CN115744983A - Vanadium-zinc sulfide ion battery positive electrode material and preparation method and application thereof - Google Patents
Vanadium-zinc sulfide ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- -1 Vanadium-zinc sulfide Chemical compound 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 230000035484 reaction time Effects 0.000 claims description 2
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- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
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- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical group [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002033 PVDF binder Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 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 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention provides a vanadium-zinc sulfide ion battery positive electrode material, a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) Dispersing a vanadium source and a vulcanizing agent in a solvent to obtain a first reaction liquid, carrying out solvothermal reaction on the reaction liquid, carrying out solid-liquid separation, washing, and drying to obtain VS4; 2) At VS 4 Adding glucose into the aqueous solution to obtain a second reaction solution, performing hydrothermal reaction, performing solid-liquid separation, washing and drying to obtain the D-VS 4 Namely the vanadium sulfide zinc ion battery anode material. VS prepared by the invention 4 The material is used as the positive electrode of the zinc ion battery, and the prepared zinc ion battery has high rate performance, high specific capacity and excellent cycling stability, and the current density is 10Ag ‑1 Under the test condition, the specific capacity of the material reaches 139mA h g ‑1 The cycle time is more than 8000 cycles, and the capacity retention rate reaches 72.0%.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a vanadium sulfide zinc ion battery positive electrode material and a preparation method and application thereof.
Background
The non-uniformity and unpredictability of the distribution of renewable energy forces us to develop energy storage systems (EES). Lithium Ion Batteries (LIBs) have been widely used in various fields for the past several decades due to their excellent electrochemical properties. However, the shortage of natural reserves of lithium resources and the danger of flammable electrolytes limit their further development. In contrast, water-based Zinc Ion Batteries (ZIBs) are expected to become next-generation hot rechargeable batteries due to their advantages of abundant zinc reserves, convenient assembly, environmental friendliness, high safety, high theoretical capacity, and the like. Despite the many advantages of ZIBs, the lack of suitable cathode materials limits their further applications. To date, many materials have been developed for ZIBs positive electrodes to store zinc ions, such as manganese-based oxides, vanadium-based oxides, and prussian blue analogs. However, most of them show low capacity or poor cycle stability. For example, manganese-based oxides have poor rate performance and cycling stability, vanadium-based oxides have lower average operating voltages, and prussian blue analogs have lower capacities. Therefore, there is an urgent need to develop high-performance ZIBs positive electrode materials having excellent zinc ion storage properties.
In recent years, layered Transition Metal Sulfides (TMSs), such as MoS 2 、SnS 2 、WS 2 And VS 2 Has received much attention due to its graphene-like crystal structure and unique physicochemical properties. The layered channel not only can promote the rapid diffusion of ions, but also can relieve the volume change of the host material caused in the ion embedding/extracting process. In TMSs materials, VS 2 The V valence state is rich and the theoretical capacity is high in the electrochemical process, so that the V valence state is often used as a positive electrode material of ZIBs, and the good cycle stability and rate capability are shown. As a VS 2 Is an analogue of (2), VS 4 Having more sulfur atoms, the lattice space ratio VS 2 Much larger, these reasons may be VS 4 Has better electrochemical performance. However, in practical applications, the VS 4 Polysulfide is generated due to the intercalation/deintercalation of zinc ions, and pulverization and structural collapse of the material are easily caused. Therefore, there is an urgent need for VS 4 The material is further treated to enhance its electrochemistryAnd (4) performance.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a vanadium-zinc sulfide battery positive electrode material, and a preparation method and application thereof, which are used for solving the problems of VS in the prior art 4 When the material is applied to the positive electrode of a zinc ion battery, the problems of poor cycle stability and low specific capacity are presented.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a positive electrode material of a vanadium zinc sulfide ion battery, comprising the steps of:
1) Dispersing a vanadium source and a vulcanizing agent in a solvent to obtain a first reaction liquid, carrying out solvothermal reaction on the reaction liquid, carrying out solid-liquid separation, washing and drying to obtain VS 4 ；
2) At VS 4 Adding glucose into the aqueous solution to obtain a second reaction solution, performing hydrothermal reaction, performing solid-liquid separation, washing and drying to obtain the D-VS 4 Namely the vanadium sulfide zinc ion battery anode material. This step is carried out by means of a weak reduction of glucose during the hydrothermal reaction to give D-VS 4 The overall valence of the medium V is reduced, and the medium V has more sulfur defects and ion active sites, so that the reversible capacity of the medium V is increased. In addition, a carbon layer is formed on the surface layer of D-VS4 by the carbonization of glucose in the hydrothermal process, and the stability and the electronic conductivity of the structure can be greatly improved due to the existence of the carbon layer, so that the integral electrochemical performance of the material is improved.
