CN113948705A - Preparation method of two-dimensional hollow carbon confinement transition metal oxide composite material for lithium ion battery anode - Google Patents
Preparation method of two-dimensional hollow carbon confinement transition metal oxide composite material for lithium ion battery anode Download PDFInfo
- Publication number
- CN113948705A CN113948705A CN202111203948.3A CN202111203948A CN113948705A CN 113948705 A CN113948705 A CN 113948705A CN 202111203948 A CN202111203948 A CN 202111203948A CN 113948705 A CN113948705 A CN 113948705A
- Authority
- CN
- China
- Prior art keywords
- composite material
- dimensional
- transition metal
- metal oxide
- carbon
- 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.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 preparation method of a two-dimensional hollow carbon confinement transition metal oxide composite material for a lithium ion battery anode. Two-dimensional leafy ZIF-L (M) (M represents transition metal) is used as a sacrificial template, tannic acid is used as a strong competitive ligand for coordination etching, a cavity is introduced on the basis of maintaining a ZIF-L (M) two-dimensional leafy structure, the material has larger specific surface area to enrich reaction active sites, and meanwhile, in high-temperature carbonization, a framework formed by macromolecular tannic acid can effectively prevent metal particles from agglomerating to prepare high-density discrete metal oxide nanoparticles. On the basis of inheriting the advantages of a two-dimensional material structure, the composite material prepared by the invention avoids the unfavorable self-accumulation of the two-dimensional material with large specific surface area, and the anisotropic mechanical structure of the two-dimensional material has the advantages of better relieving the strain caused by the volume effect in the lithium intercalation/deintercalation process of the metal oxide high-activity material, meeting the requirements of the anode material of the lithium ion battery on service capacity and service life, and having potential application prospect in the field of alkali metal ion batteries.
Description
Technical Field
The invention belongs to the technical field of anode materials of alkali metal ion batteries, and particularly relates to a preparation method of a two-dimensional hollow carbon confinement transition metal oxide composite material.
Background
With the steady improvement of living standard of people and the rapid development of global economy, the strong demand of human society for energy sources increasingly leads to the over development of fossil energy sources and the exhaustion of reserves, and causes the problems of environmental pollution, greenhouse effect and the like. Since the 21 st century, the 'environmental problem' and 'energy crisis' become increasingly prominent, and the acceleration of energy structure transformation is a key measure for seeking for the symbiotic development of people and nature. New energy sources represented by solar energy, wind energy and tidal energy are rapidly developed, but the discontinuity, intermittence and regionality of energy supply greatly restrict the application development; in addition, the popularization of automobiles is brought by the high-speed urbanization process, and the exhaust emission of the automobiles causes serious air pollution. In view of this, developing a green chemical energy storage device with high power, high energy, long lifetime and high safety is a major scientific challenge and opportunity for energy material and device research in the current scientific community. The lithium ion battery with high specific energy density, high output voltage, long cycle life and cleanness and safety becomes a research hotspot of energy science. In the early 90 s of the 20 th century, it was found that the substitution of a carbon material having a graphite structure for a metallic lithium negative electrode achieved high energy density and long cycle life of a lithium secondary battery, and research on lithium ion batteries was started from this. Subsequently, the concept of lithium ion battery was proposed by the japanese sony corporation in 1991, and the lead was LiCoO2The commercialization of the lithium ion battery is realized for the anode and the cathode made of the stone tar carbon material, and the research of the lithium ion battery is promoted to step into a brand new stage. However, the performance of the graphite cathode of the commercially used lithium ion battery has been developed to the theoretical limit, and the application market expansion of the lithium ion battery is severely restricted. Therefore, an alternative cathode material developed for application in large electric vehicles and integrated power grids is lithium ionThe subcells play a key role in high performance energy storage system competition.
