CN108217725B - Hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2Preparation method and application of O) material - Google Patents
Hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2Preparation method and application of O) material Download PDFInfo
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Abstract
The invention relates to a hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2O) material is prepared by mixing vanadyl acetate VO (Ac)2Sequentially dissolving the zinc chloride and the zinc chloride into a dimethylformamide solvent according to a molar ratio of 1: 1.5-1: 4, uniformly stirring to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, placing the reaction kettle into an oven, heating to 120-180 ℃, reacting at a constant temperature for 3-36 h, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol respectively, centrifuging, filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O). The hydrated basic zinc pyrovanadate prepared by the method has higher reversible specific capacity, excellent electrochemical cycle performance and good rate capability, and can be used as a novel negative electrode material to be applied to a lithium ion battery system.
Description
Technical Field
The invention belongs to the technical field of micro-nano material synthesis, and particularly relates to hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2O) material and its preparation method and application.
Background
A Lithium Ion Battery (Lithium Ion Battery) is a secondary Battery (rechargeable Battery) that mainly works by moving Lithium ions between a positive electrode and a negative electrode, and has the advantages of light weight, large capacity, no memory effect, and the like, and thus is widely used. Lithium ion batteries have been commercialized for decades and are widely used in various electronic devices. Lithium ion battery mainThe lithium ion battery comprises a positive electrode material, a negative electrode material, electrolyte, a diaphragm and a battery shell, wherein the physical and chemical activities of the positive electrode material and the negative electrode material are the key points of the performance of the lithium ion battery. Therefore, the development of an electrode material with excellent performance, environmental friendliness and low cost has become a hot spot of common research of researchers in the battery field. In particular, the energy density and electrochemical performance of lithium ion batteries depend on the physical and chemical properties of the positive and negative electrode materials. And the selection of the negative electrode material is one of the key factors for improving the energy density and safety of the battery. Compared with other parts of the lithium ion battery, the development of the negative electrode material of the lithium ion battery is relatively mature, and a plurality of negative electrode materials for the lithium ion battery, such as carbon materials, silicon-based materials, tin-based materials, lithium titanate, transition metal oxides and the like, are disclosed in the prior art. The graphite carbon material has mature technology in commercial application, stable market price, good performance in the aspects of safety and cycle life, low price and no toxicity, and is a common cathode material. However, the specific capacity of the graphite which is commercialized at present is only 372mAh g-1Greatly limiting its application. In recent years, other researchers try to replace the traditional carbon material with other emerging materials as the negative electrode material of the lithium ion battery, such as zinc vanadate materials, the material has a charge and discharge capacity far higher than that of a graphite carbon material, has a special channel structure, can be used as a lithium ion intercalation/deintercalation carrier, and is expected to become a novel high-power and high-specific-capacity negative electrode material of the lithium ion battery. The patent application with the application number of CN 103236531A discloses a lithium ion battery zinc vanadate negative electrode material and a preparation method thereof, and the novel lithium ion battery negative electrode material zinc vanadate Zn with good crystallization property is prepared by taking pyro-vanadate zinc as a precursor3(VO4)2The preparation of the material needs high-temperature treatment, the procedure is complex, the energy consumption is high, the prepared cathode material has large particles, the electronic conductivity and the ionic conductivity are low, the multiplying power performance is poor, and the material is not suitable for the application of high-power batteries.
Disclosure of Invention
In view of the problems of the prior art, the first purpose of the present invention is to provide a hydrated basic cokeZinc vanadate (Zn)3V2O7(OH)2·2H2The basic zinc pyrovanadate prepared by the method has a special shape structure and high theoretical capacity, and the basic zinc pyrovanadate containing crystal water also contributes to the specific capacity, so that the traditional viewpoint is broken through, and the basic zinc pyrovanadate is a potential ideal negative electrode material suitable for lithium ion batteries.
The hydrated basic zinc pyrovanadate (Zn) is prepared by the method3V2O7(OH)2·2H2O) preparation method of material, comprising the following steps:
mixing vanadyl acetate VO (Ac)2Sequentially dissolving the zinc chloride and the zinc chloride into a dimethylformamide solvent, uniformly stirring to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 120-180 ℃, reacting at a constant temperature for 3-36 h, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol respectively, centrifugally filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O) a material, wherein: the vanadyl acetate VO (Ac)2The molar ratio of the zinc chloride to the zinc chloride is 1: 1.5-1: 4.
