CN111634955A - Co3V2O8Preparation method of/C composite electrode material - Google Patents

Co3V2O8Preparation method of/C composite electrode material Download PDF

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CN111634955A
CN111634955A CN202010482415.2A CN202010482415A CN111634955A CN 111634955 A CN111634955 A CN 111634955A CN 202010482415 A CN202010482415 A CN 202010482415A CN 111634955 A CN111634955 A CN 111634955A
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许应珍
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Dongguan Xiaowa Technology Co ltd
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Abstract

Co3V2O8The invention discloses a preparation method of a/C composite electrode material, which relates to the technical field of preparation of lithium ion battery materials, and comprises the following steps: firstly preparing a cobalt-containing solution and a vanadium-containing solution,then, ammonia water is used as a precipitator, a non-ionic block copolymer P123 is used as a surfactant, and Co is obtained by controlling the dropping rate and the hydrothermal temperature3V2O8Nanorods, then using polyvinyl alcohol as carbon source by adding Co3V2O8Mixing with carbon source for heat treatment to obtain carbon-coated Co3V2O8And (4) nanorods. The preparation method is simple and rapid, the synthesized product has controllable appearance, and the composite material has higher specific charge capacity and excellent discharge performance and has certain potential value in the field of lithium ion batteries.

Description

Co3V2O8Preparation method of/C composite electrode material
Technical Field
The invention relates to the technical field, in particular to Co3V2O8A preparation method of the/C composite electrode material.
Background
The lithium ion battery has the advantages of high voltage, small self-discharge, no toxicity, environmental protection, good cycle stability and the like, and is widely concerned by governments, scientific researchers and the like since the emergence of the green energy.
The transition metal oxide is considered to have the potential of becoming a novel high-energy lithium ion battery cathode material, and the oxide has high theoretical specific capacity, good safety performance, rich resources, low price and easy obtainment. Among the many negative electrode materials currently under investigation, cobalt oxide-cobalt vanadate (Co)3V2O8) The lithium battery has a unique crystal structure, large tap density, high theoretical specific capacity and high safety, and meanwhile, the synergistic effect of cobalt and vanadium can greatly improve the performances of the lithium battery such as rate, capacity and stability, and the like, so that the lithium battery has a great commercial application prospect. However, cobalt vanadate, as a transition metal oxide, also has the disadvantages of poor conductivity, low cycle stability, and the like.
In the prior art, the research on cobalt vanadate micron materials is more, and Chinese patent application 2016109284563 applies to Co by a carbothermal decomposition method3V2O8The surface coating C can effectively improve the circulation stability of the material, but the cobalt vanadate prepared by the method has larger size, and the mixed powder is directly burned, so that the carbon is difficult to realize uniform coating. Chinese patent application 2016109681407 uses addition of CO (NH)2)2Method of synthesizing spherical Co3V2O8. Fangfang Wu et al (Hydrothermal Synthesis of Unique Hollow prism of Co., Ltd.)3V2O8·n H2O, A New Anode Material for Lithium-Ion Batteries) and synthesizing Co with hollow structure by hydrothermal method3V2O8Micron material. Le Hu et al (Co)3V2O8The composite material of reduced Graphene and cobalt vanadate is prepared by a hydrothermal method, so that the specific capacitance of cobalt vanadate is greatly improved. At present, less reports are provided for the uniform carbon coating of the cobalt vanadate nanorods.
Disclosure of Invention
The invention aims to provide reasonably designed Co aiming at the defects and shortcomings of the prior art3V2O8The preparation method of the/C composite electrode material comprises the step ofGlycol and deionized water are used as reaction solvents, a specific surfactant-nonionic block copolymer P123 is selected, and then stable and uniformly dispersed Co is ensured to be obtained by controlling parameters such as dropping rate, hydrothermal temperature and the like3V2O8And finally, taking inert gas as carrier gas to realize that carbon source powder completes the uniform decomposition and coating process of the cobalt vanadate in the carrier gas, thereby obtaining the composite electrode material with higher charge specific capacity and excellent discharge performance. The product of the invention has controllable appearance and size, uniform size distribution and certain potential value in the field of lithium ion batteries.
