CN109768233B - NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material - Google Patents
NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material Download PDFInfo
- Publication number
- CN109768233B CN109768233B CN201811518515.5A CN201811518515A CN109768233B CN 109768233 B CN109768233 B CN 109768233B CN 201811518515 A CN201811518515 A CN 201811518515A CN 109768233 B CN109768233 B CN 109768233B
- Authority
- CN
- China
- Prior art keywords
- nico
- electrode material
- lithium ion
- drying
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a NiCo lithium ion battery2S4The preparation method of the graphene composite negative electrode material comprises the following steps: (1) sequentially pretreating the resin; (2) adding resin into a catalyst metal salt solution, wherein the metal salt solution is a mixture of a nickel salt solution and a cobalt salt solution, stirring, drying and crushing; (3) adding a pore-forming agent, uniformly stirring and drying; (4) under the protection of inert atmosphere, high-temperature treatment is carried out at 500-900 ℃ for 1-3h, cooling is carried out to room temperature, and then washing, filtering and drying are carried out; (5) preparing a mixed solution with a sulfur-containing compound, carrying out hydrothermal reaction at the temperature of 160-; (6) under the protection of inert atmosphere, high-temperature treatment is carried out for 1-3h at the temperature of 500-. The battery cathode material prepared by the method has the advantages of good conductivity, large specific surface area and excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of lithium battery cathode materials, in particular to a lithium ion battery NiCo2S4A preparation method of a graphene composite negative electrode material.
Background
In recent years, the problems of environmental pollution and energy shortage are becoming more serious, and development of new energy sources with high efficiency, green and environmental protection is urgently needed, and among them, lithium ion batteries have the advantages of high voltage, high charging and discharging energy density, small and light weight, high power density, long service life and the like, and are widely applied to energy storage devices such as portable electronic equipment, electric automobiles and the like. The continuous expansion of the application field of lithium ion batteries and the rapid demand of people for portable electronic products promote the continuous research and development of novel lithium ion electrode materials with high power density, high energy density, long service life, low price and environmental friendliness.
However, the commercial graphite anode material at the present stage has the problems of low specific capacity and the like, and a feasible scheme for designing and preparing an electrode material with excellent performance is urgent. Transition metal sulfides are widely spotlighted because they are widely available and have abundant active sites, and thus can be used as diversified electrode materials. However, poor cycle performance is caused by the problems of poor conductivity, severe volume expansion and the like of the transition metal sulfide.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a NiCo lithium ion battery2S4A preparation method of a graphene composite negative electrode material aims to solve the problems that a transition metal sulfide is easy to agglomerate and react with an electrolyte to decompose, so that the energy density of a lithium ion battery negative electrode material is not high, the cycle performance is not ideal and the like.
In order to achieve the purpose, the invention provides a lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following steps:
(1) sequentially carrying out pretreatment, cleaning and drying on the resin;
(2) adding the resin dried in the step (1) into a catalyst metal salt solution, wherein the metal salt solution is a mixture of a nickel salt solution and a cobalt salt solution, stirring, drying and crushing;
(3) adding a pore-forming agent into the substance obtained after the crushing in the step (2), uniformly stirring and drying;
(4) treating the substance obtained after the crushing in the step (3) at the high temperature of 500-900 ℃ for 1-3h under the protection of inert atmosphere, cooling to room temperature, washing with water, filtering and drying;
(5) preparing a mixed solution of the substance obtained after drying in the step (4) and a sulfur-containing compound, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 160-;
(6) treating the dried substance in the step (5) at the high temperature of 500-700 ℃ for 1-3h under the protection of inert atmosphere, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Preferably, in the above technical solution, the resin in step (1) is one or a mixture of two or more of ion exchange resin, chelating resin, epoxy resin and phenolic resin.
Preferably, in the above technical solution, the pretreatment in step (1) is an alkali treatment and an acid treatment in sequence.
Preferably, in the above technical scheme, the concentration of the catalyst metal salt in the step (2) is 0.05-0.2mol/L, the catalyst metal salt is a mixture of two of nickel salt and cobalt salt, and the molar ratio of the mixture of the nickel salt and the cobalt salt is 1:1-1: 5; wherein the nickel salt is nickel acetate tetrahydrate, nickel chloride hexahydrate, nickel nitrate hexahydrate or nickel sulfate hexahydrate; the cobalt salt is cobalt acetate tetrahydrate, cobalt chloride hexahydrate, cobalt nitrate hexahydrate or cobalt sulfate heptahydrate.
