethyl alcohol, ethylene glycol and glycerol in a volume ratio of 2:7: 1.
Further, the ammonium salt in the step (1) is NH with a molar ratio of 9:14F and NH4A mixture of Br and amide which is a mixture of urea and N, N-dimethylformamide in a molar ratio of 4: 1.
Further, the average molecular weight of polyvinylpyrrolidone (PVP) in the step (1) is 40000.
Further, the drying in the step (3) is vacuum drying, the drying temperature is 70-90 ℃, and the drying time is 12-16 h.
Further, the biphase ZnTiO in the step (4)3The two phases of (a) are a hexagonal phase and a cubic phase.
Compared with the prior art, the invention has the following technical effects:
1. the biphase ZnTiO prepared by the invention3The composite cathode material is in a rod-like structure, uniform in particle size and stable in structure. The porous structure and the one-dimensional shape are beneficial to the diffusion of electrolyte, more lithium storage space is provided, and the volume expansion/contraction in the process of lithium ion insertion/extraction is relieved.
2. The material synthesized by the method has uniform and consistent particles and good dispersibility, and the obtained material is a micron-sized rod, so that the electrochemical performance of the material is improved.
3. The material obtained by the invention has considerable reversible capacity of a wide potential window, excellent rate capability and stable cycle life, so that the material has high practical use value and can effectively meet the practical requirements of various applications of lithium ion batteries.
4. The lithium ion battery cathode material prepared by the invention has higher theoretical capacity and rapid charge and discharge performance, and improves the energy density and power density of the lithium ion battery.
Drawings
FIG. 1 shows two-phase ZnTiO compounds obtained in example 1 of the present invention3XRD pattern of the composite cathode material;
FIG. 2 shows two-phase ZnTiO compounds obtained in example 1 of the present invention3SEM image of the composite negative electrode material;
FIG. 3 shows the biphasic ZnTiO material obtained in example 1 of the present invention3Cycle performance curve of the composite negative electrode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The polyvinylpyrrolidone (PVP) used in each example had an average molecular weight of 40000.
Example 1
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of ethanol, glycol and glycerol, wherein the volume ratio of absolute ethanol, glycol and glycerol in the mixed solution is 2:7:1, and stirring for 3 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 2h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 3h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 24 hours to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 24 hours in an oven at 70 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying for 16h at the temperature of 80 ℃ to obtain a precursor;
(4) putting the precursor into a muffle furnace, burning for 3h at 600 ℃, cooling to room temperature, and grinding for 10 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
The obtained biphase ZnTiO3The XRD pattern of the composite cathode material is shown in figure 1, and the obtained hexagonal phase ZnTiO and the cubic phase ZnTiO are3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800nm (figure 2). The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium battery is charged and discharged at 1000mA/g, the first lithium removal capacity is 414.7mAh/g, and the reversible lithium removal capacity after 100 cycles is 287.2mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability (figure 3).
Example 2
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of ethanol, glycol and glycerol, wherein the volume ratio of absolute ethanol, glycol and glycerol in the mixed solution is 2:7:1, and stirring for 2 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 1h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 2h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 20h to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 22h in an oven at 60 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying at 70 ℃ for 12h to obtain a precursor;
(4) putting the precursor into a muffle furnace, burning for 2h at 500 ℃, cooling to room temperature, and grinding for 5 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
Hexagonal phase and cubic phase ZnTiO obtained3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800nm. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium battery is charged and discharged at 1000mA/g, the first lithium removal capacity is 401.5mAh/g, and the reversible lithium removal capacity after 100 cycles is 266.1mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 3
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of ethanol, glycol and glycerol, wherein the volume ratio of absolute ethanol, glycol and glycerol in the mixed solution is 2:7:1, and stirring for 3 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 2h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 3h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 24h to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 26h in an oven at 80 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying for 16h at 90 ℃ to obtain a precursor;
(4) putting the precursor into a muffle furnace, burning for 4h at 700 ℃, cooling to room temperature, and grinding for 10 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
Hexagonal phase and cubic phase ZnTiO obtained3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800 nm. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium is charged and discharged at 1000mA/g, the first lithium removal capacity is 408.9mAh/g for 100 timesThe reversible lithium removal capacity after circulation is 255.7mAh/g, and the excellent high rate performance and the excellent circulation stability are shown.
Example 4
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of ethanol, glycol and glycerol, wherein the volume ratio of absolute ethanol, glycol and glycerol in the mixed solution is 2:7:1, and stirring for 2 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 2h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 2h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 24h to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 23h in an oven at 70 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying for 15h at the temperature of 80 ℃;
(4) putting the precursor into a muffle furnace, burning for 4h at 600 ℃, cooling to room temperature, and grinding for 6 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
Hexagonal phase and cubic phase ZnTiO obtained3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800 nm. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium battery is charged and discharged at 1000mA/g, the first lithium removal capacity is 410.4mAh/g, and the reversible lithium removal capacity after 100 cycles is 266.4mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 5
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) will be provided withDissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of ethanol, glycol and glycerol, wherein the volume ratio of absolute ethanol, glycol and glycerol in the mixed solution is 2:7:1, and stirring for 3 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 1h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 2h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 22h to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 25h in an oven at 60 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying for 13h at 90 ℃ to obtain a precursor;
(4) putting the precursor into a muffle furnace, burning for 2h at 700 ℃, cooling to room temperature, and grinding for 8 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
Hexagonal phase and cubic phase ZnTiO obtained3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800 nm. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium battery is charged and discharged at 1000mA/g, the first lithium removal capacity is 409.3mAh/g, and the reversible lithium removal capacity after 100 cycles is 269.6mAh/g, so that the lithium battery shows excellent high rate performance and cycling stability.