Preferably, in the step 1), the solvent is a mixed solution of water and ethylene glycol, the volume ratio of the water to the ethylene glycol in the mixed solution of water and ethylene glycol is (3-5): 7, and preferably, the water is adopted to dissolve the vanadium source, the ethylene glycol is adopted to dissolve the vulcanizing agent, and then the mixture is mixed to prepare the vanadium-containing composite material.
Preferably, in the step 1), the molar ratio of the vanadium source to the vulcanizing agent is 1 (1-10), such as 1 (1-3), 1 (3-5) and 1 (5-10).
Preferably, in the step 1), the concentration of the vanadium source in the first reaction solution is 0.002 to 0.1mol/L, such as 0.002 to 0.06mol/L, and 0.06 to 0.1mol/L.
Preferably, in step 1), the temperature of the solvothermal reaction is 100 to 200 ℃, such as 100 to 150 ℃,150 to 200 ℃, and the reaction time is 10 to 50 hours, such as 10 to 50h, and 10 to 50 hours.
Preferably, in step 1), the vanadium source is sodium orthovanadate or sodium metavanadate, and the vulcanizing agent is thioacetamide or thiourea.
Preferably, in the step 2), VS is contained in the second reaction solution 4 The concentration of (B) is 0.0025-0.125 mol/L, such as 0.0025-0.025 mol/L, 0.025-0.05 mol/L, 0.05-0.125 mol/L.
Preferably, in step 2), the VS 4 The molar ratio of the glucose to the glucose is 1 (0.1-10), and specifically 1 (0.1-1), 1 (1-5) and 1 (5-10).
The invention also provides the vanadium sulfide zinc ion battery anode material prepared by the preparation method.
The invention also provides application of the vanadium sulfide zinc ion battery positive electrode material as a positive electrode active substance in a zinc ion battery.
As described above, the present invention has the following advantageous effects:
(1) The preparation method is simple and universal, the used reagent is cheap, no special requirements are required on equipment, and batch production can be realized.
(2) VS prepared by the invention 4 The zinc ion battery has the advantages of uniform size, stable structure and excellent zinc ion battery performance.
(3) VS prepared by the invention 4 The material is used as the positive electrode of the zinc ion battery, and the prepared zinc ion battery has high rate performance, high specific capacity and excellent cycling stability, and the current density is 10Ag -1 Under the test condition, the specific capacity of the catalyst reaches 139mA h g -1 The cycle time is more than 8000 cycles, and the capacity retention rate reaches 72.0%.
Drawings
FIG. 1 shows VS prepared in example 1 4 (a) And D-VS 4 (b) SEM image of (d).
FIG. 2 shows VS prepared in example 1 4 (a) And D-VS 4 (b) XRD pattern of (a).
FIG. 3 shows asVS prepared in example 1 4 (a) And D-VS 4 (b) An EPR map of (1).
FIG. 4 shows the D-VS prepared in example 1 4 A TEM image of (a).
FIG. 5 shows VS 4 And D-VS 4 The material is used as a multiplying power performance diagram of a zinc ion battery assembled by a positive electrode under different current density test conditions.