Preferably, in the above technical scheme, the mass ratio of the substance obtained in step (3) to the pore-forming agent is 1:1-1:5, and the pore-forming agent is one or a mixture of two or more of potassium hydroxide, potassium bicarbonate, sodium hydroxide and sodium bicarbonate.
Preferably, in the above technical scheme, the inert atmosphere in the step (4) is one or a mixture of two or more of argon, nitrogen, hydrogen or helium, and the flow rate of the inert atmosphere is controlled to be 30-100 cc/min.
Preferably, in the above technical solution, the high temperature treatment in step (4) is performed in a tube furnace or an atmosphere muffle furnace, and the temperature rise rate before the high temperature treatment is 1-10 ℃/min.
Preferably, in the above technical scheme, the sulfur-containing compound in step (5) is one or a mixture of two or more of thiourea, L-methionine, cysteine and cystine.
Preferably, in the above technical scheme, the mass ratio of the substance obtained after drying in the step (4) and the sulfur-containing compound added in the step (5) is 1:1-1: 5.
Preferably, in the above technical solution, the inert atmosphere in step (6) is one or a mixture of two or more of argon, nitrogen, hydrogen, and helium.
The invention relates to a lithium ion battery NiCo2S4The reaction principle of the preparation method of the graphene composite negative electrode material is as follows:
graphene has excellent conductivity, high electron mobility, large specific surface area, and is capable of effectively inhibiting volume expansion and maintaining structural integrity. The transition metal sulfide has wide sources and abundant active sites, and can be used as diversified electrode materials. The two materials are combined to prepare the composite material, so that the material performance is remarkably improved. In the nickel and cobalt-based sulfide, the ternary cathode material can provide more abundant chemical reactions, and the electrochemical performance of the material is improved. This synergistic effect between nickel and cobalt enhances the conductivity of the material and provides a buffer layer to improve the volume expansion that occurs during continuous charging and discharging. Cobalt element can provide a high theoretical capacity for the material, while nickel element is hybridized with other metals, so that the conductivity of the material is enhanced, and the transmission properties of lithium ions and electrons are improved. Suppression of NiCo by introduction of high specific surface area graphene2S4The volume expansion in the charging and discharging process and the good conductivity of the graphene solve the problem of NiCo2S4The capacity is attenuated in the charging and discharging process, so that the lithium ion battery cathode material with high power density and high energy density is prepared.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a lithium ion battery NiCo2S4The preparation method of the/graphene composite negative electrode material enables metal ions with catalytic action to be effectively and uniformly exchanged by utilizing the resinAnd uniformly distributing metal ions in the resin, and carrying out localized catalytic graphitization to form the graphene layer. The carbon material is subjected to pore forming by adding the pore forming agent, and the shape of the final product is regulated and controlled by changing the using amount of the pore forming agent, so that the graphene powder with the three-dimensional hierarchical pore structure with different specific surface areas and different pore size distributions is obtained. NiCo2S4The graphene in-situ composite material improves the conductivity of the material, is beneficial to the transmission of electrons, and effectively inhibits NiCo by the graphene inhibition of a porous structure2S4The agglomeration relieves the volume change in the circulation process, and improves the circulation stability and the lithium storage capacity of the material. The invention has the advantages of low cost of raw materials, easy control of the synthesis process, easy realization of industrial large-scale production and contribution to promoting the application of the transition metal sulfide in the aspect of lithium ion battery cathode materials.
(2) The method adopts a high-temperature sintering method and a hydrothermal method to prepare the NiCo of the lithium ion battery2S4The/graphene composite negative electrode material does not need to add a template agent and introduce a carbon material as a substrate, a precursor Ni-Co/graphene is directly synthesized by adopting resin which exchanges nickel and cobalt elements through a high-temperature sintering method, and the precursor is subjected to hydrothermal reaction with thiourea to form NiCo in situ2S4[ graphene ]. The cathode material has a large specific surface area, shortens the electron transmission and lithium ion insertion/extraction paths, and relieves NiCo in the charge and discharge processes2S4Volume expansion of the nanoparticles; NiCo improves the reversible capacity and cycling stability of lithium ion batteries due to the synergistic effect between nickel and cobalt elements2S4Graphene is an ideal negative electrode material.
