CN113428897A - Preparation method of vanadium-based cathode material based on surface modification for enhancing cycle stability - Google Patents
Preparation method of vanadium-based cathode material based on surface modification for enhancing cycle stability Download PDFInfo
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Abstract
The invention provides a preparation method of a vanadium-based cathode material based on surface modification enhanced circulation stability, which comprises the steps of using formic acid to acidify a vanadium source dissolved in deionized water to obtain a first mixed solution, adding a cobalt source and lithium hydroxide into the first mixed solution, stirring to obtain a second mixed solution, transferring the second mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction to obtain a flocculent solid product; placing the flocculent solid product in a specific gas in a flowing state, and standing at a certain temperature to obtain a surface-modified vanadium-based cathode material; the vanadium source is vanadate containing ammonium ions, and the cobalt source is acid salt containing cobalt ions. According to the invention, vanadate with ammonium ions is used as a vanadium source, cobalt ions in acid salt are used as intercalation metal ions, and the battery has ultrahigh mass specific capacity when a zinc metal is used as a negative electrode material for assembling a half battery, so that the charge-discharge cycle performance of the battery can be obviously improved after low-temperature annealing in a specific gas environment.
Description
Technical Field
The invention belongs to the technical field of preparation of positive electrode materials of zinc ion batteries, and particularly relates to a preparation method of a vanadium-based positive electrode material based on surface modification for enhancing cycle stability.
Background
With the rapid development of the industrial revolution, the importance of electric energy in the contemporary society is increasingly prominent, and in the process of continuous development of electric energy, the research of energy storage equipment is also increasingly important. In the past decades, lithium ion batteries have been widely used in mobile energy storage devices due to their high theoretical specific capacity and good cycle life. However, as electric vehicles and wearable battery devices develop, the problem of lithium resource shortage is becoming more and more obvious, and meanwhile, the safety problem of lithium ion batteries is also very challenging due to the problems of the use of organic electrolytes and lithium dendrites and the like. The water system zinc ion battery is an ideal substitute of the lithium ion battery due to low cost, high volume specific capacity and high safety.
However, the use of the zinc ion battery still faces the problems of less cycle times, low specific mass capacity, low discharge voltage platform and the like, and the problems are mainly caused by the positive electrode material of the zinc ion battery, so the research on the positive electrode material is the key to the success of the zinc ion battery.
At present, the positive electrode material of the zinc ion battery mainly comprises a manganese-based material, a vanadium-based material, a Prussian blue analogue and the like. Among them, vanadium-based materials are of great interest because of their high theoretical specific capacity (about 550mAh/g), abundant chemical valence (+3, +4, +5), and good cycling stability. Due to the chemical bond composition of vanadium, various layered oxides can be synthesized, and the layered oxides have obvious advantages in combination of rapid de-intercalation of zinc ions and redox sites, leading to extensive research.
However, since the strong electrostatic force of zinc ions exists in the form of hydrated ions in the aqueous electrolyte, a larger interlayer distance is required for the insertion of large-sized hydrated zinc ions in the layered structure during the charge and discharge processes, and because the layers of the layered material are connected by van der waals force, the continuous de-intercalation of the hydrated zinc ions destroys the layered structure, thereby destroying the cycling stability of the battery and causing the capacity attenuation of the battery. Therefore, constructing a more stable layered structure is an endeavor goal of many researchers.
Disclosure of Invention
The invention aims to provide a method for preparing a vanadium-based cathode material based on surface modification enhanced cycle stability, which aims to overcome the defects of the prior art, takes vanadate with ammonium ions as a vanadium source, takes cobalt ions in acid salt as intercalation metal ions, has ultrahigh specific mass capacity when a zinc metal is taken as a cathode material to assemble a half battery, and can obviously improve the charge-discharge cycle performance of the battery after low-temperature annealing in a specific gas environment.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a vanadium-based cathode material based on surface modification for enhancing cycle stability comprises the following steps:
acidifying a vanadium source dissolved in deionized water by using formic acid to obtain a first mixed solution, adding a cobalt source and lithium hydroxide into the first mixed solution, stirring to obtain a second mixed solution, and transferring the second mixed solution into a high-pressure reaction kettle to perform hydrothermal reaction to obtain a flocculent solid product;
centrifugally collecting and drying the flocculent solid product, placing the flocculent solid product in a specific gas in a flowing state, and standing for a period of time at a certain temperature to obtain a surface-modified vanadium-based cathode material;
the vanadium source is vanadate containing ammonium ions, and the cobalt source is acid salt containing cobalt ions.