Further, the heating time of the reaction kettle in the technical scheme of the invention in the oven is preferably 18-30 h.
Furthermore, the heating time of the reaction kettle in the technical scheme of the invention in the oven is preferably 24 h.
Further, the vanadyl acetate VO (Ac) in the technical scheme of the invention2The molar ratio to zinc chloride is preferably 1:1.5 or 1: 4.
Further, the heating temperature of the reaction kettle in the technical scheme of the invention in the oven is preferably 130-140 ℃.
Further, in the technical scheme of the invention, the temperature of the vacuum drying is preferably 60-80 ℃, and the drying time is preferably 8-12 h.
Further, the product in the technical scheme of the invention is washed by distilled water and absolute ethyl alcohol alternately, and the obtained product is preferably washed by distilled water and absolute ethyl alcohol alternately for 2-3 times respectively.
In the technical scheme of the invention, the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining.
Further, the vanadyl acetate VO (Ac) in the technical scheme of the invention2The purity grade of the zinc chloride raw material is analytically pure or chemically pure.
The invention also aims to provide hydrated basic zinc pyrovanadate (Zn) prepared by the method3V2O7(OH)2·2H2O) the use of the material in lithium ion batteries.
The invention provides an electrode, wherein the raw material components of the electrode comprise hydrated basic zinc pyrovanadate (Zn) prepared by the method3V2O7(OH)2·2H2O) material as an electrode active material.
The invention provides a lithium ion battery, and a negative electrode material of the lithium ion battery comprises hydrated basic zinc pyrovanadate (Zn) prepared by the method3V2O7(OH)2·2H2O) material.
The invention has the advantages and positive effects that:
(1) the invention adopts a solvothermal method to synthesize hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2O) material, the method has low cost, simple operation, mild reaction condition, no need of high-temperature ignition for preparation, low energy consumption, high purity of the synthesized product and good crystallinity, the synthesized product is hydrated basic zinc pyrovanadate, and the unit cell parameter of the synthesized product is consistent with the standard map JCPDS FileCardNO.50-0570;
(2) the product of the invention is hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2O) a material, wherein the valence of vanadium is pentavalent;
(3) the dimethyl formamide adopted by the invention not only serves as a solvent, but also serves as a template agent in the inventionThe effect is favorable for the self-assembly of ions in the reaction liquid to generate hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2O) a microsphere structure;
(4) the solvothermal reaction time of the invention has important influence on the product morphology: when the synthesis time is 3 hours, the product is in an irregular small particle shape; when the synthesis time is 6h, the product is flaky; when the synthesis time is 12h, microspheres are formed in the product; when the synthesis time is 16h, the size distribution of the microspheres in the product is not uniform; when the time is 24 hours, the formed microspheres have uniform size distribution, and the structure of the self-assembled microspheres is the most complete;
(5) the hydrated basic zinc pyrovanadate material synthesized by the method has good multiplying power circulation performance, and when the current density is 100mA g-1After 100 cycles, the specific capacity can be kept at 500mAh g-1The electrochemical performance of the product with the synthesis time of 24h is optimal, and when the current density is 100mA g-1The specific capacity of the product can be maintained to be 1240.76mAh g after 100 times of circulation-1When the current density is 1000mA g-1The specific capacity is still 771.29mAh g-1The charging platform of the material is about 1V;
(6) the hydrated alkali type zinc pyrovanadate material synthesized by the method has small impedance and large lithium ion diffusion coefficient, the product prepared within 24 hours of synthesis time has the minimum impedance and the maximum lithium ion diffusion coefficient, the polarization degree of the battery is small in the charging/discharging process, and when the current density is 5Ag-1When it is used, its specific capacity is 598.8mAhg-1Therefore, when the hydrated basic zinc pyrovanadate material prepared by the method is used as a negative electrode material of a lithium ion battery, the whole battery system has high lithium storage performance, excellent cycle performance and excellent electrochemical performance, and has great advantages and wide application prospect compared with materials in the prior art;
(7) the invention has rich and cheap raw material sources, and plays a role in promoting the development and utilization of mineral resources in Hubei province and Huxi province.