(3) The method has the advantages of low production cost, easy control of the synthesis process, high yield and realization of large-scale preparation; preparation of the resulting NiCo2S4When the graphene composite electrode material is used as a lithium ion battery cathode, the conductivity is good, the specific surface area is large, the cycling stability is excellent, and the graphene composite electrode material has potential application prospects in the fields of portable electronic equipment, hybrid electric vehicles and the like.
Drawings
FIG. 1 is a rootA lithium ion battery NiCo prepared according to example 1 of the invention2S4A microscopic morphology scanning electron microscope characterization image of the graphene composite negative electrode material.
FIG. 2 shows a NiCo lithium ion battery prepared according to example 1 of the present invention2S4A transmission electron microscope characterization image of the microscopic morphology of the graphene composite negative electrode material.
FIG. 3 shows a NiCo lithium ion battery prepared according to example 1 of the present invention2S4X-ray diffraction analysis diagram of the/graphene composite negative electrode material.
FIG. 4 shows a NiCo lithium ion battery prepared according to example 1 of the present invention2S4The nitrogen adsorption and desorption curve and the aperture distribution diagram of the graphene composite negative electrode material are shown.
FIG. 5 shows a NiCo lithium ion battery prepared according to example 1 of the present invention2S4The electrochemical performance diagram of the/graphene composite negative electrode material.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.2mol/L cobalt acetate tetrahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium hydroxide pore-forming agent into the substance obtained after crushing in the step (2) according to the mass ratio of 1:1, uniformly stirring, and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, then heating to 850 ℃ at 2 ℃/min, carrying out high-temperature treatment for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the dried substance in the step (4) and thiourea according to the mass ratio of 1:1, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing with water and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
The composite negative electrode material prepared in the example was tested
As shown in FIG. 1 and FIG. 2, FIG. 1 shows the NiCo of the lithium ion battery prepared in this example2S4A characterization figure of a scanning electron microscope for the microstructure of the graphene composite negative electrode material, and fig. 2 shows a NiCo of the lithium ion battery prepared by the embodiment2S4A transmission electron microscope characterization image of the microscopic morphology of the graphene composite negative electrode material. It can be seen from the figure that the three-dimensional porous corrugated structure of graphene provides a large specific surface area for the material, and the graphene is coated with NiCo2S4 nanoparticles, so that the agglomeration of the nanoparticles is inhibited.
As shown in FIG. 3, FIG. 3 shows the NiCo of the lithium ion battery prepared in this example2S4X-ray diffraction analysis chart of/graphene composite negative electrode material, NiCo2S4And JCPDS No.20-0782 standard card NiCo2S4The peaks of (1) were consistent and a hump of the graphene (002) crystal face was clearly visible.
FIG. 4 shows a NiCo lithium ion battery prepared in this example2S4The nitrogen adsorption and desorption curve and the pore size distribution diagram of the graphene composite negative electrode material are shown in the BET specific surface area of 1036.5m in fig. 4a2(ii)/g; in FIG. 4b, it can be seen thatThe composite electrode material mainly comprises micropores, and in addition, some mesopores and macropores.
FIG. 5 shows a NiCo lithium ion battery prepared in this example2S4The electrochemical performance diagram of the/graphene composite negative electrode material can be seen from the cycle performance diagram of fig. 5a, after 500 cycles of charge and discharge at a large current density of 2000mA/g, the discharge capacity of the composite electrode material still remains 481.6 mAh/g. As can be seen from the rate performance graph of FIG. 5b, the discharge capacity of the composite electrode material is 755.4mAh/g at a small current density of 200 mA/g; the results show that: NiCo of lithium ion battery2S4The/graphene composite negative electrode material shows excellent cycling stability and excellent rate performance.
Example 2
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.1mol/L cobalt chloride hexahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium hydroxide pore-forming agent into the substance obtained after crushing in the step (2) according to the mass ratio of 1:2, uniformly stirring, and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, then heating to 850 ℃ at 2 ℃/min, carrying out high-temperature treatment for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the dried substance in the step (4) and thiourea according to the mass ratio of 1:2, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing with water and drying;
(6) putting the substance obtained after drying in the step (5) into a tube furnace, and heating from room temperature at a heating rate of 5 ℃/min under the protection of 40cc/min argon flowTreating at 500 deg.C for 2h, cooling to room temperature to obtain NiCo of lithium ion battery2S4A/graphene composite negative electrode material.