Preferably, the vanadium source is ammonium metavanadate or ammonium vanadate.
Preferably, the cobalt source is cobalt nitrate.
Preferably, the mass ratio of the vanadium source to formic acid is (3.5-4): 1.
preferably, the molar ratio of the vanadium source to the cobalt source is (0.2-0.4): 1.
preferably, the mass ratio of the cobalt source to the sodium lithium hydroxide is (3-4): 1.
preferably, the temperature of the hydrothermal reaction is 180-200 ℃, and the reaction time is 12-24 h.
Preferably, the gas is at least one of nitrogen, carbon dioxide, hydrogen, argon, oxygen.
Preferably, the flow rate of the gas is 30-50 mL/min.
Preferably, the temperature is 200-300 ℃, and the standing time is 3-5 h.
Preferably, the conditions of centrifugation and drying of the flocculent solid product are: centrifuging at 8000rpm for 3-5 min, and drying at 70 deg.C in air.
The invention has the beneficial effects that:
1. according to the surface-modified vanadium-based positive electrode material, vanadate containing ammonium ions is used as a vanadium source, cobalt ions in acid salt are used as intercalation ions, the pH value of a solution is changed through formic acid to reach a proper pH value, vanadium oxide with a layered nano-belt structure is hydrothermally synthesized, and then the surface of the material is treated at a low temperature of 200-300 ℃ under the condition of pure gas to obtain the surface-modified vanadium-based positive electrode material. In the material, the layered vanadium oxide is a main material structure, ammonium ions and cobalt ions play a role in connecting a framework between the layered structures, the spacing of the layered structures can be expanded, and the layered structures are fixed in a molecular bond combination mode, the large spacing relieves the structural damage caused by material deformation when zinc ions are de-intercalated, simultaneously reduces the energy required by zinc ion de-intercalation, provides conditions for the rapid de-intercalation of the zinc ions, and cobalt ions with rich valence state also play a certain contribution role in the charge-discharge cycle process of the battery; the further treatment of the inert gas at low temperature can increase oxygen vacancies in the material and reduce crystal water in the material, thereby reducing the structural instability caused by the falling of the crystal water in the circulation process, further enhancing the structural stability of the surface of the material, ensuring that the structure is not damaged in the repeated charging and discharging process, enhancing the molecular bond energy of the crystal face of the material (111) by the low-temperature annealing treatment of the inert gas, and further improving the damage resistance of the layer structure. Based on water-based electrolyte, when the material is applied to a zinc ion battery, the material has excellent specific capacity, high cycle stability and higher energy density than common vanadium-based materials and other manganese-based materials.
2. The preparation method provided by the invention is easy to operate, the experimental limit condition is loose, the repeatability is high, the cost is low, the environment is not polluted, and the prepared surface-modified layered doped nanobelt structure vanadium-based material has higher specific mass capacity and good cycling stability; after the surface modification treatment, the cycle stability of the original material is greatly improved, and a method guide is provided for the research of other materials.
Drawings
FIG. 1a is an SEM image of a material obtained by a comparative example of the present invention.
FIG. 1b is an SEM image of the material obtained in example 1 of the present invention.
FIG. 1c is a TEM image of a material obtained by comparative example of the present invention.
FIG. 1d is a TEM image of the material obtained in example 1 of the present invention.
FIG. 1e is a high resolution TEM image of the material obtained in the comparative example of the present invention.
FIG. 1f is a high resolution TEM image of the material obtained in example 1 of the present invention.
Figure 2a is an XRD pattern of the material obtained in example 1 of the present invention and comparative example.
FIG. 2b is a Raman test chart of the materials obtained in example 1 of the present invention and comparative example.
FIG. 3a is a graph of the cycle of the magnification of the material obtained in example 1 of the present invention.
FIG. 3b is a graph showing the charge and discharge cycles of the materials obtained in example 1 of the present invention and comparative example.
FIG. 3c is a charge-discharge graph of a charge-discharge test of the material obtained in the comparative example of the present invention.
FIG. 3d is a charge-discharge curve of the charge-discharge test of the material obtained in example 1 of the present invention.
FIG. 4 is a graph showing the charge-discharge cycle test of equal current for the materials obtained in comparative examples 1 to 3 of the present invention.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways.