Drawings
FIG. 1 is E, according to embodiment 1 of the present invention5 hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2O) X-ray diffraction results of the material;
FIG. 2 shows hydrated basic zinc pyrovanadate (Zn) prepared in embodiments 1 to 4 of the present invention3V2O7(OH)2·2H2O) scanning electron micrographs of the material;
FIG. 3 shows the hydrated basic zinc pyrovanadate (Zn) prepared in example 5 of the present invention3V2O7(OH)2·2H2O) scanning electron micrographs of the material;
FIG. 4 shows the hydrated basic zinc pyrovanadate (Zn) prepared in example 5 of the present invention3V2O7(OH)2·2H2O) transmission electron micrographs of the material;
FIG. 5 shows the hydrated basic zinc pyrovanadate (Zn) prepared in example 5 of the present invention3V2O7(OH)2·2H2O) thermogravimetric analysis of the material;
FIG. 6 (a) shows hydrated basic zinc pyrovanadate (Zn) prepared in example 5 of the present invention3V2O7(OH)2·2H2O) XPS graph of material, (b) Zn 2p high resolution spectrum; (c) is a V2 p high resolution map spectrum; (d) is an O1 s high resolution spectrum.
FIG. 7 shows hydrated basic zinc pyrovanadate (Zn) prepared in examples 1 to 5 of the present invention3V2O7(OH)2·2H2O) cycle performance profile of the material.
FIG. 8 shows hydrated basic zinc pyrovanadate (Zn) prepared in examples 1 to 5 of the present invention3V2O7(OH)2·2H2O) a graph of the rate cycling performance of the material.
FIG. 9 shows the hydrated basic zinc pyrovanadate (Zn) prepared in example 5 of the present invention3V2O7(OH)2·2H2O) a charge-discharge curve of the material;
FIG. 10 shows hydrated basic zinc pyrovanadate (Zn) prepared in examples 1 to 5 of the present invention3V2O7(OH)2·2H2O) an electrochemical impedance spectrum of the material;
FIG. 11 shows hydrated basic zinc pyrovanadate (Zn) prepared in examples 1 to 5 of the present invention3V2O7(OH)2·2H2O) a linear fit plot of the Warburg impedance of the material.
Detailed Description
The technical solution of the present invention is further explained in detail by the following specific examples and the accompanying drawings. The following embodiments are merely exemplary of the present invention, which is not intended to limit the present invention in any way, and those skilled in the art may modify the present invention in many ways by applying the teachings set forth above to equivalent embodiments with equivalent modifications. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention.
Example 1
A hydrated basic zinc pyrovanadate (Zn) as described in this example3V2O7(OH)2·2H2O) material is prepared by the following steps:
adding 1mmol of vanadyl acetate VO (Ac)2Sequentially dissolving 1.5mmol of zinc chloride and 100 ml of dimethylformamide solvent, uniformly stirring to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, placing the reaction kettle into an oven, heating to 120 ℃, reacting at constant temperature for 3 hours, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol for 3 times alternately, centrifuging, filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O) material.
The product of this example, hydrated basic zinc pyrovanadate (Zn) obtained as described above3V2O7(OH)2·2H2O) the X-ray diffraction result of the material is shown as (a) in figure 1, and the scanning electron microscope result of the product is shown as (a) in figure 2.
As can be seen from the results of X-powder diffraction test, this example isDiffraction angles of the compounds prepared in the example are 12.29 degrees, 20.95 degrees, 30.10 degrees, 32.06 degrees, 34.19 degrees, 36.46 degrees, 42.65 degrees, 51.63 degrees, 52.72 degrees, 61.24 degrees and 62.58 degrees which correspond to crystal faces of (001), (011), (012), (111), (020), (021), (022), (023), (122), (220) and (024), and diffraction peaks of the compounds are completely consistent with a standard spectrum (JCPDS File Card No.50-0570), which indicates that the products synthesized in the example are Zn with a hexagonal structure3V2O7(OH)2·2H2O。
As can be seen from the scanning electron microscope results of the products, most of the products prepared by the embodiment are irregular small particles.
Example 2
A hydrated basic zinc pyrovanadate (Zn) as described in this example3V2O7(OH)2·2H2O) material is prepared by the following steps:
adding 1mmol of vanadyl acetate VO (Ac)2Sequentially dissolving the zinc chloride and 2mmol of zinc chloride into 100 ml of dimethylformamide solvent, uniformly stirring to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, reacting at a constant temperature for 6h, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol alternately for 3 times, centrifuging, filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O) material.
