CN111268727B - Calcium vanadate composite material and preparation method and application thereof - Google Patents
Calcium vanadate composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to a calcium vanadate composite material and a preparation method thereof, and also relates to an application of the calcium vanadate composite material. The calcium vanadate composite material is prepared from a graphene material and CaV 4 O 9 The resulting sheet-like composite; the graphene material and CaV 4 O 9 The mass ratio of (1): (35-40). The calcium vanadate composite material of the invention converts CaV 4 O 9 The graphene material is compounded with the graphene material, so that the graphene material has better conductivity and electrochemical performance. When the calcium vanadate composite material is used as a positive electrode active material of a water-based zinc ion battery, the electrochemical performance is excellent, and the calcium vanadate composite material has good cycle stability and excellent rate performance.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a calcium vanadate composite material and a preparation method thereof, and also relates to an application of the calcium vanadate composite material.
Background
Lead-acid batteries, nickel-cadmium, nickel-hydrogen and lithium ion batteries are more commonly used in the market. Lead-acid and nickel-cadmium batteries respectively contain a large amount of harmful and environmentally-polluting heavy metals of lead and cadmium; the nickel-metal hydride battery adopts expensive rare metal and has high self-discharge rate; lithium belongs to rare metal, resources are scarce, and price is high, so that the application of the lithium ion battery in a large-scale electric energy storage system is limited. Therefore, in the field of power batteries, a secondary battery system with low cost, abundant resources and environmental protection needs to be found.
At present, a water system zinc ion battery taking zinc as a negative electrode attracts people's special attention, and unlike univalent metal ions, the charge quantity carried by bivalent zinc ions in the charging and discharging process is doubled, and the power density of the battery is high. For aqueous zinc ion batteries, the positive electrode active material is a key factor that limits their development. Currently, research on positive active materials of water-based zinc ion batteries mainly focuses on vanadium-based materials and manganese-based materials, wherein the vanadium-based materials show relatively stable constant current charging electrical properties. However, the vanadium-based materials commonly used at present are mainly materials with poor conductivity such as vanadium pentoxide and vanadium disulfide, so that the electrochemical properties such as high rate performance, cycling stability and the like of the water-based zinc ion battery are poor.
Disclosure of Invention
The invention aims to provide a calcium vanadate composite material which has better conductivity and electrochemical performance.
The invention also aims to provide a preparation method of the calcium vanadate composite material.
The invention also aims to provide an application of the calcium vanadate composite material as a water-based zinc ion positive electrode active material, and the calcium vanadate composite material has better electrochemical performance when being used as the water-based zinc ion positive electrode active material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a calcium vanadate composite material is prepared from graphene material and CaV 4 O 9 Formed sheet-like composite material, the graphene material and CaV 4 O 9 The mass ratio of (1): (35-40).
CaV 4 O 9 The material has good electrochemical performance, and the graphene material has good conductivity. The calcium vanadate composite material consists of CaV 4 O 9 Is compounded with graphene material byFor CaV 4 O 9 The control of the mass ratio of the calcium vanadate to the graphene material enables the calcium vanadate composite material to have excellent electrochemical performance and conductivity. Meanwhile, the calcium vanadate composite material disclosed by the invention is of a sheet structure and is high in tap density. When the calcium vanadate composite material is used as a positive electrode active material of a water-based zinc ion battery, the water-based zinc ion battery has better electrochemical performance due to the excellent property of the calcium vanadate composite material.
Preferably, the graphene material is at least one of graphene, graphene Oxide (GO) and reduced graphene oxide.
The preparation method of the calcium vanadate composite material comprises the following steps: carrying out hydrothermal reaction on a vanadium source, a calcium source, a graphene material and glycerol in water, and then carrying out solid-liquid separation to obtain a precursor; then carrying out heat treatment on the precursor at the temperature of 300-600 ℃ in a protective atmosphere to obtain the composite material; the vanadium source is vanadium pentoxide.
The calcium vanadate composite material prepared by the preparation method provided by the invention has smaller particles and uniform particle size distribution, increases the effective reaction area of the electrode and a zinc ion inlet and outlet channel when being used as an electrode material of a water-system zinc ion battery, and reduces the polarization effect of the electrode.
In the preparation process of the present invention, caV 4 O 9 The calcium-vanadium composite material is formed by calcium element in a calcium source and a vanadium source through a hydrothermal reaction, and the glycerol plays roles in reducing 5-valent vanadium to 4-valent vanadium and controlling the appearance in the hydrothermal reaction process. In order to increase the reaction rate, it is preferred that both the calcium source and the vanadium source be present as ions in water during the hydrothermal reaction.