The invention provides a preparation method of a vanadium-based cathode material based on surface modification enhanced circulation stability, which comprises the following steps of firstly, preparing a high-capacity ion intercalation layered nano-belt structure material by taking vanadate containing ammonium ions as a vanadium source and cobalt ions in acid salt as intercalation ions through hydrothermal reaction, providing a more smooth ion channel for embedding and removing zinc ions, and enabling the cobalt ions and the ammonium ions to jointly play a role of a layered structure supporting framework so as to improve the stability of the layered structure; and then the treatment is carried out, and the low-temperature treatment under a specific atmosphere can strengthen the molecular bond on the surface of the material and stabilize the structure of the material.
In a specific embodiment, a vanadium source dissolved in deionized water is acidified by formic acid to obtain a first mixed solution, a cobalt source and lithium hydroxide are added into the first mixed solution, a second mixed solution is obtained by stirring, and the second mixed solution is transferred into a high-pressure reaction kettle to carry out hydrothermal reaction to obtain a flocculent solid product;
centrifugally collecting and drying the flocculent solid product, placing the flocculent solid product in a specific gas in a flowing state, and standing for a period of time at a certain temperature to obtain a surface-modified vanadium-based cathode material;
the vanadium source is vanadate containing ammonium ions, and the cobalt source is acid salt containing cobalt ions.
In a preferred embodiment, the vanadium source is ammonium metavanadate or ammonium vanadate, and the cobalt source is cobalt nitrate.
In another preferred embodiment, the mass ratio of the vanadium source to the formic acid is (3.5-4): 1.
the mass ratio of the cobalt source to the sodium hydroxide lithium is (3-4): 1.
in a more specific embodiment, the temperature of the hydrothermal reaction is 180-200 ℃, and the reaction time is 12-24 hours.
In other preferred embodiments, the gas is at least one of nitrogen, carbon dioxide, hydrogen, argon, and oxygen.
In a more specific embodiment, the flow rate of the gas is 30 to 50mL/min,
in another specific embodiment, the temperature is 200-300 ℃, and the standing time is 3-5 hours.
Preferably, the conditions of centrifugation and drying of the flocculent solid product are: centrifuging at 8000rpm for 3-5 min, and drying at 70 deg.C in air.
The above preparation process and the surface-modified vanadium-based cathode material are further described below with reference to specific examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents, and the like used in the following embodiments are commercially available unless otherwise specified.
[ example 1 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in nitrogen atmosphere-1And (3) raising the temperature to 300 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 2 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in nitrogen atmosphere-1And (3) raising the temperature to 300 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 3 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
370mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, stirred for ten minutes, then 1.2mL of formic acid is added, and stirring is continued for one hour to enable full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in nitrogen atmosphere-1And (3) raising the temperature to 300 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 4 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
185mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to fully react and uniformly disperse to obtain a solution B.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in nitrogen atmosphere-1And (3) raising the temperature to 300 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030. Examples 2-4 were tested under different concentrations of formic acid and cobalt nitrate, with other reaction conditions being unchanged.
[ example 5 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in nitrogen atmosphere-1And (3) raising the temperature to 200 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 6 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
In oxygen atmosphere at 5 deg.C for min-1And (3) raising the temperature to 200 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 7 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in carbon dioxide gas environment-1And (3) raising the temperature to 200 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 8 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
Under argon atmosphere at 5 deg.C for min-1And (3) raising the temperature to 200 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 9 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
In a mixed gas of hydrogen and argon (1: 4 gas concentration ratio) environment at 5 deg.C for min-1And (3) raising the temperature to 200 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ example 10 ]
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
At 5 deg.C for min in air environment-1And (3) raising the temperature to 200 ℃, keeping the gas flow rate at 30mL/min for 3h, and collecting a sample when the tubular furnace is cooled to room temperature to obtain the surface-modified layered vanadium-based nanobelt material.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
Comparative example 1
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
555mg of cobalt nitrate hexahydrate is dissolved in 64mL of deionized water, 1.2mL of formic acid is added after stirring for ten minutes, and stirring is continued for one hour to ensure full reaction and uniform dispersion, so that a solution B is obtained.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
Comparative example 2
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
130mg of ferric chloride is dissolved in 64mL of deionized water, stirred for ten minutes, then 1.2mL of formic acid is added, and stirring is continued for one hour to fully react and uniformly disperse to obtain a solution B.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
Comparative example 3
296mg of ammonium metavanadate was dissolved in 64mL of deionized water, and the solution was heated in a water bath at 50 ℃ for 30min to promote dissolution. After stirring was continued for 30 minutes, 120mg of lithium hydroxide was added and stirred for one hour to be sufficiently dissolved, to obtain a mixed solution A.