The product of this example, hydrated basic zinc pyrovanadate (Zn) obtained as described above3V2O7(OH)2·2H2O) the X-ray diffraction result of the material is shown as (b) in figure 1, and the scanning electron microscope result of the product is shown as (b) in figure 2.
As can be seen from the results of X-ray powder diffraction test, the compound prepared in this example had diffraction angles of 12.29 °, 20.95 °, 30.10 °, 32.06 °, 34.19 °, 36.46 °, 42.65 °, 51.63 °, 52.72 °, 61.24 ° and 62.58 ° corresponding to the (001), (011), (012), (111), (020), (021), (022), (023), (122), (220) and (024) crystal planes, respectively, and had diffraction peaks corresponding to the standard pattern (JCPDS File Card No.50-0570)The results are completely consistent, and show that the product synthesized by the embodiment is Zn with a hexagonal structure3V2O7(OH)2·2H2O。
As can be seen from the scanning electron microscope results of the products, most of the products prepared by the embodiment have a sheet structure.
Example 3
A hydrated basic zinc pyrovanadate (Zn) as described in this example3V2O7(OH)2·2H2O) material is prepared by the following steps:
adding 1mmol of vanadyl acetate VO (Ac)2Sequentially dissolving the zinc chloride and 2.5mmol of zinc chloride into 100 ml of dimethylformamide solvent, uniformly stirring to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 180 ℃, reacting at a constant temperature for 12 hours, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol for 3 times alternately, centrifuging, filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O) material.
The product of this example, hydrated basic zinc pyrovanadate (Zn) obtained as described above3V2O7(OH)2·2H2O) the X-ray diffraction result of the material is shown as (c) in figure 1, and the scanning electron microscope result of the product is shown as (c) in figure 2.
As can be seen from the results of X-ray powder diffraction test, the diffraction angles of the compound prepared in the example are 12.29 degrees, 20.95 degrees, 30.10 degrees, 32.06 degrees, 34.19 degrees, 36.46 degrees, 42.65 degrees, 51.63 degrees, 52.72 degrees, 61.24 degrees and 62.58 degrees, which correspond to the crystal planes of (001), (011), (012), (111), (020), (021), (022), (023), (122), (220) and (024), respectively, and the diffraction peaks thereof are completely consistent with the standard map (JCPDS File Card No.50-0570), which indicates that the product synthesized in the example is Zn with hexagonal structure3V2O7(OH)2·2H2O。
The scanning electron microscope result of the product shows that most of the product prepared by the embodiment has a microsphere structure formed by assembling nano sheets.
Example 4
A hydrated basic zinc pyrovanadate (Zn) as described in this example3V2O7(OH)2·2H2O) material is prepared by the following steps:
adding 1mmol of vanadyl acetate VO (Ac)2Dissolving the zinc chloride and 4mmol of zinc chloride into 100 ml of dimethylformamide solvent in sequence, stirring uniformly to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, placing the reaction kettle into an oven, heating to 160 ℃, reacting at a constant temperature for 18h, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol alternately for 3 times, centrifuging, filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O) material.
The product of this example, hydrated basic zinc pyrovanadate (Zn) obtained as described above3V2O7(OH)2·2H2O) the X-ray diffraction result of the material is shown as (d) in figure 1, and the scanning electron microscope result of the product is shown as (d) in figure 2.
As can be seen from the results of X-ray powder diffraction test, the diffraction angles of the compound prepared in the example are 12.29 degrees, 20.95 degrees, 30.10 degrees, 32.06 degrees, 34.19 degrees, 36.46 degrees, 42.65 degrees, 51.63 degrees, 52.72 degrees, 61.24 degrees and 62.58 degrees, which correspond to the crystal planes of (001), (011), (012), (111), (020), (021), (022), (023), (122), (220) and (024), respectively, and the diffraction peaks thereof are completely consistent with the standard map (JCPDS File Card No.50-0570), which indicates that the product synthesized in the example is Zn with hexagonal structure3V2O7(OH)2·2H2O。
The scanning electron microscope result of the product shows that most of the product prepared by the embodiment has a microsphere structure assembled by nano sheets.