In order to achieve the purpose, the invention adopts the following technical scheme: the method comprises the following steps:
step 1, adding a cobalt source into ethylene glycol, stirring at room temperature to completely dissolve the cobalt source to obtain a cobalt-containing solution, adding a vanadium source into deionized water, and stirring at room temperature to completely dissolve the vanadium source to obtain a vanadium-containing solution; the cobalt source is cobalt acetylacetonate, the vanadium source is ammonium metavanadate, and the volume ratio of the ethylene glycol to the deionized water is 30mL:25-30 mL;
step 2, sequentially adding a non-ionic block copolymer and a vanadium-containing solution into the cobalt-containing solution obtained in the step 1, stirring for 10-20min, then dropwise adding a precipitator while stirring, and continuously stirring at room temperature for 3-5h after dropwise adding is completed to obtain a precursor solution, wherein the precipitator is an ammonia water solution, the non-ionic block copolymer is P123, the dropwise adding speed is 3-5mL/min, and the molar ratio Co of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is V =3:2-3: 2.5;
step 3, adding the precursor solution obtained in the step 2 into a 100mL autoclave with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at the temperature of 110-120 ℃ for 10-12h, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step 4, placing the product dried in the step 3 in a muffle furnace for heat treatment, wherein the heat treatment temperature is 200-300 ℃, the heat treatment time is 1-2h, the heat treatment atmosphere is air atmosphere, and the heat treatment is carried outPost-obtaining Co3V2O8Nano-rod powder;
step 5, the Co obtained in the step 4 is used3V2O8Adding nanorod powder and polyvinyl alcohol (PVA) powder into a ball mill for ball milling, controlling the ball milling rotation speed to be 400-600rmin, and controlling the ball milling time to be 0.5-2h to ensure that the raw materials are uniformly mixed, and after the ball milling is finished, placing the mixed powder into a drying box for drying, wherein the drying temperature is 70 ℃, and the drying time is 1-2 h;
step 6, conveying the mixed powder dried in the step 5 to a high-temperature heat treatment furnace by using argon or nitrogen for calcining heat treatment, wherein the heat treatment temperature is 450-850 ℃, the heat treatment time is 6-10h, and naturally cooling to room temperature after calcining is finished to obtain Co3V2O8The outer surface of the composite material is a carbon coating layer, and the inner layer of the composite material is Co3V2O8And (4) nanorods.
Preferably, in the step 2, the dropping rate is preferably 3 to 4.5mL/min, more preferably 4 mL/min.
Preferably, in the step 2, the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution, Co: V =3: 2.
Preferably, in the step 3, the temperature of the low-temperature hydrothermal reaction is 110 ℃ and the time of the low-temperature hydrothermal reaction is 12 hours.
Preferably, in the step 3, the washing times of the washing with deionized water and absolute ethyl alcohol are 3 to 5 times, preferably 5 times, and the drying is drying in air at 60 to 80 ℃.
Preferably, the length of the nanorod is 200-300nm, and the length-diameter ratio is 6-9.
Preferably, in the step 6, the heat treatment temperature is 550 ℃ and the heat treatment time is 6 hours.
The invention has the beneficial effects that:
the invention takes ammonia water as a precipitator, takes ethylene glycol and deionized water as reaction solvents, selects a specific surfactant-nonionic block copolymer P123, and then ensures to obtain a stable polymer by controlling parameters such as dropping speed, hydrothermal temperature and the like,Uniformly dispersed Co3V2O8And finally, taking inert gas as carrier gas to realize that carbon source powder completes the uniform decomposition and coating process of the cobalt vanadate in the carrier gas, thereby obtaining the composite electrode material with higher charge specific capacity and excellent discharge performance. The product of the invention has controllable appearance and size, uniform size distribution and certain potential value in the field of lithium ion batteries.