390mg of nickel chloride is dissolved in 64mL of deionized water, stirred for ten minutes, added with 1.2mL of formic acid, and stirred for one hour to ensure full reaction and uniform dispersion, thus obtaining a solution B.
And pouring the solution B into the solution A, and continuing stirring for 1h to fully react. Then pouring the obtained solution into a tetrafluoroethylene hydrothermal reaction kettle, sealing and screwing the solution by using a stainless steel metal shell, and carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃.
Washing and centrifuging the product obtained by the hydrothermal reaction for three times, wherein the centrifugation condition is 8000r/min, and keeping for 3 min. The product was dried at 70 ℃ overnight.
Fully grinding the materials, uniformly mixing PVDF, commercial acetylene black and the preparation materials according to the proportion of 1:2:7, adding an organic solvent NMP to prepare a viscous honey shape, uniformly coating the viscous honey shape on carbon paper by a blade coating method by using a coating machine of Kejing company, drying at 70 ℃ overnight, compacting under 20MPa, and preparing the zinc ion battery by using a battery case of type 2030.
[ TEST ]
In the samples tested below, the material of example 1 was the material after the low-temperature surface treatment, and the material of comparative example 1 was the material before the low-temperature surface treatment.
1. Topography testing
The surface microtopography was tested by scanning tunneling electron microscopy (SEM).
As shown in fig. 1, fig. 1a and 1b are SEM images of the material before and after the low temperature surface treatment, respectively. FIGS. 1c and 1d are TEM topography before and after low temperature surface treatment, respectively. It can be seen from the figure that the nanobelt material prepared by the hydrothermal reaction and the material after the low-temperature annealing treatment of the gas have no obvious difference in the morphology characterization of the SEM and the TEM. Based on the optimal material selection and the optimal addition proportion of the process, the material has extremely elongated nanostructure structure, is a good choice for preparing the self-supporting electrode material, can be very easily filtered to form a film under the vacuum filtration condition through testing, and has higher flexibility and toughness after freeze drying.
Fig. 1e and 1f are high resolution TEM images of the material before and after low temperature surface treatment, respectively. The material surface before gas treatment has obvious gray pits, which are the damages to the material surface caused by the irradiation of high-energy electron beams in the TEM shooting process, and the treated nanobelt material surface is smooth, which indicates that the material is less damaged by the test conditions. This indicates that the low temperature annealing treatment has a beneficial effect on the lattice stability of the material surface, providing a guarantee for the stability of the material in the long-cycle process.
2. XRD test
X-ray photoelectron Spectroscopy (XPS) A sample was analyzed for elements and their contents by a Thermo Scientific ESCALAB 250Xi model X-ray photoelectron spectrometer, USA.
FIG. 2a is a comparison card of XRD pdf of the materials before and after low temperature surface treatment, and it can be seen that the main diffraction peaks of the XRD patterns of the materials before and after treatment are not changed. Fig. 2b is a raman test chart of the material before and after the low temperature surface treatment, and it can also be seen that there is no peak shift before and after the treatment. The low-temperature surface modification process does not change the properties of the material, the redox process in the circulating process does not change fundamentally, the capacity of the anode material is slightly influenced (about ten percent), and the charge-discharge platform does not change, so that the method only plays a role in structural stability, and no new substance or new phase is generated in the implementation process.
3. Stability test
The capacitance performance of the two-electrode system was tested using a Korotkoff electrochemical workstation. In the two-electrode system, zinc metal is used as a negative electrode, a glass fiber membrane is used as a diaphragm, and three 2M zinc methane sulfonate aqueous solutions are used as electrolyte. The current density of the charge and discharge test is set to 0.5-20A g-1And the voltage range is 0.3-1.7V.