Example 5
A hydrated basic zinc pyrovanadate (Zn) as described in this example3V2O7(OH)2·2H2O) material is prepared by the following steps:
adding 1mmol of vanadyl acetate VO (Ac)2Dissolving the zinc chloride and 4mmol of zinc chloride into 100 ml of dimethylformamide solvent in sequence, stirring uniformly to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, placing the reaction kettle into an oven, heating to 140 ℃, reacting at a constant temperature for 24h, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol alternately for 3 times, centrifuging, filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate (Zn) product3V2O7(OH)2·2H2O) material.
The product of this example, hydrated basic zinc pyrovanadate (Zn) obtained as described above3V2O7(OH)2·2H2O) is shown in (e) in FIG. 1, the scanning electron microscope result of the product is shown in FIG. 3, the transmission electron microscope result of the product is shown in FIG. 4, and the thermogravimetric analysis result of the product is shown in FIG. 5.
As can be seen from the results of X-ray powder diffraction test, the diffraction angles of the compound prepared in the example are 12.29 degrees, 20.95 degrees, 30.10 degrees, 32.06 degrees, 34.19 degrees, 36.46 degrees, 42.65 degrees, 51.63 degrees, 52.72 degrees, 61.24 degrees and 62.58 degrees, which correspond to the crystal planes of (001), (011), (012), (111), (020), (021), (022), (023), (122), (220) and (024), respectively, and the diffraction peaks thereof are completely consistent with the standard map (JCPDS File Card No.50-0570), which indicates that the product synthesized in the example is Zn with hexagonal structure3V2O7(OH)2·2H2And the crystallinity of the compound prepared in the embodiment is better according to the diffraction intensity of XRD.
The scanning electron microscope result of the product shows that the product prepared by the embodiment has a regular microsphere structure, and the microsphere structure is formed by assembling regular nanosheets. The transmission electron microscope result of the product further shows that the thickness of the nano-sheet self-assembled into the microsphere structure of the embodiment is about 10 nm.
The thermogravimetric analysis of fig. 5 can further confirm that the weight loss rate of the product at different temperatures is 12.32% when the temperature is increased from 100 ℃ to 600 ℃, and the theoretical weight loss rate of the product is close to 11.27% after 1% of the absorbed water is deducted.
Example 6
The hydrated basic zinc pyrovanadate (Zn) prepared in the above examples 1 to 5 is respectively added3V2O7(OH)2· 2H2O) carrying out electrochemical performance test on the material, wherein the test method comprises the following steps:
the products from the examples were each prepared as electrodes (active material to acetylene black, binder ratio 7:2:1), pressed on a nickel screen and dried in a vacuum oven at 120 ℃ for 24 hours. The electrolyte contains 1M LiPF6In the mixed solution of ethylene carbonate and dimethylethylene carbonate (1: 1), the separator was Celgard 2400, and the reference electrode was a lithium plate. And (3) assembling a simulation battery in the glove box, testing the battery performance in a charging and discharging voltage range (0.01-3.00V) and a current density (100 mA/g). The impedance was tested by the Shanghai Chenghua electrochemical workstation (CHI 600A).
Hydrated basic zinc pyrovanadate (Zn) prepared in embodiments 1-5 of the invention3V2O7(OH)2·2H2O) are shown in fig. 7 and 8, respectively.
As can be seen from FIG. 8, the hydrated basic zinc pyrovanadate (Zn) prepared by the invention3V2O7(OH)2·2H2O) all had excellent rate performance, as can be seen from the rate cycle performance graph of the product prepared in example 5, at a current density of 100mAg, respectively-1、200mAg-1、500mAg-1、800mAg-1、1000mAg-1、2000mAg-1、 5000mAg-1Charging and discharging in time, the specific discharge capacity is 1130.2mAg-1、1051.3mAg-1、885.0mA g-1、829.3mAg-1、771.3mAg-1、716.4mAg-1、598.8mAh g-1When the current density is recovered to 100mAg-1The discharge capacity is restored to 1256.6mAh g-1The best rate performance of the product synthesized in example 5 is demonstrated.