The specific implementation mode is as follows:
example 1:
co3V2O8The preparation method of the/C composite electrode material comprises the following steps:
step 1, adding cobalt acetylacetonate into 30mL of ethylene glycol, stirring for 30min at room temperature to completely dissolve the cobalt acetylacetonate to obtain a cobalt-containing solution, adding ammonium metavanadate into 25mL of deionized water, and stirring for 30min at room temperature to completely dissolve the ammonium metavanadate to obtain a vanadium-containing solution;
step 2, sequentially adding a non-ionic block copolymer P123 and a vanadium-containing solution into the cobalt-containing solution obtained in the step 1, wherein the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is controlled to be 3:2, stirring for 10-20min after mixing, then dropwise adding an ammonia water solution while stirring, wherein the dropwise adding speed is controlled to be about 4 mL/min, and after the dropwise adding is finished, continuously stirring at room temperature for 3-5h to obtain a precursor solution;
step 3, adding the precursor solution obtained in the step 2 into a 100mL high-pressure kettle with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at the temperature of 110 ℃ for 12 hours, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step 4, placing the dried product obtained in the step 3 in a muffle furnace, heating to 250 ℃ for heat treatment for 2 hours to obtain Co after heat treatment3V2O8Nano-rod powder;
observing the obtained nano rod through SEM, wherein the length of the nano rod is about 300nm, and the length-diameter ratio is about 8;
step 5, step 4Obtained Co3V2O8Adding nanorod powder and polyvinyl alcohol (PVA) powder into a ball mill for ball milling, controlling the ball milling rotation speed to be 400-600rmin, and controlling the ball milling time to be 0.5-2h to ensure that the raw materials are uniformly mixed, and after the ball milling is finished, placing the mixed powder into a drying box for drying, wherein the drying temperature is 70 ℃, and the drying time is 1-2 h;
and 6, conveying the mixed powder dried in the step 5 to a high-temperature heat treatment furnace by using nitrogen for calcining heat treatment, wherein the heat treatment temperature is 450 ℃, the heat treatment time is 10 hours, and naturally cooling to room temperature after calcining to obtain Co3V2O8The outer surface of the composite material is a carbon coating layer, and the inner layer of the composite material is Co3V2O8And (4) nanorods.
Example 2:
co3V2O8The preparation method of the/C composite electrode material comprises the following steps:
step 1, adding cobalt acetylacetonate into 30mL of ethylene glycol, stirring for 30min at room temperature to completely dissolve the cobalt acetylacetonate to obtain a cobalt-containing solution, adding ammonium metavanadate into 25mL of deionized water, and stirring for 30min at room temperature to completely dissolve the ammonium metavanadate to obtain a vanadium-containing solution;
step 2, sequentially adding a non-ionic block copolymer P123 and a vanadium-containing solution into the cobalt-containing solution obtained in the step 1, wherein the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is controlled to be 3:2, stirring for 10-20min after mixing, then dropwise adding an ammonia water solution while stirring, wherein the dropwise adding speed is controlled to be about 4 mL/min, and after the dropwise adding is finished, continuously stirring at room temperature for 3-5h to obtain a precursor solution;
step 3, adding the precursor solution obtained in the step 2 into a 100mL high-pressure kettle with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at the temperature of 115 ℃ for 12 hours, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step 4, placing the dried product in the step 3 in a muffle furnace, heating to 200 ℃ for heat treatment and heatingThe treatment time is 2h, and Co is obtained after the heat treatment3V2O8Nano-rod powder;
step 5, the Co obtained in the step 4 is used3V2O8Adding nanorod powder and polyvinyl alcohol (PVA) powder into a ball mill for ball milling, controlling the ball milling rotation speed to be 400-600rmin, and controlling the ball milling time to be 0.5-2h to ensure that the raw materials are uniformly mixed, and after the ball milling is finished, placing the mixed powder into a drying box for drying, wherein the drying temperature is 70 ℃, and the drying time is 1-2 h;
and 6, conveying the mixed powder dried in the step 5 to a high-temperature heat treatment furnace by using nitrogen for calcination heat treatment, wherein the heat treatment temperature is 600 ℃, the heat treatment time is 10 hours, and naturally cooling to room temperature after calcination is finished to obtain Co3V2O8The outer surface of the composite material is a carbon coating layer, and the inner layer of the composite material is Co3V2O8And (4) nanorods.