Fig. 3a is a magnification cycle chart of the material after the surface treatment, fig. 3b is a charge-discharge cycle chart before and after the low-temperature surface treatment, and it can be seen from the chart that the cycle stability of the material after the surface modification treatment is far better than that of the untreated material when the material is tested under the current density of 5A/g. The ion diffusion rate is an important index of the rate performance of the reactive ion battery, and is the direct reflection of the de-intercalation rate and the easiness of zinc ions among materials, tests of a constant current intermittent titration method can find that the ion diffusion rate of the materials subjected to surface treatment in circulation is slightly lower than that of the materials before treatment, but the ion diffusion rate is integrally higher than or equal to that of the same materials, the high-speed de-intercalation of ions at a high-pressure part is inhibited, the higher the ion de-intercalation rate is, the higher the destructiveness to a layered structure is, the inhibition can reduce the damage to the materials in the charge-discharge process, the ion diffusion rate is kept stable in the whole charge-discharge process, and the stability of the material structure can be further protected through the surface treatment.
Fig. 3c and 3d are charge and discharge curves of charge and discharge tests before and after surface treatment, respectively, and it can be seen that the material after multiple cycles is still capable of maintaining stable charge and discharge platforms, which are the reflection of ion deintercalation and electrochemical reaction, indicating the cycle process of the material, the coincidence of the charge and discharge platforms proves the good reversibility of the material, and the retention of the voltage platform after multiple charges and discharges proves the stability of the structure, without the structure being damaged in the process of repeated charges.
The material obtained by the comparative examples 1-3 is subjected to the equal current charge-discharge cycle test, and the test results are shown in fig. 4, it can be seen that the specific capacity of the material doped with cobalt ions is obviously higher than that of the other two ions when the material is subjected to the equal current charge-discharge cycle test, but the stability of the material of the invention (the comparative example 1 is the material of the invention which is not subjected to the surface treatment) is not better than that of the comparative examples 2 and 3 under the condition of not being subjected to the surface treatment, which is probably because the material structures of the comparative examples 2 and 3 have too small interlayer spacing, zinc ions are difficult to embed at all, and only ion exchange can be carried out on the outer surface, so the material is not damaged, the stability is good, but the capacity is lower.
Therefore, in combination with the above test on the material of example 1, it can be proved that the material structure of the present invention has a larger interval, which can relieve the structural damage caused by the material deformation when the zinc ions are deintercalated, and at the same time, reduce the energy required for deintercalation of the zinc ions, and provide conditions for the rapid deintercalation of the zinc ions, which is the effect brought by the ammonium ions and the cobalt ions playing a role of connecting the skeleton between the layered structures, and being capable of opening the interval of the layered structure and fixing the layered structure in a form of molecular bond.
It can also be seen that the cycling stability of the cobalt ion intercalated material is slightly poor without gas surface treatment, which may be that the larger interlayer spacing and the multiple valence states have some effect on the structural stability when combined with zinc ions.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (11)
1. A preparation method of a vanadium-based cathode material based on surface modification for enhancing cycle stability is characterized by comprising the following steps:
acidifying a vanadium source dissolved in deionized water by using formic acid to obtain a first mixed solution, adding a cobalt source and lithium hydroxide into the first mixed solution, stirring to obtain a second mixed solution, and transferring the second mixed solution into a high-pressure reaction kettle to perform hydrothermal reaction to obtain a flocculent solid product;
centrifugally collecting and drying the flocculent solid product, placing the flocculent solid product in a specific gas in a flowing state, and standing for a period of time at a certain temperature to obtain a surface-modified vanadium-based cathode material;
the vanadium source is vanadate containing ammonium ions, and the cobalt source is acid salt containing cobalt ions.
2. The method for preparing the vanadium-based cathode material with enhanced cycling stability based on surface modification according to claim 1, wherein the vanadium source is ammonium metavanadate or ammonium vanadate.
3. The method for preparing the vanadium-based cathode material with the enhanced cycling stability based on the surface modification as claimed in claim 2, wherein the cobalt source is cobalt nitrate.
4. The preparation method of the vanadium-based cathode material based on surface modification for enhancing cycle stability according to claim 1 or 2, wherein the mass ratio of the vanadium source to formic acid is (3.5-4): 1.
5. the preparation method of the vanadium-based cathode material based on surface modification for enhancing cycle stability according to claim 1 or 3, wherein the molar ratio of the vanadium source to the cobalt source is (0.2-0.4): 1.
6. the preparation method of the vanadium-based cathode material based on surface modification for enhancing cycle stability according to claim 1 or 3, wherein the mass ratio of the cobalt source to the sodium lithium hydroxide is (3-4): 1.