FIG. 9 shows the current density of 100mAg-1At a voltage range of 0.0Charge and discharge curves of the product obtained in example 5 at 1-3V. As can be seen from FIG. 9, the initial charge and discharge capacities of the product were 1179.6mAh g respectively-1、 1598.7mAhg-1The coulombic efficiency is 73.8 percent, and the charge and discharge capacity of the second circulation are 1120.4mAh g-1、 1222.1mAh g-1The coulombic efficiency was 91.7%. The formation of a solid electrolyte membrane results in a first coulombic inefficiency. When the material is cycled for 100 times, the discharge capacity is kept to 1240.76mAh g-1。
Example 7
The hydrated basic zinc pyrovanadate (Zn) prepared in the above examples 1 to 5 is respectively added3V2O7(OH)2· 2H2O) the material is subjected to impedance performance test by the following method: the products of the examples were fabricated into electrodes with substantially the same amount of active material and similar area, assembled into simulated cells, tested by Shanghai Chenghua electrochemical workstation (CHI 600A for measuring impedance under selected test frequency range of 0.01-0.01
The scan rate was 0.1mV/sec, according to the formula:
by applying the Warburg coefficient AwAnd (4) determining. To deduce the variation trend of the diffusion and absorption number of the lithium ions.
Hydrated basic zinc pyrovanadate (Zn) prepared in embodiments 1-5 of the invention3V2O7(OH)2·2H2O) electrochemical impedance profile of the material is shown in fig. 10. It can be seen that the impedance of the products obtained in examples 1 to 5 is 136.5 Ω, 105.1 Ω, 75.48 Ω, 64.47 Ω and 26.71 Ω, respectively, i.e. the impedance of the material obtained in example 5 is the smallest. In addition, the linear fitting to the Warburg impedance is respectively carried out by fitting to the Warburg coefficient AwCalculation of (A) (the slope of the straight line shown in FIG. 11) found that A is the same as that of the products obtained in examples 1 to 5wAre respectively 201.11 omegas-1/2、151.22Ωs-1/2、98.55Ωs-1/2、 76.93Ωs-1/2、49.63Ωs-1/2Thereby estimating their corresponding lithium ion diffusion coefficients, and measuringTest results show that the lithium ion diffusion coefficients of the products prepared in the embodiments 1 to 5 of the invention are all large, and the product prepared in the embodiment 5 is used as A of an electrodewThe minimum and thus the maximum lithium ion diffusion coefficient further illustrate that the material prepared in example 5 exhibits more excellent electrochemical performance.
Claims (3)
1. Hydrated basic zinc pyrovanadate Zn3V2O7(OH)2·2H2The preparation method of the O material is characterized by comprising the following steps: the method comprises the following steps:
mixing vanadyl acetate VO (Ac)2Sequentially dissolving the zinc chloride and the zinc chloride into a dimethylformamide solvent, uniformly stirring to obtain a dark green solution, transferring the dark green solution into a stainless steel reaction kettle, putting the reaction kettle into an oven, heating to 140 ℃, reacting at a constant temperature for 24 hours, cooling to room temperature, washing the obtained product with distilled water and absolute ethyl alcohol respectively, centrifugally filtering, and drying in vacuum to obtain a hydrated basic zinc pyrovanadate Zn product3V2O7(OH)2·2H2O material, wherein: the vanadyl acetate VO (Ac)2The molar ratio of the zinc chloride to the zinc chloride is 1: 1.5-1: 4.
2. Hydrated basic zinc pyrovanadate Zn according to claim 13V2O7(OH)2·2H2The preparation method of the O material is characterized by comprising the following steps: the vanadyl acetate VO (Ac)2The molar ratio to zinc chloride is 1:1.5 or 1: 4.
3. Hydrated basic zinc pyrovanadate Zn according to claim 1 or 23V2O7(OH)2·2H2The preparation method of the O material is characterized by comprising the following steps: the temperature of the vacuum drying is 60-80 ℃, and the drying time is 8-12 h.
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| "Zn3(OH)2V2O7•2H2O and Zn3(VO4)2 3D microspheres as anode materials for lithium-ion batteries";S. Y. Zhang et al.;《J Mater Sci》;20130124;第48卷;摘要 * |
| "Zn3V2O7(OH)2(H2O)2 and Zn3V2O8 nanostructures: controlled fabrication and photocatalytic performance";Rui Shi et al.;《J. Mater. Chem》;20110314;第21卷;第6314页左栏第二段实验部分以及图3 * |
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