FIG. 6 shows VS prepared for example 1 4 And D-VS 4 The material is used as the positive electrode of a zinc ion battery assembled by 0.1A g -1 After 10 cycles of activation with small current, 10A g -1 Cycling performance plot at current density.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be understood that the process equipment or devices not specifically mentioned in the following examples are conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that a combinational connection relationship between one or more devices/apparatuses mentioned in the present invention does not exclude that other devices/apparatuses may also be present before or after the combinational device/apparatus or that other devices/apparatuses may also be interposed between the two devices/apparatuses explicitly mentioned, unless otherwise stated. Moreover, unless otherwise indicated, the numbering of the method steps is only a convenient tool for identifying each method step, and is not intended to limit the order of the method steps or the scope of the invention, and changes or modifications in the relative relationship thereof may be regarded as the scope of the invention without substantial change in the technical content.
Example 1
(1) Taking a clean beaker, measuring 15ml of deionized water, pouring into the beaker, and weighing 3mmol of NaVO 3 Pouring into a beaker, adding the magnetic beads, and stirring on a stirring table for 30min; during this period, another clean beaker was taken, 35ml of ethylene glycol was measured, the beaker was poured, 15mmol of TAA was measured and added to the beaker, magnetic beads were added, and the beaker was stirred on a stirring table for 30min. Then, mixing the two solutions, and stirring for 1h again;
(2) The mixed solution is transferred to a 100ml reaction kettle and reacted for 24 hours at the temperature of 160 ℃. After the reaction is finished, sucking out the solid product by using a rubber head dropper, transferring the solid product into a centrifugal tube for centrifugation, wherein the washing solvent is deionized water, changing the washing solvent into ethanol after three times of centrifugal washing, carrying out three times of centrifugal washing again, and finally placing the washing product in a vacuum oven at 60 ℃ for 12 hours to obtain VS 4 A material;
(3) Taking a clean beaker, measuring 40ml of deionized water, pouring into the beaker, and weighing 1mmol of the VS dried in the step (2) 4 Pouring the materials into a beaker, adding magnetic beads, and stirring for 10min on a stirring table; then adding 1mmol glucose in the stirring process of the solution, and stirring for 50min again;
(4) The mixed solution is transferred to a 50ml reaction kettle and reacted for 24 hours at the temperature of 100 ℃. After the reaction is finished, sucking out the solid product by using a rubber-tipped dropper, transferring the solid product into a centrifugal tube for centrifugation, taking deionized water as a washing solvent, centrifugally washing for three times, and placing the washed product in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain D-VS 4 A material;
VS from example 1 4 And D-VS 4 The morphology and composition of (A) are characterized, and the results are shown in FIGS. 1 to 4, and VS can be seen from the SEM image of FIG. 1 4 And D-VS 4 The samples were all 500-700nm spheres. As can be seen from the XRD pattern of fig. 2: D-VS 4 Diffraction Peak and VS of sample 4 The standard peaks are consistent, demonstrating no phase change of the material before and after modification. As can be seen from the EPR map of fig. 3: D-VS 4 Ratio VS 4 With a greater peak intensity, demonstrating the D-VS synthesized after addition of glucose 4 Has more polysulfide defects, which can increase the ion storage sites in the material and improve the electrochemical performance of the material. From D-VS in FIG. 4 4 It can be seen from the TEM image that D-VS 4 The surface of the sample ball is provided with a carbon layer with the thickness of about 2nm, the carbon layer can play a certain role in inhibiting structural collapse in material circulation, and the conductivity of the material can be increased. In addition, the presence of regions of lattice disorder on the other hand evidences the presence of defects.