Transition Metal Oxide (TMOs) anode materials based on a switching mechanism
The lithium ion storage and release are carried out, and compared with the de-intercalation mechanism of commercial graphite, the lithium ion electrochemical storage device has excellent energy storage advantages. However, the high active material with superior lithium storage specific capacity is often accompanied by drastic volume change in electrochemical reaction, which greatly restricts the development of commercial application thereof. TMOs are dispersed into a carbon skeleton to construct a composite material, so that the insufficient conductivity of the high-activity material can be greatly improved, the skeleton can be stabilized, and the purposes of optimizing the reversible specific capacity, the cycle life and the rate capability of the electrode material are finally achieved. In recent years, due to the unique structure and surface state of graphene, its exploration and development has opened a new era in the research of similar two-dimensional materials. The two-dimensional carbon-based material is an important research direction for developing the TMOs/carbon composite negative electrode material due to abundant reactive sites, rapid ion diffusion kinetics, excellent electron transport characteristics and unique anisotropic mechanical properties of the two-dimensional carbon-based material. However, the self-stacking effect of two-dimensional materials in the pressed electrode seriously impairs the outstanding electrochemical performance of a single two-dimensional structure. Therefore, the dense packing faced by two-dimensional materials is improved based on unique structural design, in order to develop a TMOs/carbon composite material having excellent lithium storage properties.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional hollow carbon confinement transition metal-based material for a lithium ion battery anode, which is characterized in that the anode electrode material of the lithium ion battery with the two-dimensional hollow carbon confinement transition metal-based material is prepared by a coordination etching process through a sacrificial template method, has excellent specific capacity and stability in lithium intercalation/deintercalation reaction of the lithium ion battery, and can meet the requirements of application and development of the related fields of alkali metal ion batteries.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. preparation of two-dimensional foliated ZIF-L (M)
Quickly injecting deionized water dissolved with 2-methylimidazole into deionized water dissolved with transition metal salt, stirring at room temperature for 3-6 hours, centrifugally washing the precipitate with deionized water, and drying to obtain purple two-dimensional leafy ZIF-L (M); wherein, the transition metal salt is cobalt nitrate or the combination of cobalt nitrate and zinc nitrate or nickel nitrate or copper nitrate, and M represents any one of Co, ZnCo, NiCo and CuCo;
2. tannic acid coordination etch ZIF-L (M)
Injecting the ethanol solution dispersed with the two-dimensional leafy ZIF-L (M) into an ethanol/water mixed solution dissolved with tannic acid, stirring at room temperature for 10-30 minutes, centrifugally washing the precipitate with ethanol, and drying to obtain tan two-dimensional leafy hollow-structure tannic acid-M;
3. preparation of transition metal @ carbon composite material by carbothermic reduction
Placing tannic acid-M with a two-dimensional leaf-shaped hollow structure in a porcelain boat, and carrying out high-temperature heat treatment in a tube furnace under the atmosphere of inert gas to obtain a transition metal @ carbon composite material;
4. preparation of transition metal oxide @ carbon composite material by low-temperature oxidation
The transition metal @ carbon composite material is placed in a porcelain boat, low-temperature oxidation treatment is carried out in a tubular furnace in the air atmosphere, and the transition from metal to metal oxide in the transition metal @ carbon composite material is completed on the premise that the carbon skeleton is not oxidized, so that the transition metal oxide @ carbon composite material, namely the two-dimensional hollow carbon confinement transition metal oxide composite material, is obtained.
In the step 1, the molar ratio of the 2-methylimidazole to the transition metal salt is preferably 1: 6-8.
In the step 2, the concentration of tannic acid dissolved in the ethanol/water mixture is preferably 0.5 to 1mg mL-1The volume concentration of the ethanol in the ethanol/water mixed solution is 25 to 50 percent.
In the step 2, the mass ratio of the two-dimensional leafy ZIF-L (M) to the tannic acid is preferably 1: 2.5-4.