In order to fully contact the vanadium source and the calcium source during the hydrothermal reaction, preferably, the hydrothermal reaction of the vanadium source, the calcium source, the graphene material and glycerol in water is specifically: mixing a mixed solution A formed by a calcium source, a graphene material, glycerol and water with a mixed solution B formed by a vanadium source and hydrogen peroxide, and then carrying out hydrothermal reaction. The mixed solution A is prepared by the following method: mixing a calcium source, a graphene material, glycerol and water, then carrying out ultrasonic treatment for 0.5-1.5 hours, and then stirring for 0.5-1.5 hours. The mixed solution B is prepared by the following method: mixing a vanadium source with hydrogen peroxide and stirring for 1-3 h. The mixed solution A and the mixed solution B are mixed and then stirred for 1.5 to 2.5 hours before hydrothermal reaction so as to fully mix the two mixed solutions. Wherein the hydrogen peroxide has the function of dissolving the vanadium source.
The chemical composition of the synthesized calcium vanadate is regulated and controlled by controlling the molar ratio of vanadium to calcium in the used vanadium source and calcium source, preferably, the molar ratio of vanadium element in the vanadium source to calcium element in the calcium source is (3-5): 1.
preferably, the mass of the graphene material is 1-3% of the total mass of the vanadium source, the calcium source and the graphene material.
The calcium source is at least one of calcium chloride and calcium hydroxide.
The performance of the product is optimized by adjusting the parameters of the hydrothermal reaction, preferably, the temperature of the hydrothermal reaction is 180-220 ℃, and the time is 12-78 hours.
The heat treatment process causes the formation of CaV 4 O 9 Preferably, the heat treatment is performed by firstly keeping the temperature at 300-450 ℃ for 7-9 h and then keeping the temperature at 500-600 ℃ for 1.5-2.5 h. In the heat treatment, the atmosphere to be used is an atmosphere of nitrogen, carbon dioxide, an inert gas such as argon, or the like. The equipment used in the heat treatment can be any one of a tube furnace, a box furnace, a rotary furnace, a tunnel kiln and a roller kiln.
The technical scheme for applying the calcium vanadate composite material as the cathode material of the water-based zinc ion battery is as follows:
an application of the calcium vanadate composite material as a positive electrode active material of a water-based zinc ion battery.
When the calcium vanadate composite material is used as a positive electrode active material of a water-based zinc ion battery, the calcium vanadate composite material has high cycling stability and excellent high rate performance. At 3000mA · g -1 The current density of the zinc ion battery is higher when the charging voltage range is 0.4-1.6V, and the capacity is kept well after 5000 cycles.
Drawings
FIG. 1 is an SEM photograph of a calcium vanadate composite material according to example 1 of the invention;
FIG. 2 is an SEM photograph of a calcium vanadate composite material according to example 1 of the invention;
FIG. 3 is an SEM photograph of a calcium vanadate composite material according to example 1 of the invention;
FIG. 4 is an XRD pattern of a calcium vanadate composite material according to example 1 of the present invention;
fig. 5 is a voltage-capacity relationship curve of the first 5 cycles of the aqueous zinc-ion battery according to example 3 of the present invention;
fig. 6 is a graph of long cycle performance at a current density of 3000mA/g for water-based zinc-ion batteries of example 3 of the present invention and comparative example 2, where 1 is a plot of coulombic efficiency versus cycle number for the water-based zinc-ions of example 3; 2 is a change curve of the specific capacity of the water-based zinc ions along with the cycle times in the cycle process of the embodiment 3, and the specific capacity change of the battery during charging is coincided with the specific capacity change of the battery during discharging; and 3, a change curve of the specific capacity of the aqueous zinc ions in the circulation process along with the circulation times in the comparative example 2 is shown, and the specific capacity change of the battery in the charging process is superposed with the specific capacity change of the battery in the discharging process.
Detailed Description
The present invention will be further described with reference to the following specific examples.
1. Examples of calcium vanadate composites
Example 1
The calcium vanadate composite material of the embodiment is made of CaV 4 O 9 The sheet material formed by compounding with Graphene Oxide (GO) has a mass ratio of 38.8:1.
2. examples of the preparation of calcium vanadate composites
Example 2
This embodiment is a method for preparing a calcium vanadate composite material in embodiment 1, including the following steps:
(1) 0.0741g of Ca (OH) 2 0.01g of GO, 10mL of deionized water and 10mL of glycerol are mixed, subjected to ultrasonic treatment for 1 hour, and stirred for 1 hour to obtain a mixed solution A;
(2) Mixing 0.3679g of V 2 O 5 Is added into10mL of deionized water and 5mL of H 2 O 2 Stirring the formed mixed solution (namely hydrogen peroxide) for 2 hours at a constant temperature of 20 ℃ to obtain a mixed solution B;
(3) Mixing the mixed solution A and the mixed solution B, stirring for 2h, placing in a hydrothermal kettle, and keeping the temperature at 200 ℃ for 48h; then naturally cooling, filtering, sequentially washing the obtained solid with deionized water and ethanol, and drying to obtain a precursor;
(4) And (3) under the argon atmosphere, firstly, preserving heat for 8h at the temperature of 400 ℃, then, heating to 500 ℃, preserving heat for 2h, and then, naturally cooling to obtain the catalyst.