Example 6
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of ethanol, glycol and glycerol, wherein the volume ratio of absolute ethanol, glycol and glycerol in the mixed solution is 2:7:1, and stirring for 2 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 1h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 3h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 23h to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 26h in an oven at 60 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying at 70 ℃ for 14h to obtain a precursor;
(4) putting the precursor into a muffle furnace, burning for 3h at 600 ℃, cooling to room temperature, and grinding for 7 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
Hexagonal phase and cubic phase ZnTiO obtained3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800 nm. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium battery is charged and discharged at 1000mA/g, the first lithium removal capacity is 403.5mAh/g, and the reversible lithium removal capacity after 100 cycles is 270.6mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 7
A preparation method of a dual-phase zinc metatitanate anode material comprises the following steps:
(1) dissolving 7mmol of zinc acetate, 2mmol of zinc citrate, 1mmol of zinc gluconate, 6mmol of tetrabutyl titanate and 4mmol of isopropyl titanate in a mixed solution of 50ml of absolute ethyl alcohol, ethylene glycol and glycerol, wherein the volume ratio of the three is 2:7:1, and stirring for 3 hours to obtain a solution A; adding 18mmol of NH4F、2mmol NH4Br, 24mmol urea and 6mmol N, N-dimethylformamide are dissolved in 50ml ethylene glycol, stirred for 2h, then 0.03mmol polyvinylpyrrolidone is added, stirred for 2h, and marked as solution B;
(2) rapidly mixing the solution A and the solution B, vigorously stirring for 21h to form a uniform solution, transferring the uniform solution into a 150mL polytetrafluoroethylene reaction kettle, and then reacting for 24h in an oven at 80 ℃;
(3) after the reaction is finished, cooling to room temperature, centrifugally washing, and then putting into a vacuum drying oven for vacuum drying for 16h at 70 ℃ to obtain a precursor;
(4) putting the precursor into a muffle furnace, burning for 3h at 500 ℃, cooling to room temperature, and grinding for 10 minutes to obtain the lithium ion battery cathode material hexagonal phase and cubic phase ZnTiO3A material.
Hexagonal phase and cubic phase ZnTiO obtained3The composite cathode material is in a rod-shaped structure, the particle size distribution is uniform, the length is 3-5 mu m, and the diameter is about 800 nm. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2032 type button lithium ion battery is assembled in a glove box filled with argon gas, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V at different current densities. When the lithium battery is charged and discharged at 1000mA/g, the first lithium removal capacity is 401.8mAh/g, and the reversible lithium removal capacity after 100 cycles is 261.4mAh/g, so that excellent high rate performance and excellent cycle stability are shown.
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a dual-phase zinc metatitanate anode material is characterized by comprising the following steps:
(1) dissolving a zinc source and a titanium source in an alcohol solution, and uniformly stirring to obtain a solution A; dissolving ammonium salt and amide in ethylene glycol, uniformly stirring, then adding polyvinylpyrrolidone, uniformly stirring, and marking as a solution B;
(2) mixing the solution A and the solution B, stirring to form a uniform solution, transferring the uniform solution into a reaction kettle, and reacting at the temperature of 60-80 ℃ for 22-26 h;
(3) after the reaction is finished, cooling to room temperature, centrifuging, washing and drying to obtain a precursor;
(4) the precursor is placed at 500-700 ℃ for burning for 2-4h, cooled to room temperature,thus obtaining the biphase ZnTiO3And (3) a negative electrode material.
2. The preparation method of the dual-phase zinc metatitanate anode material of claim 1, wherein the molar ratio of the zinc source to the titanium source in step (1) is 1:1, and the ratio of the zinc source/titanium source to the quantity of the alcoholic solution in solution A is 1:5 by volume (mol: L).
3. The preparation method of the dual-phase zinc metatitanate anode material as claimed in claim 1, wherein the molar ratio of ammonium salt to amide in step (1) is 1:1.5, the volume ratio (mol: L) of the total amount of ammonium salt and amide in solution B to ethylene glycol is 1: 1; the mass volume ratio (mol: L) of polyvinylpyrrolidone to ethylene glycol was 0.0006: 1.
4. The method for preparing a dual-phase zinc metatitanate anode material according to claim 1, wherein the solution A and the solution B in the step (2) are mixed according to the ratio of the total amount of the zinc source and the titanium source to the total amount of the ammonium salt and the amide being 2: 5.