In the step 3, a high-temperature heat treatment method is preferableThe method comprises the following steps: the temperature is raised to 200-300 ℃ and kept for 0.5-1 hour, and then raised to 500-700 ℃ and kept for 1-2 hours. Further preferably, the heating rate of the high-temperature heat treatment is 1-2 ℃ min-1。
In the step 4, the temperature of the low-temperature oxidation treatment is preferably 180-240 ℃ for 3-6 hours. Further preferably, the heating rate of the low-temperature oxidation treatment is 5-10 ℃ min-1。
The invention has the following beneficial effects:
1. the invention takes two-dimensional leafy ZIF-L (M) as a sacrificial template, and introduces an internal cavity on the basis of keeping the two-dimensional leafy structure of the original ZIF-L (M) through tannic acid coordination etching, thereby realizing larger reaction specific surface area and enriching effective reaction active sites in the reaction process; meanwhile, a polymer network formed by macromolecular tannic acid can effectively delocalize metal ions, so that the unfavorable agglomeration of the polymer network under the high-temperature carbothermic reduction is prevented; finally, the two-dimensional hollow carbon composite material with the ultrafine nano metal oxide particles densely distributed is obtained. On the basis of inheriting the advantages of the two-dimensional material structure, the composite material avoids the adverse self-accumulation effect of the two-dimensional material with a large specific surface. Meanwhile, the strain caused by the volume effect in the lithium intercalation/deintercalation process of the metal oxide high-activity material can be better relieved by the anisotropic mechanical structure of the two-dimensional material.
2. Compared with the graphite anode used by commercial lithium ion batteries, the two-dimensional hollow carbon confinement transition metal oxide composite material prepared by the coordination etching process shows excellent specific capacity and cycling stability, and has reference significance for developing a new generation of high-performance alkali metal ion batteries.
3. The preparation method is simple, the raw materials are cheap and easy to obtain, and the method is suitable for industrial large-scale production.
Drawings
FIG. 1 is a high power SEM image of two-dimensional foliated ZIF-L (Co) prepared in example 1.
FIG. 2 is a high power SEM image of two-dimensional lobed hollow structured tannic acid-Co prepared in example 1.
Figure 3 is a high power SEM image of the metallic cobalt @ carbon composite (Co/C) prepared in example 1.
FIG. 4 is a tricobalt tetraoxide @ carbon composite (Co) prepared in example 13O4High power SEM spectrum of/C).
FIG. 5 is a tricobalt tetraoxide @ carbon composite (Co) prepared in example 13O4High power TEM pattern of/C).
FIG. 6 is a tricobalt tetraoxide @ carbon composite (Co) prepared in example 13O4XRD pattern of/C).
FIG. 7 is a tricobalt tetraoxide @ carbon composite (Co) prepared in example 13O4/C) button cell assembled as anode material and metallic lithium as counter electrode at 200mAg-1Cycling performance plot at current density.
FIG. 8 is a tricobalt tetraoxide @ carbon composite (Co) prepared in example 13O4/C) assembling the button cell as anode material and the metal lithium as counter electrode at 200, 400, 800, 1600, 3200, 6400mAg-1Graph of rate performance at current density.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, to which, however, the scope of the invention is not limited.
Example 1
1. Preparation of two-dimensional foliated ZIF-L (Co)
Quickly injecting 40mL of deionized water dissolved with 1mmol of 2-methylimidazole into 40mL of deionized water dissolved with 8mmol of cobalt nitrate hexahydrate, stirring for 4 hours at room temperature, centrifugally washing and precipitating with deionized water, and drying in an oven at 60 ℃ to obtain a purple product, namely a two-dimensional leafy ZIF-L (Co) sacrificial template, as shown in figure 1.
2. Tannic acid coordination etch ZIF-L (Co)
Injecting 20mL of ethanol solution dispersed with 100mg of two-dimensional leafy ZIF-L (Co) into 300mL of ethanol/water mixed solution (the volume concentration of ethanol is 30%) dissolved with 300mg of tannic acid, stirring for 15 minutes at room temperature, centrifugally washing the precipitate with ethanol, and drying in an oven at 60 ℃ to obtain a tawny product, namely the two-dimensional leafy hollow-structure tannic acid-Co, as shown in figure 2, wherein the obtained product retains the basic skeleton of the sacrificial template.