3. Examples of the use of calcium vanadate composite as a cathode active material for aqueous zinc-ion batteries
Example 3
In this embodiment, the calcium vanadate composite material in example 1 is used as a positive electrode active material to assemble a water-based zinc ion battery, and the specific assembly method is as follows:
the calcium vanadate composite material of example 1 was mixed with Super P (conductive carbon black), PTFE (polytetrafluoroethylene) in the following ratio of 6:3:1, adding 5mL of alcohol, stirring for 2 hours, blowing the slurry into a viscous state by cold air, uniformly pressing the material by using a spoon until the material is semi-cured, taking out the material and putting the material on a smooth glass plate, lubricating the material by using the alcohol, spreading weighing paper on the smooth glass plate, and rolling and pressing the material by using a glass rod to form a film; and drying the prepared film, pressing the film on a stainless steel net for further drying, and cutting the film to obtain the positive pole piece.
And (3) putting the positive pole piece, the glass fiber (diaphragm) and the zinc sheet (negative pole) into the shell in sequence, then dripping a zinc trifluoromethanesulfonate aqueous solution with the concentration of 3mol/L as an electrolyte, and then sealing by using a sealing machine to obtain the button cell.
4. Comparative examples section
Comparative example 1
CaV of this comparative example 4 O 9 Prepared by the method comprising the following steps:
(1) 0.0741g of Ca (OH) 2 Mixing with 10mL of deionized water and 10mL of glycerol, performing ultrasonic treatment for 1h, and stirring for 1h to obtain a mixed solution A;
(2) Will be 0.3679g of V 2 O 5 Added to a mixture of 10mL of deionized water and 5mL of H 2 O 2 Stirring the formed mixed solution (namely hydrogen peroxide) for 2 hours at the constant temperature of 20 ℃ to obtain a mixed solution B;
(3) Mixing the mixed solution A and the mixed solution B, stirring for 2h, placing in a hydrothermal kettle, and keeping the temperature at 200 ℃ for 48h; then naturally cooling, filtering, washing the obtained solid with deionized water and ethanol in sequence, and drying to obtain a precursor;
(4) And (3) under the argon atmosphere, firstly, preserving heat for 8h at the temperature of 400 ℃, then, heating to 500 ℃, preserving heat for 2h, and then, naturally cooling to obtain the catalyst.
Comparative example 2
This comparative example is the CaV of comparative example 1 4 O 9 An aqueous zinc ion battery was assembled as a positive electrode active material by the assembly method in example 3.
5. Test examples
Test example 1
SEM test was performed on the calcium vanadate composite material of example 1, and the test results are shown in fig. 1 to 3. It can be known from fig. 1 to 3 that calcium vanadate and flocculent graphene oxide are uniformly mixed and overlapped, and in the charging and discharging process, the high conductivity of the graphene oxide layer provides a channel for the rapid electron transfer for calcium vanadate and the volume change of calcium vanadate is relieved by the strong toughness. As can be seen from fig. 2 and 3, calcium vanadate has a lamellar structure, and graphene oxide has a flocculent form.
Test example 2
XRD test was performed on the calcium vanadate composite material of example 1, and the test results are shown in fig. 4. Comparing the measured XRD with a standard card (JCPDS: 01-070-4469), the calcium vanadate composite material and CaV 4 O 9 The standard card peak contrast is good, and the addition of graphene oxide does not cause CaV 4 O 9 A heterogeneous phase is generated.
Test example 3
The aqueous zinc ion battery assembled in example 3 was charged at 100mA · g -1 The current density of (2) is activated for 5 times at a charge-discharge voltage of 0.4-1.6V, and the change of the current density in the activation process is shown in FIG. 5. ByAs can be seen from FIG. 5, the capacity of the battery gradually increased during the activation process, and the maximum discharge capacity reached 345.8mAh g -1 。
After 5 activations at 3000mA g -1 The cycle performance test was performed at the current density of (2) and compared with the cycle performance of the aqueous zinc ion in comparative example 2, and the test results are shown in fig. 6. In fig. 6, curve 1 is a graph of the coulomb efficiency of the aqueous zinc ions of example 3 versus the number of cycles; the curve 2 is a change curve of the specific capacity of the water-based zinc ions along with the cycle number in the cycle process of the embodiment 3, and the specific capacity change of the battery during charging is superposed with the specific capacity change of the battery during discharging; the curve 3 is the change curve of the specific capacity of the water system zinc ions along with the cycle times in the cycle process of the comparative example 2, and the specific capacity change of the battery during charging is superposed with the specific capacity change of the battery during discharging.