Example 3:
co3V2O8The preparation method of the/C composite electrode material comprises the following steps:
step 1, adding cobalt acetylacetonate into 30mL of ethylene glycol, stirring at room temperature for 30min to completely dissolve the cobalt acetylacetonate to obtain a cobalt-containing solution, adding ammonium metavanadate into 30mL of deionized water, and stirring at room temperature for 30min to completely dissolve the ammonium metavanadate to obtain a vanadium-containing solution;
step 2, sequentially adding a non-ionic block copolymer P123 and a vanadium-containing solution into the cobalt-containing solution obtained in the step 1, wherein the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is controlled to be 3:2, stirring for 10-20min after mixing, then dropwise adding an ammonia water solution while stirring, wherein the dropwise adding speed is controlled to be about 4 mL/min, and after the dropwise adding is finished, continuously stirring at room temperature for 3-5h to obtain a precursor solution;
step 3, adding the precursor solution obtained in the step 2 into a 100mL high-pressure kettle with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at 120 ℃ for 10 hours, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step 4, placing the dried product obtained in the step 3 in a muffle furnace, heating to 300 ℃ for heat treatment for 1h to obtain Co3V2O8Nano-rod powder;
step 5, the Co obtained in the step 4 is used3V2O8Adding nanorod powder and polyvinyl alcohol (PVA) powder into a ball mill for ball milling, controlling the ball milling rotation speed to be 400-600rmin, and controlling the ball milling time to be 0.5-2h to ensure that the raw materials are uniformly mixed, and after the ball milling is finished, placing the mixed powder into a drying box for drying, wherein the drying temperature is 70 ℃, and the drying time is 1-2 h;
and 6, conveying the mixed powder dried in the step 5 to a high-temperature heat treatment furnace by using nitrogen for calcining heat treatment, wherein the heat treatment temperature is 700 ℃, the heat treatment time is 8 hours, and naturally cooling to room temperature after calcining to obtain Co3V2O8The outer surface of the composite material is a carbon coating layer, and the inner layer of the composite material is Co3V2O8And (4) nanorods.
Example 4:
co3V2O8The preparation method of the/C composite electrode material comprises the following steps:
step 1, adding cobalt acetylacetonate into 30mL of ethylene glycol, stirring for 30min at room temperature to completely dissolve the cobalt acetylacetonate to obtain a cobalt-containing solution, adding ammonium metavanadate into 25mL of deionized water, and stirring for 30min at room temperature to completely dissolve the ammonium metavanadate to obtain a vanadium-containing solution;
step 2, sequentially adding a non-ionic block copolymer P123 and a vanadium-containing solution into the cobalt-containing solution obtained in the step 1, wherein the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is controlled to be 3:2, stirring for 10-20min after mixing, then dropwise adding an ammonia water solution while stirring, wherein the dropwise adding speed is controlled to be about 4 mL/min, and after the dropwise adding is finished, continuously stirring at room temperature for 3-5h to obtain a precursor solution;
step 3, adding the precursor solution obtained in the step 2 into a 100mL high-pressure kettle with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at the temperature of 110 ℃ for 10 hours, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step 4, placing the dried product obtained in the step 3 in a muffle furnace, heating to 300 ℃ for heat treatment for 2 hours to obtain Co after heat treatment3V2O8Nano-rod powder;
step 5, the Co obtained in the step 4 is used3V2O8Adding nanorod powder and polyvinyl alcohol (PVA) powder into a ball mill for ball milling, controlling the ball milling rotation speed to be 400-600rmin, and controlling the ball milling time to be 0.5-2h to ensure that the raw materials are uniformly mixed, and after the ball milling is finished, placing the mixed powder into a drying box for drying, wherein the drying temperature is 70 ℃, and the drying time is 1-2 h;
and 6, conveying the mixed powder dried in the step 5 to a high-temperature heat treatment furnace by using nitrogen for calcining heat treatment, wherein the heat treatment temperature is 850 ℃, the heat treatment time is 6 hours, and naturally cooling to room temperature after calcining is finished to obtain Co3V2O8The outer surface of the composite material is a carbon coating layer, and the inner layer of the composite material is Co3V2O8And (4) nanorods.
Example 5:
co3V2O8The preparation method of the electrode material comprises the following steps:
step 1, adding cobalt acetylacetonate into 30mL of ethylene glycol, stirring for 30min at room temperature to completely dissolve the cobalt acetylacetonate to obtain a cobalt-containing solution, adding ammonium metavanadate into 25mL of deionized water, and stirring for 30min at room temperature to completely dissolve the ammonium metavanadate to obtain a vanadium-containing solution;
step 2, adding a vanadium-containing solution into the cobalt-containing solution obtained in the step 1, wherein the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is controlled to be 3:2, stirring for 10-20min after mixing, then dropwise adding an ammonia water solution while stirring, wherein the dropwise adding speed is controlled to be about 4 mL/min, and after dropwise adding is completed, continuously stirring at room temperature for 3-5h to obtain a precursor solution;
step 3, adding the precursor solution obtained in the step 2 into a 100mL high-pressure kettle with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at the temperature of 110 ℃ for 12 hours, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step 4, placing the dried product obtained in the step 3 in a muffle furnace, heating to 250 ℃ for heat treatment for 2 hours to obtain Co after heat treatment3V2O8Powder;
the obtained powder was observed by SEM, and the morphology of the obtained powder was spheroidal when no surfactant was added.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.