3. Preparation of metallic cobalt @ carbon composite material by carbothermic reduction
Placing tannic acid-Co with two-dimensional leaf-shaped hollow structure in a porcelain boat, and in a tube furnace under argon atmosphere, firstly heating at 1 deg.C for min-1The temperature is raised to 200 ℃ at the temperature raising rate, the temperature is kept for 0.5 hour to stabilize the basic skeleton of the material, and then the temperature is raised for 1 min-1The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 1 hour, the conversion from cobalt ions in the tannic acid-Co to metal cobalt and the conversion from the tannic acid to carbon are completed, and the metal cobalt @ carbon composite material (marked as Co/C), namely the two-dimensional leaf-shaped hollow carbon limited-area metal cobalt composite material, is obtained. As shown in fig. 3, the uniformly dispersed metallic cobalt particles are densely distributed on the two-dimensional lobed carbon skeleton.
4. Preparation of cobaltosic oxide @ carbon composite material by low-temperature oxidation
Placing the metal cobalt @ carbon composite material (Co/C) in a porcelain boat, and heating at 10 ℃ for min in the air atmosphere of a tube furnace-1The temperature is raised to 200 ℃ at the temperature raising rate and is kept for 6 hours, the conversion from the metal cobalt in the metal cobalt @ carbon composite material to the cobaltosic oxide is completed on the premise of ensuring that the carbon skeleton is not oxidized, and the metal cobalt oxide @ carbon composite material (marked as Co) is obtained3O4and/C), namely a two-dimensional hollow carbon-limited metal cobalt oxide composite material. As shown in fig. 4, the leafy carbon skeleton did not collapse. Two-dimensional leaf-like Co3O4The internal cavity of/C and TEM image of ultrafine cobaltosic oxide particles are shown in FIG. 5. In FIG. 6, Co3O4The XRD pattern of/C shows that low temperature oxidation achieves complete conversion of metallic cobalt to cobaltosic oxide.
Example 2
1. Preparation of two-dimensional foliated ZIF-L (ZnCo)
And quickly injecting 40mL of deionized water dissolved with 1mmol of 2-methylimidazole into 40mL of deionized water dissolved with 4mmol of cobalt nitrate hexahydrate and 4mmol of zinc nitrate hexahydrate, stirring for 4 hours at room temperature, centrifugally washing and precipitating with deionized water, and drying in an oven at 60 ℃ to obtain a purple product, namely the two-dimensional leafy ZIF-L (ZnCo) sacrificial template.
2. Tannic acid coordination etch ZIF-L (ZnCo)
Injecting 20mL of ethanol solution dispersed with 100mg of two-dimensional leaf ZIF-L (ZnCo) into 300mL of ethanol/water mixed solution (the volume concentration of ethanol is 30%) dissolved with 300mg of tannic acid, stirring for 15 minutes at room temperature, centrifugally washing the precipitate with ethanol, and drying in an oven at 60 ℃ to obtain a tawny product, namely the two-dimensional leaf hollow-structure tannic acid-ZnCo.
3. Preparation of ZnCo @ carbon composite material by carbothermic reduction
Placing tannic acid-ZnCo with two-dimensional leaf-shaped hollow structure in a porcelain boat, and heating at 1 deg.C for min in argon atmosphere of a tube furnace-1The temperature is raised to 200 ℃ at the temperature raising rate, the temperature is kept for 0.5 hour to stabilize the basic skeleton of the material, and then the temperature is raised for 1 min-1The temperature is raised to 600 ℃ at the temperature raising rate, and the temperature is kept for 1 hour, so that the conversion from cobalt ions to metal cobalt in the tannic acid-ZnCo, from zinc ions to zinc oxide and from the tannic acid to carbon is completed, and the ZnCo @ carbon composite material, namely the two-dimensional leaf-shaped hollow carbon confinement ZnCo composite material, is obtained.