As can be seen from fig. 6, the coulombic Efficiency (coulombic Efficiency) of the aqueous zinc-ion battery using the calcium vanadate composite material of the present invention as the positive electrode active material was close to 100%, and the coulombic Efficiency was stable. As can be seen from the curve 2, the water-based zinc ion battery using the calcium vanadate composite material as the positive electrode active material has higher initial specific capacity which is as high as 380 mAh.g -1 On the other hand, the specific capacity of the battery is gradually stable with the increase of the cycle number, but the specific capacity is still higher (up to 228.2 mAh.g) -1 ) The capacity is still 152.0mAh g after 5000 weeks of circulation -1 . While in a single CaV 4 O 9 The aqueous zinc ion battery using the positive electrode active material had poor battery capacity and cycle performance (curve 3).
Electrochemical performance test results further prove that the calcium vanadate composite material can be used as a positive electrode active material of a water-based zinc ion battery, and has excellent cycle stability and rate capability.
Claims (8)
1. The calcium vanadate composite material for the anode active material of the water-based zinc-ion battery is characterized by comprising a graphene material and CaV 4 O 9 Formed sheet-like composite material, the graphene material and CaV 4 O 9 The mass ratio of (1): (35-40); the calcium vanadate composite material is prepared by adopting a method comprising the following steps of: carrying out hydrothermal reaction on a vanadium source, a calcium source, a graphene material and glycerol in water, and then carrying out solid-liquid separation to obtain a precursor; then carrying out heat treatment on the precursor at the temperature of 300-600 ℃ under the protective atmosphere to obtain the material; the vanadium source is vanadium pentoxide; the heat treatment is to keep the temperature at 300-450 ℃ for 7-9 h and then keep the temperature at 500-600 ℃ for 1.5-2.5 h.
2. The calcium vanadate composite material for the positive electrode active material of the aqueous zinc-ion battery according to claim 1, wherein the graphene material is at least one of graphene, graphene oxide, and reduced graphene oxide.
3. A method for preparing a calcium vanadate composite material according to claim 1 or 2, comprising the steps of: carrying out hydrothermal reaction on a vanadium source, a calcium source, a graphene material and glycerol in water, and then carrying out solid-liquid separation to obtain a precursor; then carrying out heat treatment on the precursor at the temperature of 300-600 ℃ under the protective atmosphere to obtain the material; the vanadium source is vanadium pentoxide; the heat treatment is to preserve heat for 7 to 9 hours at the temperature of 300 to 450 ℃ and then preserve heat for 1.5 to 2.5 hours at the temperature of 500 to 600 ℃.
4. The method for preparing the calcium vanadate composite material according to claim 3, wherein the molar ratio of the vanadium element in the vanadium source to the calcium element in the calcium source is (3-5): 1.
5. the preparation method of the calcium vanadate composite material according to claim 3, wherein the mass of the graphene material is 1-3% of the total mass of the vanadium source, the calcium source and the graphene material.
6. The method for preparing a calcium vanadate composite according to any one of claims 3 to 5, wherein the calcium source is at least one of calcium chloride and calcium hydroxide.
7. The method for preparing a calcium vanadate composite material according to any one of claims 3 to 5, wherein the temperature of the hydrothermal reaction is 180 to 220 ℃ and the time is 12 to 78 hours.
8. Use of a calcium vanadate composite material as defined in claim 1 or 2 as an active material for a positive electrode of an aqueous zinc ion battery.
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| CN112038606A (en) * | 2020-09-09 | 2020-12-04 | 吉林师范大学 | Preparation method of polydopamine-derived carbon-coated calcium vanadate nanosheet composite material |
| CN112374537A (en) * | 2020-11-02 | 2021-02-19 | 四川大学 | Preparation method of metal vanadate nano composite material |
| CN113277557B (en) * | 2021-05-14 | 2023-10-24 | 宁德新能源科技有限公司 | Amorphous calcium vanadate, preparation method thereof, battery cathode and battery |
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| CN103285851A (en) * | 2013-06-26 | 2013-09-11 | 青岛农业大学 | Graphene and vanadate composite nano-fiber photocatalyst and preparation method thereof |
| EP2755259A1 (en) * | 2013-01-10 | 2014-07-16 | Belenos Clean Power Holding AG | Self-assembled composite of graphene oxide and H4V3O8 |
| CN106784777A (en) * | 2017-02-20 | 2017-05-31 | 武汉理工大学 | Alkaline earth metal vanadate electrode material and its preparation method and application |
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| EP2755259A1 (en) * | 2013-01-10 | 2014-07-16 | Belenos Clean Power Holding AG | Self-assembled composite of graphene oxide and H4V3O8 |
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