7. the preparation method of the vanadium-based positive electrode material based on surface modification for enhancing cycle stability according to claim 1, wherein the hydrothermal reaction temperature is 180-200 ℃ and the reaction time is 12-24 h.
8. The method for preparing the vanadium-based cathode material with the surface modification-based enhanced cycling stability according to claim 1, wherein the gas is at least one of nitrogen, carbon dioxide, hydrogen, argon and oxygen.
9. The method for preparing the vanadium-based cathode material with the enhanced cycling stability based on the surface modification as claimed in claim 1 or 8, wherein the flow rate of the gas is 30-50 mL/min.
10. The preparation method of the vanadium-based positive electrode material based on surface modification for enhancing cycle stability according to claim 1, wherein the temperature is 200-300 ℃, and the standing time is 3-5 h.
11. The method for preparing the vanadium-based cathode material with enhanced cycling stability based on surface modification according to claim 1, wherein the conditions of centrifugation and drying of the flocculent solid product are as follows: centrifuging at 8000rpm for 3-5 min, and drying at 70 deg.C in air.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101051685A (en) * | 2007-04-11 | 2007-10-10 | 南开大学 | Method for preparing transition metal vanadate one dimension electrode material and its use |
| CN101058440A (en) * | 2007-02-09 | 2007-10-24 | 合肥工业大学 | Preparation of positive electrode material Li(1+x)V3O8 of lithium ion cell and doping method |
| CN106784816A (en) * | 2016-12-23 | 2017-05-31 | 石家庄学院 | Alkali formula vanadic acid cobalt micron sheet material and preparation method thereof |
| US20170207492A1 (en) * | 2015-06-08 | 2017-07-20 | Brian D. Adams | Electrode materials for rechargeable zinc cells and batteries produced therefrom |
| CN107170967A (en) * | 2017-05-05 | 2017-09-15 | 武汉理工大学 | Pre- intercalated layered barium oxide nano material of bivalent metal ion and its preparation method and application |
| CN107482169A (en) * | 2017-07-28 | 2017-12-15 | 苏州协鑫集成储能科技有限公司 | Vanadic acid cobalt lithium and its preparation method and application |
| CN109585800A (en) * | 2018-09-26 | 2019-04-05 | 吉林大学 | Vanadic acid cobalt and redox graphene composite negative pole material and preparation method |
| CN110474044A (en) * | 2019-09-05 | 2019-11-19 | 山东大学 | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof |
-
2021
- 2021-06-25 CN CN202110712441.4A patent/CN113428897B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058440A (en) * | 2007-02-09 | 2007-10-24 | 合肥工业大学 | Preparation of positive electrode material Li(1+x)V3O8 of lithium ion cell and doping method |
| CN101051685A (en) * | 2007-04-11 | 2007-10-10 | 南开大学 | Method for preparing transition metal vanadate one dimension electrode material and its use |
| US20170207492A1 (en) * | 2015-06-08 | 2017-07-20 | Brian D. Adams | Electrode materials for rechargeable zinc cells and batteries produced therefrom |
| CN106784816A (en) * | 2016-12-23 | 2017-05-31 | 石家庄学院 | Alkali formula vanadic acid cobalt micron sheet material and preparation method thereof |
| CN107170967A (en) * | 2017-05-05 | 2017-09-15 | 武汉理工大学 | Pre- intercalated layered barium oxide nano material of bivalent metal ion and its preparation method and application |
| CN107482169A (en) * | 2017-07-28 | 2017-12-15 | 苏州协鑫集成储能科技有限公司 | Vanadic acid cobalt lithium and its preparation method and application |
| CN109585800A (en) * | 2018-09-26 | 2019-04-05 | 吉林大学 | Vanadic acid cobalt and redox graphene composite negative pole material and preparation method |
| CN110474044A (en) * | 2019-09-05 | 2019-11-19 | 山东大学 | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| LONGTAO MA ET AL.: "Achieving both high voltage and high capacity in aqueous zinc-ion battery for record high energy density", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| MENG LIAO ET AL.: "A deep-cycle aqueous zinc-ion battery containing an oxygen-deficient vanadium oxide cathode", 《ANGEWANDE CHEMIE INTERNATIONAL EDITION》 * |
| TONGYE WEI ET AL.: "Highly reversible and long-life cycling aqueous zinc-ion battery based on ultrathin (NH4)2V10O25•8H2O nanobelts", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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