5. The preparation method of the dual-phase zinc metatitanate anode material as claimed in claim 1, wherein the stirring time of the solution A in the step (1) is 2-3h, the stirring time of the solution B after adding ethylene glycol is 1-2h, and the stirring time of the solution B after adding polyvinylpyrrolidone is 2-3 h; the stirring time after the mixing in the step (2) is 20-24 h.
6. The preparation method of the dual-phase zinc metatitanate anode material as claimed in claim 1, wherein the molar ratio of the zinc source in step (1) is 7: 2: 1 a mixture of zinc acetate, zinc citrate and zinc gluconate; the titanium source was a mixture of tetrabutyl titanate and isopropyl titanate in a molar ratio of 3: 2.
7. The preparation method of the dual-phase zinc metatitanate anode material of claim 1, wherein the alcohol solution in the step (1) is a mixed solution of absolute ethyl alcohol, ethylene glycol and glycerol in a volume ratio of 2:7: 1.
8. The preparation method of the dual-phase zinc metatitanate anode material as claimed in claim 1, wherein the ammonium salt in step (1) is NH with a molar ratio of 9:14F and NH4A mixture of Br and amide which is a mixture of urea and N, N-dimethylformamide in a molar ratio of 4: 1.
9. The preparation method of the dual-phase zinc metatitanate anode material of claim 1, wherein the drying in the step (3) is vacuum drying, the drying temperature is 70-90 ℃, and the drying time is 12-16 h.
10. The preparation method of the dual-phase zinc metatitanate anode material of claim 1, wherein the dual-phase ZnTiO in the step (4)3The two phases of (a) are a hexagonal phase and a cubic phase.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009298649A (en) * | 2008-06-13 | 2009-12-24 | Sumitomo Metal Mining Co Ltd | Oxide sintered compact, target, transparent conductive film obtained by using the same, and conductive laminate |
| US20140127106A1 (en) * | 2012-11-02 | 2014-05-08 | The Board Of Trustees Of The University Of Illinois | Regenerable oxide-based adsorbent |
| CN105016380A (en) * | 2015-08-19 | 2015-11-04 | 徐州工程学院 | Low-temperature solid-phase synthesis method of ZnTiO3 micro crystal |
| CN106024398A (en) * | 2016-08-03 | 2016-10-12 | 浙江悦昇新能源科技有限公司 | Dye-sensitized Zn2TiO4 nano-crystalline film for solar cell and preparation method of film |
| EP3088363A1 (en) * | 2013-12-27 | 2016-11-02 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| CN107098381A (en) * | 2017-05-16 | 2017-08-29 | 哈尔滨商业大学 | The preparation method of the zinc titanate catalysis material of special appearance |
| CN112158800A (en) * | 2020-10-13 | 2021-01-01 | 浙江奚态生物科技有限公司 | Porous V2O3-ZnTiO3rGO composite hydrogen storage material and preparation method thereof |
-
2021
- 2021-11-29 CN CN202111428811.8A patent/CN114132957B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009298649A (en) * | 2008-06-13 | 2009-12-24 | Sumitomo Metal Mining Co Ltd | Oxide sintered compact, target, transparent conductive film obtained by using the same, and conductive laminate |
| US20140127106A1 (en) * | 2012-11-02 | 2014-05-08 | The Board Of Trustees Of The University Of Illinois | Regenerable oxide-based adsorbent |
| EP3088363A1 (en) * | 2013-12-27 | 2016-11-02 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| CN105016380A (en) * | 2015-08-19 | 2015-11-04 | 徐州工程学院 | Low-temperature solid-phase synthesis method of ZnTiO3 micro crystal |
| CN106024398A (en) * | 2016-08-03 | 2016-10-12 | 浙江悦昇新能源科技有限公司 | Dye-sensitized Zn2TiO4 nano-crystalline film for solar cell and preparation method of film |
| CN107098381A (en) * | 2017-05-16 | 2017-08-29 | 哈尔滨商业大学 | The preparation method of the zinc titanate catalysis material of special appearance |
| CN112158800A (en) * | 2020-10-13 | 2021-01-01 | 浙江奚态生物科技有限公司 | Porous V2O3-ZnTiO3rGO composite hydrogen storage material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| POOYA TAHAY ET.AL: "Synthesis of cubic and hexagonal ZnTiO3 as catalyst support in steam reforming of methanol: Study of physical and chemical properties of copper catalysts on the H2 and CO selectivity and coke formation", 《I N T E RNA T I ONAL JOURNAL OF HYDROGEN ENERGY》, vol. 45 * |
| 周孝林;曾宪光;林小力;陈建;高远洋;: "球形Li_2ZnTi_3O_8的制备及电化学性能研究", 四川轻化工大学学报(自然科学版), no. 02 * |
| 李俊生;吴家瑞;徐美艳;夏至;谭冲;左金龙;: "聚乙烯吡咯烷酮辅助液相沉淀法制备立方相ZnTiO_3棒及其光催化降解罗丹明B的研究", 化工新型材料, no. 03 * |
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