Example 3
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.3mol/L cobalt chloride hexahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium bicarbonate pore-forming agent into the substance obtained after the crushing in the step (2) according to the mass ratio of 1:3, uniformly stirring and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, then heating to 850 ℃ at 2 ℃/min, carrying out high-temperature treatment for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the dried substance in the step (4) and thiourea according to the mass ratio of 1:3, transferring the mixed solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, filtering, washing with water, and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 4
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.4mol/L cobalt acetate tetrahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium bicarbonate pore-forming agent into the substance obtained after the crushing in the step (2) according to the mass ratio of 1:4, uniformly stirring and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, then heating to 850 ℃ at 2 ℃/min, carrying out high-temperature treatment for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the dried substance in the step (4) and thiourea according to the mass ratio of 1:4, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing with water and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 5
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.5mol/L cobalt chloride hexahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium hydroxide pore-forming agent into the substance obtained after crushing in the step (2) according to the mass ratio of 1:5, uniformly stirring, and drying;
(4) putting the dried substance in the step (3) into a tube furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, heating to 800 ℃ at 2 ℃/min, treating at high temperature for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the dried substance in the step (4) and thiourea according to the mass ratio of 1:5, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing with water and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 6
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.2mol/L cobalt chloride hexahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium hydroxide pore-forming agent into the substance obtained after crushing in the step (2) according to the mass ratio of 1:2, uniformly stirring, and drying;
(4) putting the dried substance in the step (3) into a tube furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, heating to 800 ℃ at 2 ℃/min, treating at high temperature for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the dried substance obtained in the step (4) and L-methionine according to the mass ratio of 1:4, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 7
Lithium ionNiCo of sub-battery2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.2mol/L cobalt chloride hexahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium hydroxide pore-forming agent into the substance obtained after crushing in the step (2) according to the mass ratio of 1:3, uniformly stirring, and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, then heating to 850 ℃ at 2 ℃/min, carrying out high-temperature treatment for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the substance obtained after drying in the step (4) and L-methionine according to the mass ratio of 1:4, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 8
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.2mol/L cobalt acetate tetrahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium hydroxide pore-forming agent into the substance obtained after crushing in the step (2) according to the mass ratio of 1:2, uniformly stirring, and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, then heating to 850 ℃ at 2 ℃/min, carrying out high-temperature treatment for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the substance dried in the step (4) and cysteine according to the mass ratio of 1:5, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing with water, and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 9
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.2mol/L cobalt chloride hexahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium bicarbonate pore-forming agent into the substance obtained after the crushing in the step (2) according to the mass ratio of 1:3, uniformly stirring and drying;
(4) putting the dried substance in the step (3) into a tube furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, heating to 800 ℃ at 2 ℃/min, treating at high temperature for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the substance dried in the step (4) and cysteine according to the mass ratio of 1:5, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 200 ℃ for 24 hours, filtering, washing with water, and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
Example 10
Lithium ion battery NiCo2S4The preparation method of the graphene composite negative electrode material comprises the following operation steps:
(1) sequentially carrying out alkali treatment and acid treatment on the ion exchange resin, cleaning and drying;
(2) adding the ion exchange resin obtained after drying in the step (1) into a mixed solution of 0.1mol/L nickel acetate tetrahydrate and 0.2mol/L cobalt acetate tetrahydrate, stirring for 12h, removing the solution, drying and crushing;
(3) adding a potassium bicarbonate pore-forming agent into the substance obtained after the crushing in the step (2) according to the mass ratio of 1:1, uniformly stirring and drying;
(4) putting the dried substance in the step (3) into a tubular furnace, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, heating to 900 ℃ at 2 ℃/min, treating at high temperature for 2h, cooling to room temperature, washing for 12h, filtering and drying;
(5) preparing a mixed solution of the substance dried in the step (4) and cysteine according to the mass ratio of 1:5, transferring the mixed solution into a reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, filtering, washing with water, and drying;
(6) putting the dried substance in the step (5) into a tube furnace, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min under the protection of argon flow of 40cc/min, carrying out high-temperature treatment for 2h, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. Lithium ion battery NiCo2S4The preparation method of the/graphene composite negative electrode material is characterized by comprising the following steps:
(1) sequentially carrying out pretreatment, cleaning and drying on the resin;
(2) adding the resin dried in the step (1) into a catalyst metal salt solution, wherein the metal salt solution is a mixture of a nickel salt solution and a cobalt salt solution, stirring, drying and crushing;
(3) adding a pore-forming agent into the substance obtained after the crushing in the step (2), uniformly stirring and drying;
(4) treating the substance obtained after the crushing in the step (3) at the high temperature of 500-900 ℃ for 1-3h under the protection of inert atmosphere, cooling to room temperature, washing with water, filtering and drying;
(5) preparing a mixed solution of the dried substance obtained in the step (4) and a sulfur-containing compound, wherein the mass ratio of the dried substance to the sulfur-containing compound is 1:1-1:5, transferring the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 160 ℃ and 200 ℃ for 12-24h, and filtering, washing and drying the mixed solution; the sulfur-containing compound is one or a mixture of more than two of thiourea, L-methionine, cysteine and cystine;
(6) treating the dried substance in the step (5) at the high temperature of 500-700 ℃ for 1-3h under the protection of inert atmosphere, and cooling to room temperature to obtain the NiCo of the lithium ion battery2S4A/graphene composite negative electrode material.