Claims (4)

1. Co3V2O8The preparation method of the/C composite electrode material is characterized by comprising the following steps: the method comprises the following steps:
adding a cobalt source into ethylene glycol, stirring at room temperature to completely dissolve the cobalt source to obtain a cobalt-containing solution, adding a vanadium source into deionized water, and stirring at room temperature to completely dissolve the vanadium source to obtain a vanadium-containing solution; the cobalt source is cobalt acetylacetonate, the vanadium source is ammonium metavanadate, and the volume ratio of the ethylene glycol to the deionized water is 30mL:25-30 mL;
step (2), sequentially adding a non-ionic block copolymer and a vanadium-containing solution into the cobalt-containing solution obtained in the step (1), stirring for 10-20min, then dropwise adding a precipitator while stirring, and after dropwise adding is completed, continuously stirring at room temperature for 3-5h to obtain a precursor solution, wherein the precipitator is an ammonia water solution, the non-ionic block copolymer is P123, the dropwise adding speed is 3-5mL/min, and the molar ratio Co of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution is V =3:2-3: 2.5;
step (3), adding the precursor solution obtained in the step (2) into a 100mL high-pressure kettle with a polytetrafluoroethylene lining for low-temperature hydrothermal reaction at the temperature of 110-120 ℃ for 10-12h, naturally cooling to room temperature after the reaction is finished, centrifugally collecting a product, washing with deionized water and absolute ethyl alcohol, and drying in the air;
step (4), placing the dried product in the step (3) in a muffle furnace for heat treatment, wherein the heat treatment temperature is 200-300 ℃, the heat treatment time is 1-2h, the heat treatment atmosphere is air atmosphere, and Co is obtained after heat treatment3V2O8Nano-rod powder; the length of the nanorod is 200-300nm, and the length-diameter ratio is 6-9;
step (5) of mixing the Co obtained in step (4)3V2O8Adding nanorod powder and polyvinyl alcohol (PVA) powder into a ball mill for ball milling, controlling the ball milling rotation speed to be 400-600rmin, and controlling the ball milling time to be 0.5-2h to ensure that the raw materials are uniformly mixed, and after the ball milling is finished, placing the mixed powder into a drying box for drying, wherein the drying temperature is 70 ℃, and the drying time is 1-2 h;
step (6), conveying the mixed powder dried in the step (5) to a high-temperature heat treatment furnace by using argon or nitrogen for calcining heat treatment, wherein the heat treatment temperature is 450-850 ℃, the heat treatment time is 6-10h, and naturally cooling to room temperature after calcining is finished to obtain Co3V2O8The outer surface of the composite material is a carbon coating layer, and the inner layer of the composite material is Co3V2O8And (4) nanorods.
2. Co according to claim 13V2O8The preparation method of the/C composite electrode material is characterized by comprising the following steps: in the step (2), the dropping rate is 3-4.5mL/min, preferably 4 mL/min.
3. Co according to claim 13V2O8The preparation method of the/C composite electrode material is characterized by comprising the following steps: in the step (2), the step (c),the molar ratio of cobalt in the cobalt-containing solution to vanadium in the vanadium-containing solution, Co: V =3: 2.
4. Co according to claim 13V2O8The preparation method of the/C composite electrode material is characterized by comprising the following steps: in the step (3), the washing times of the washing with deionized water and absolute ethyl alcohol are 3 to 5 times, preferably 5 times, and the drying is drying in air at 60 to 80 ℃.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106384814A (en) * 2016-10-31 2017-02-08 电子科技大学 C-layer-cladding Co3V2O8 composite material and preparation method thereof
CN110943213A (en) * 2019-12-17 2020-03-31 济南大学 MOF-derived porous carbon box loaded with Co3V2O8Composite negative electrode material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106384814A (en) * 2016-10-31 2017-02-08 电子科技大学 C-layer-cladding Co3V2O8 composite material and preparation method thereof
CN110943213A (en) * 2019-12-17 2020-03-31 济南大学 MOF-derived porous carbon box loaded with Co3V2O8Composite negative electrode material and preparation method and application thereof

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