VS from example 1 was separately added 4 And D-VS 4 Grinding the active material serving as the positive electrode material of the zinc ion battery, conductive carbon black and PVDF according to the proportion of 7; punching Ti foil coated with active substance into positive plate with diameter of 12mm by using a punching machine, assembling a zinc ion battery by using Zn foil as negative electrode and 3M zinc trifluoromethanesulfonate as electrolyte in a battery packaging machine by selecting 2032 stainless steel battery case, and adopting VS for two types 4 And D-VS 4 The performance of the zinc ion battery as the active material of the positive electrode material of the zinc ion battery is characterized, and the results are shown in fig. 5 and fig. 6, and it can be seen from fig. 5 that D-VS is adopted 4 Zinc ion battery used as active material of positive electrode material of zinc ion battery and having specific capacity to volume ratio VS under different current densities 4 High at 10Ag -1 The current density can still reach 140mA h g -1 The specific capacity of (A). It can be seen from FIG. 6 that the D-VS is adopted 4 Zinc ion battery as active material of positive electrode material of zinc ion battery is made of 10Ag -1 The long cycle performance graph under the test condition is that after being activated by small current, the specific capacity of the long cycle performance graph reaches 139mA h g -1 The cycle time is more than 8000 cycles, and the capacity retention rate reaches 72.0 percent, which is far higher than that of VS which is not modified by glucose 4 Performance of zinc ion batteries as positive electrode material active materials for zinc ion batteries.
Example 2
Example 2 is different from example 1 in that the reaction condition in step (4) is 120 ℃ for 24h, and the rest of the process is identical.
D-VS prepared by the present example 4 As zinc ion electricityThe current density of the zinc ion battery with the active material of the battery anode material is 1 Ag -1 Under the test condition of (2), the specific capacity reaches 187mA h g -1 The cycle time is 150 cycles. At a current density of 5Ag -1 Under the test condition, the specific capacity of the catalyst can reach 132mA h g -1 The cycle time is 1000 cycles.
Example 3
Example 3 differs from example 1 in that in step (1), naVO is used as a reaction raw material 3 Substitution to Na 3 VO 4 The rest of the process is completely the same.
D-VS prepared by the present example 4 The current density of the zinc ion battery as the active material of the positive electrode material of the zinc ion battery is 1 Ag -1 Under the test condition of (2), the specific capacity of the material reaches 236mA h g -1 The cycle time is 200 cycles, and the current density is 10Ag -1 Under the test condition, the specific capacity of the catalyst reaches 170mA h g -1 The cycle time is 3000 cycles.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a vanadium sulfide zinc ion battery positive electrode material is characterized by comprising the following steps:
1) Dispersing a vanadium source and a vulcanizing agent in a solvent to obtain a first reaction liquid, carrying out solvothermal reaction on the reaction liquid, carrying out solid-liquid separation, washing and drying to obtain VS 4 ；
2) At VS 4 Adding glucose into the aqueous solution to obtain a second reaction solution, performing hydrothermal reaction, performing solid-liquid separation, washing and drying to obtain the D-VS 4 Namely the vanadium sulfide zinc ion battery anode material.
2. The method of claim 1, wherein: in the step 1), the solvent is a mixed solution of water and glycol.
3. The production method according to claim 1, characterized in that: in the step 1), the molar ratio of the vanadium source to the vulcanizing agent is 1 (1-10).
4. The production method according to claim 1, characterized in that: in the step 1), the concentration of the vanadium source in the first reaction liquid is 0.002-0.1 mol/L.
5. The production method according to claim 1, characterized in that: in the step 1), the temperature of the solvothermal reaction is 100-200 ℃, and the reaction time is 10-50 h.
6. The production method according to claim 1, characterized in that: in the step 1), the vanadium source is sodium orthovanadate or sodium metavanadate, and the vulcanizing agent is thioacetamide or thiourea.
7. The method of claim 1, wherein: in step 2), VS in the second reaction solution 4 The concentration of (b) is 0.0025-0.125 mol/L.
8. The production method according to claim 1, characterized in that: in step 2), the VS 4 The molar ratio to glucose was 1: (0.1-10).
9. The vanadium sulfide zinc ion battery positive electrode material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the positive electrode material for a vanadium sulfide zinc ion battery according to claim 9 as a positive electrode active material in a zinc ion battery.
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| CN202211427853.4A CN115744983A (en) | 2022-11-15 | 2022-11-15 | Vanadium-zinc sulfide ion battery positive electrode material and preparation method and application thereof |
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