2. The lithium ion battery NiCo of claim 12S4The preparation method of the/graphene composite negative electrode material is characterized in that the resin in the step (1) is ion exchange resin, chelating resin or epoxy resinAnd one or a mixture of two or more of phenol resin.
3. The lithium ion battery NiCo of claim 12S4The preparation method of the graphene composite negative electrode material is characterized in that the pretreatment in the step (1) is alkali treatment and acid treatment in sequence.
4. The lithium ion battery NiCo of claim 12S4The preparation method of the/graphene composite negative electrode material is characterized in that the concentration of the catalyst metal salt in the step (2) is 0.05-0.2mol/L, the catalyst metal salt is a mixture of two of nickel salt and cobalt salt, and the mixing molar ratio of the nickel salt to the cobalt salt is 1:1-1: 5;
wherein the nickel salt is nickel acetate tetrahydrate, nickel chloride hexahydrate, nickel nitrate hexahydrate or nickel sulfate hexahydrate; the cobalt salt is cobalt acetate tetrahydrate, cobalt chloride hexahydrate, cobalt nitrate hexahydrate or cobalt sulfate heptahydrate.
5. The lithium ion battery NiCo of claim 12S4The preparation method of the/graphene composite negative electrode material is characterized in that the mass ratio of the substance obtained in the step (3) to the pore-forming agent is 1:1-1:5, and the pore-forming agent is one or a mixture of more than two of potassium hydroxide, potassium bicarbonate, sodium hydroxide and sodium bicarbonate.
6. The lithium ion battery NiCo of claim 12S4The preparation method of the/graphene composite negative electrode material is characterized in that the inert atmosphere in the step (4) is one or a mixture of more than two of argon, nitrogen, hydrogen or helium, and the flow rate of the inert atmosphere is controlled to be 30-100 cc/min.
7. The lithium ion battery NiCo of claim 12S4The preparation method of the/graphene composite negative electrode material is characterized in that the high-temperature treatment in the step (4) is performed in a tubular furnace or an atmosphere furnaceThe temperature rise rate before high-temperature treatment is 1-10 ℃/min.
8. The lithium ion battery NiCo of claim 12S4The preparation method of the/graphene composite negative electrode material is characterized in that the inert atmosphere in the step (6) is one or a mixture of more than two of argon, nitrogen, hydrogen or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811518515.5A CN109768233B (en) | 2018-12-12 | 2018-12-12 | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811518515.5A CN109768233B (en) | 2018-12-12 | 2018-12-12 | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109768233A CN109768233A (en) | 2019-05-17 |
| CN109768233B true CN109768233B (en) | 2021-03-26 |
Family
ID=66450536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811518515.5A Active CN109768233B (en) | 2018-12-12 | 2018-12-12 | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109768233B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710850B (en) * | 2020-07-17 | 2021-06-29 | 吉林中溢炭素科技有限公司 | NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof |
| CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992306A (en) * | 2012-11-14 | 2013-03-27 | 中山大学 | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof |
| CN104867703A (en) * | 2015-06-04 | 2015-08-26 | 华东理工大学 | Method for preparing a metal sulfide/graphene/nickel sulfide composite thin-film material |
| CN105244482A (en) * | 2015-09-12 | 2016-01-13 | 复旦大学 | Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof |
| CN106829914A (en) * | 2017-01-22 | 2017-06-13 | 广西大学 | A kind of three-dimensional porous carbon negative pole material of lithium ion battery |
| CN106986611A (en) * | 2017-04-26 | 2017-07-28 | 浙江大学 | A kind of preparation method of reguline metal sulfide aeroge |
| CN107611380A (en) * | 2017-08-24 | 2018-01-19 | 广西大学 | A kind of preparation method of nickel oxide/stereochemical structure graphene composite material |
| KR20180106166A (en) * | 2017-03-17 | 2018-10-01 | 영남대학교 산학협력단 | Preparation method of 3D hierarchical mesoporous NiCo2S4/Ni(OH)2 core-shell nanosheet arrays on 3-dimensional conductive carbon electrode and its application to high performance supercapacitors |
-
2018
- 2018-12-12 CN CN201811518515.5A patent/CN109768233B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992306A (en) * | 2012-11-14 | 2013-03-27 | 中山大学 | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof |
| CN104867703A (en) * | 2015-06-04 | 2015-08-26 | 华东理工大学 | Method for preparing a metal sulfide/graphene/nickel sulfide composite thin-film material |
| CN105244482A (en) * | 2015-09-12 | 2016-01-13 | 复旦大学 | Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof |
| CN106829914A (en) * | 2017-01-22 | 2017-06-13 | 广西大学 | A kind of three-dimensional porous carbon negative pole material of lithium ion battery |
| KR20180106166A (en) * | 2017-03-17 | 2018-10-01 | 영남대학교 산학협력단 | Preparation method of 3D hierarchical mesoporous NiCo2S4/Ni(OH)2 core-shell nanosheet arrays on 3-dimensional conductive carbon electrode and its application to high performance supercapacitors |
| CN106986611A (en) * | 2017-04-26 | 2017-07-28 | 浙江大学 | A kind of preparation method of reguline metal sulfide aeroge |
| CN107611380A (en) * | 2017-08-24 | 2018-01-19 | 广西大学 | A kind of preparation method of nickel oxide/stereochemical structure graphene composite material |
Non-Patent Citations (2)
| Title |
|---|
| NiCo2S4 nanoparticles anchored on reduced graphene oxide sheets:In-situ synthesis and enhanced capacitive performance;Zhongchun Li et al.;《Journal of Colloid and Interface Science》;20160520;第477卷;第46-53页 * |
| Novel NiCo2S4/graphene composites synthesized via a one-step in-situ hydrothermal route for;Yunzhi Gao et al.;《Journal of Alloys and Compounds》;20170131;第704卷;第70-78页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109768233A (en) | 2019-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105895886B (en) | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof | |
| CN108767260B (en) | Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof | |
| CN108550821B (en) | Preparation method of core-shell structure nickel phosphide/carbon microspheres based on Ni-MOF | |
| CN109244427B (en) | Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode | |
| CN112349899B (en) | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN107611380B (en) | Preparation method of nickel oxide/graphene composite material with three-dimensional structure | |
| CN110790322B (en) | Core-shell nickel ferrite and preparation method thereof, nickel ferrite @ C material and preparation method and application thereof | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN108091871A (en) | A kind of porous spherical ternary cathode material of lithium ion battery and preparation method thereof | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN109473643B (en) | CoSe2Preparation method and application of graphene composite material | |
| CN111312999A (en) | Preparation method of graphene-coated nickel-iron bimetallic sulfide sodium-ion battery negative electrode material | |
| CN110627031A (en) | Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material | |
| CN110921668B (en) | Preparation method and application of transition metal carbide, carbon material and transition metal chalcogenide | |
| CN109768233B (en) | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material | |
| CN110492076B (en) | Preparation method of two-dimensional porous hexagonal metal oxide nanosheet composite material and application of composite material in potassium ion battery | |
| CN110600682A (en) | Sandwich-shaped hollow spherical lithium ion battery cathode material and preparation method thereof | |
| CN106058193A (en) | Novel negative electrode material of sodium-ion battery as well as preparation method and application thereof | |
| CN109671937B (en) | In-situ synthesis method of transition metal oxide/graphene composite material | |
| CN107742706B (en) | Preparation method and application of graphene composite metal boride and sulfur composite nano material | |
| CN108767261B (en) | Graphitized carbon material with three-dimensional micro-nano composite structure, and preparation method and application thereof | |
| CN110683589B (en) | Preparation method of cobaltosic oxide nano material | |
| CN103441249B (en) | Lithium ion battery ternary cathode material modified by nanometer SnO2 and preparation method of lithium ion battery ternary cathode material | |
| CN109626444B (en) | Porous channel submicron spherical FeS2Preparation method of (1) | |
| CN107732206B (en) | Preparation method of bimetallic oxide composite negative electrode material with multilevel structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |