CN112062160B - Preparation method and application of positive electrode material of zinc iron vanadate ion battery - Google Patents
Preparation method and application of positive electrode material of zinc iron vanadate ion battery Download PDFInfo
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- CN112062160B CN112062160B CN202010850131.4A CN202010850131A CN112062160B CN 112062160 B CN112062160 B CN 112062160B CN 202010850131 A CN202010850131 A CN 202010850131A CN 112062160 B CN112062160 B CN 112062160B
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention relates to a zinc ion battery technologyField of view to solve commercial V2O5The problem of poor cycle stability of the zinc-ion-like battery is solved, and the preparation method of the positive electrode material of the zinc-ion battery with the ferric vanadate comprises the following steps: adding a vanadium source, an iron source and a surfactant into a hydrogen peroxide solution, uniformly mixing to obtain a reaction solution, and carrying out hydrothermal reaction on the reaction solution to obtain the positive electrode material of the zinc-iron vanadate ion battery. The prepared ferric vanadate material has uniform size, stable structure and excellent zinc ion battery performance, can be used as a zinc ion battery anode material, has high rate performance, high specific capacity and excellent cycling stability, and has the current density of 1A g‑1Under the test condition, the specific capacity of the material reaches 220mAh g‑1The cycle time is 300 cycles.
Description
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a preparation method and application of a positive electrode material of a zinc ion battery containing ferric vanadate.
Background
With the increasing global demand for clean energy, there is a great deal of interest in developing high-safety, low-cost, high-performance batteries. The lithium ion battery is a main electrochemical energy storage device at present, and has been widely applied to the fields of portable electronic equipment, new energy automobiles and the like, but the lithium ion battery still has the problems of lithium resource shortage, high cost, unsafe organic electrolyte and the like, and the application of the lithium ion battery in the fields of high-safety low-cost wearable electronics and large-scale energy storage is greatly limited. In recent years, a water-based zinc ion battery has the advantages of abundant zinc resources, low cost, high safety of a water-based electrolyte, environmental friendliness and the like, and is a very important high-safety non-lithium electrochemical energy storage device. The development of low-cost and high-capacity cathode materials is always a difficult point in the research field of zinc ion batteries.
The vanadium-based material has the characteristics of a multivalent ion reaction mechanism and high capacity, and is widely considered as a very promising positive electrode material, but the vanadium-based bulk material has the problems of few active sites, poor ion-electron conductivity, slight water solubility, volume expansion in the charging and discharging processes and the like, so that the vanadium-based bulk material has short cycle life and capacity is difficult to exert. Therefore, the development of a vanadium-based positive electrode material with high capacity, high rate and long service life is urgently needed to meet the application requirements of the zinc ion battery.
Disclosure of Invention
The invention aims to overcome the commercial V2O5The problem of poor cycle stability of the zinc-ion-like battery is solved, and the preparation method of the positive electrode material of the zinc-ion battery with uniform size, stable structure and good cycle performance is provided.
The invention also provides an application of the positive electrode material of the zinc ion battery of ferric vanadate prepared by the method in the zinc ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a positive electrode material of a zinc iron vanadate ion battery is characterized by comprising the following steps: adding a vanadium source, an iron source and a surfactant into a hydrogen peroxide solution, uniformly mixing to obtain a reaction solution, and carrying out hydrothermal reaction on the reaction solution to obtain the positive electrode material of the zinc-iron vanadate ion battery.
Preferably, the vanadium source is selected from V2O5Or NH4VO3。
Preferably, the iron source is selected from Fe (NO)3)3 9H2O or FeCl3。
Preferably, the surfactant is selected from polyvinylpyrrolidone (PVP) or dodecyltrimethylammonium bromide (DTAB).
Preferably, the concentration of the hydrogen peroxide solution is 0.01-10 mol/L. .
Preferably, the feeding molar ratio of the iron salt to the vanadium source is 1: (1-50).
Preferably, the concentration of the surfactant in the reaction solution is 1-15 g/L.
Preferably, the concentration of the vanadium source in the reaction liquid is 0.01-0.1 mol/L.
Preferably, the concentration of the iron source in the reaction solution is 0.001 to 0.01 mol/L.
Preferably, the temperature of the hydrothermal reaction is 100-200 ℃ and the time is 10-30 h.
The application of the positive electrode material of the zinc ion battery containing ferric vanadate prepared by the method in the zinc ion battery is provided.
Therefore, the invention has the following beneficial effects:
(1) the preparation process is simple, the method is universal, no special requirements are required on equipment, and large-scale industrial production can be realized;
(2) the ferric vanadate material prepared by the method has uniform size, stable structure and excellent zinc ion battery performance;
(3) the ferric vanadate material can be applied as a zinc ion battery anode material, and the prepared zinc ion battery has high rate performance, high specific capacity and excellent cycling stability, and has the current density of 1A g-1Under the test condition, the specific capacity of the material reaches 220mAh g-1The cycle time is 300 cycles.
Drawings
FIG. 1 is an SEM photograph of the ferric vanadate material prepared in example 1 at different magnifications.
FIG. 2 is an XRD pattern of the iron vanadate material prepared in example 1.
Fig. 3 is a graph showing the cycle performance of a zinc ion battery using the iron vanadate material prepared in example 1.
Fig. 4 is a graph of the cycling performance of zinc ion batteries made with the iron vanadate material made in example 1 under different current density test conditions.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Take 4mlH2O2Adding into 40ml deionized water, weighing 2mmol of V2O5(0.364 g) was added to the above solution, stirred in a water bath (300 rpm) at 40 ℃ until dissolved, and then 0.2mmol of Fe (NO) was weighed3)3 9H2O (0.0808 g) was added thereto, followed by stirring for five minutes, then 0.5g PVP was added, and magnetic stirring was continued for 30 min;
(2) the mixed solution is transferred to a 50ml reaction kettle and reacted for 12 hours at the temperature of 180 ℃. After the reaction is finished, taking out the product, centrifugally washing for three times, wherein the washing solvent is deionized water, and placing the washed product in a vacuum oven at 60 ℃ for 12 hours to obtain an iron vanadate material; SEM images of the ferric vanadate material with different magnifications are shown in figure 1; the XRD pattern of the ferric vanadate material is shown in figure 2; as can be seen in connection with FIGS. 1 (a-b): the particle size of the ferric vanadate material is 2 μm, and Fe is obviously shown by XRD of figure 25V15O39(OH)9 9H2Characteristic peak of O, indicating that the sample is Fe5V15O39(OH)9 9H2O；
(3) Taking the ferric vanadate material as an active substance of a zinc ion battery positive electrode material, and mixing the ferric vanadate material with carbon black and PVDF according to the weight ratio of 8: 1: 1, adding NMP as a solvent, grinding for 30min, then blade-coating the Ti foil by using a scraper, and drying in a vacuum oven at 60 ℃;
(4) the Ti foil coated with the active material was punched into a positive plate having a diameter of 12mm by using a punch, and a Zn foil was used as a negative electrode to assemble a zinc ion battery.
The samples in this example were selected for characterization and analysis, and the results are shown in fig. 3 and 4, and the prepared zinc ion battery has high specific capacity and excellent cycling stability, and has a current density of 1A g-1Under the test condition, the specific capacity of the material reaches 220mAh g-1The cycle time reaches 300 cycles, and the capacity retention rate is 98 percent; the rate capability test shows that the current density is from low to highAfter the current density test, the current density returns to 0.2A g-1Can still reach 320mAh g under low current density-1The specific capacity of the vanadium oxide shows that the ferric vanadate material has good rate capability.
Example 2
(1) Take 1mlH2O2Adding into 40ml deionized water, weighing 04mmol NH4VO3Added to the above solution, stirred in a water bath (300 rpm) at 40 ℃ until dissolved, and 0.04mmol FeCl was weighed3Adding the PVP into the mixture, adding 0.04g of PVP after stirring for five minutes, and continuing to stir for 30min by magnetic force;
(2) the mixed solution is transferred to a 50ml reaction kettle and reacted for 10 hours at the temperature of 100 ℃. After the reaction is finished, taking out the product, centrifugally washing for three times, wherein the washing solvent is deionized water, and placing the washed product in a vacuum oven at 60 ℃ for 12 hours to obtain an iron vanadate material;
(3) taking the ferric vanadate material as an active substance of a zinc ion battery positive electrode material, and mixing the ferric vanadate material with carbon black and PVDF according to the weight ratio of 8: 1: 1, adding NMP as a solvent, grinding for 30min, then blade-coating the Ti foil by using a scraper, and drying in a vacuum oven at 60 ℃;
(4) the Ti foil coated with the active material was punched into a positive plate having a diameter of 12mm by using a punch, and a Zn foil was used as a negative electrode to assemble a zinc ion battery.
The prepared zinc ion battery has the current density of 1A g-1Under the test condition, the specific capacity of the nano-silver particles reaches 100mAh g-1The cycle time reaches 150 cycles, and the capacity retention rate is 90%.
Example 3
(1) Take 10mlH2O2Adding into 40ml deionized water, weighing 4mmol NH4VO3Added to the above solution, stirred in a water bath (300 rpm) at 40 ℃ until dissolved, and 0.4mmol FeCl was weighed3Adding the mixture, stirring for five minutes, adding 0.6g of DTAB, and continuing to stir for 30min by magnetic force;
(2) the mixed solution is transferred to a 50ml reaction kettle and reacted for 30 hours at the temperature of 200 ℃. After the reaction is finished, taking out the product, centrifugally washing for three times, wherein the washing solvent is deionized water, and placing the washed product in a vacuum oven at 60 ℃ for 12 hours to obtain an iron vanadate material;
(3) taking the ferric vanadate material as an active substance of a zinc ion battery positive electrode material, and mixing the ferric vanadate material with carbon black and PVDF according to the weight ratio of 8: 1: 1, adding NMP as a solvent, grinding for 30min, then blade-coating the Ti foil by using a scraper, and drying in a vacuum oven at 60 ℃;
(4) the Ti foil coated with the active material was punched into a positive plate having a diameter of 12mm by using a punch, and a Zn foil was used as a negative electrode to assemble a zinc ion battery.
The prepared zinc ion battery has the current density of 1A g-1Under the test condition, the specific capacity of the material reaches 150mAh g-1The cycle time reaches 200 cycles, and the capacity retention rate is 91 percent.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (5)
1. A preparation method of a positive electrode material of a zinc iron vanadate ion battery is characterized by comprising the following steps: adding a vanadium source, an iron source and a surfactant into a hydrogen peroxide solution, uniformly mixing to obtain a reaction solution, and carrying out hydrothermal reaction on the reaction solution to obtain an iron-zinc vanadate ion battery anode material;
the vanadium source is selected from V2O5Or NH4VO3；
The iron source is selected from Fe (NO)3)3 9H2O or FeCl3；
The surfactant is selected from polyvinylpyrrolidone or dodecyl trimethyl ammonium bromide;
the feeding molar ratio of the ferric salt to the vanadium source is 1: (1-50);
the temperature of the hydrothermal reaction is 100-200 ℃, and the time is 10-30 h.
2. The method for preparing the positive electrode material of the zinc iron vanadate ion battery according to claim 1, wherein the concentration of the hydrogen peroxide solution is 0.01-10 mol/L.
3. The method for preparing the positive electrode material of the zinc iron vanadate ion battery according to claim 1, wherein the concentration of the surfactant in the reaction solution is 1-15 g/L.
4. The method for preparing the positive electrode material of the zinc iron vanadate ion battery according to claim 1, wherein the concentration of a vanadium source in the reaction solution is 0.01-0.1 mol/L; the concentration of the iron source in the reaction liquid is 0.001-0.01 mol/L.
5. The application of the positive electrode material of the zinc ion battery with ferric vanadate prepared by the preparation method according to any one of claims 1 to 4 in the zinc ion battery.
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| CN113054152A (en) * | 2021-02-05 | 2021-06-29 | 中国地质大学（武汉） | 3D printing zinc ion battery positive electrode and preparation method thereof |
| CN113611846B (en) * | 2021-07-29 | 2023-04-18 | 中汽创智科技有限公司 | Electrode material of lithium battery and preparation method and application thereof |
| CN114538521B (en) * | 2022-01-14 | 2023-10-13 | 福州大学 | Potassium-doped oxygen vacancy manganese dioxide positive electrode material and preparation method and application thereof |
| CN114464764B (en) * | 2022-02-22 | 2024-03-19 | 中南大学 | Preparation method and application of polyaniline-coated ferric vanadate flexible electrode |
| CN115010943A (en) * | 2022-06-10 | 2022-09-06 | 中山大学 | Novel vanadium-oxygen coordination supermolecule cathode material and preparation method and application thereof |
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| CN104766975B (en) * | 2015-04-15 | 2017-04-12 | 深圳市德睿新能源科技有限公司 | Method for preparing ferric vanadate-graphene negative electrode composite material |
| CN110474044B (en) * | 2019-09-05 | 2021-07-16 | 山东大学 | High-performance water-based zinc ion battery positive electrode material and preparation method and application thereof |
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