4. Preparation of ZnO-Co by low-temperature oxidation3O4@ carbon composite material
Putting the ZnCo @ carbon composite material into a porcelain boat, and heating for 10 ℃ min in the air atmosphere of a tube furnace-1The temperature is raised to 200 ℃ at the temperature raising rate and is kept for 6 hours, the conversion from metal to metal oxide in the ZnCo @ carbon composite material is completed on the premise of ensuring that the carbon framework is not oxidized, and ZnO-Co is obtained3O4@ carbon composite material (noted as ZnO-Co)3O4and/C), namely a two-dimensional hollow carbon-limited metal oxide composite material.
Example 3
1. Preparation of two-dimensional lobed ZIF-L (NiCo)
Quickly injecting 40mL of deionized water dissolved with 1mmol of 2-methylimidazole into 40mL of deionized water dissolved with 4mmol of cobalt nitrate hexahydrate and 4mmol of nickel nitrate hexahydrate, stirring for 4 hours at room temperature, centrifugally washing and precipitating with deionized water, and drying in an oven at 60 ℃ to obtain a purple product, namely a two-dimensional leafy ZIF-L (NiCo) sacrificial template.
2. Tannic acid coordination etch ZIF-L (NiCo)
Injecting 20mL of ethanol solution dispersed with 100mg of two-dimensional leaf ZIF-L (NiCo) into 300mL of ethanol/water mixed solution (the volume concentration of ethanol is 30%) dissolved with 300mg of tannic acid, stirring for 15 minutes at room temperature, centrifugally washing the precipitate with ethanol, and drying in an oven at 60 ℃ to obtain a tawny product, namely the two-dimensional leaf-shaped hollow-structure tannic acid-NiCo.
3. Preparation of NiCo @ carbon composite material by carbothermic reduction
Placing tannin-NiCo with two-dimensional leaf-shaped hollow structure in a porcelain boat, and in a tube furnace in an argon atmosphere, firstly, at 1 ℃ for min-1The temperature is raised to 200 ℃ at the temperature raising rate, the temperature is kept for 0.5 hour to stabilize the basic skeleton of the material, and then the temperature is raised for 1 min-1The temperature rise rate is raised to 600 ℃, the temperature is kept for 1 hour, the conversion from cobalt ions to metal cobalt in the tannic acid-NiCo, from nickel ions to metal nickel and from tannic acid to carbon is completed, and the NiCo @ carbon composite material, namely the two-dimensional leaf-shaped hollow carbon confinement NiCo composite material, is obtained.
4. Preparation of NiO-Co by low-temperature oxidation3O4@ carbon composite material
Placing the NiCo @ carbon composite material in a porcelain boat, and performing air treatment in a tube furnace at the temperature of 10 ℃ for min-1The temperature rise rate is increased to 200 ℃ and the temperature is kept for 6 hours, the conversion from metal to metal oxide in the NiCo @ carbon composite material is completed on the premise of ensuring that the carbon framework is not oxidized, and NiO-Co is obtained3O4@ carbon composite (noted as NiO-Co)3O4and/C), namely a two-dimensional hollow carbon-limited metal oxide composite material.
Example 4
1. Preparation of two-dimensional leafy ZIF-L (CuCo)
And quickly injecting 40mL of deionized water dissolved with 1mmol of 2-methylimidazole into 40mL of deionized water dissolved with 4mmol of cobalt nitrate hexahydrate and 4mmol of copper nitrate hexahydrate, stirring for 4 hours at room temperature, centrifugally washing the precipitate with the deionized water, and drying in an oven at 60 ℃ to obtain a purple product, namely the two-dimensional leafy ZIF-L (CuCo) sacrificial template.
2. Tannic acid coordination etch ZIF-L (CuCo)
Injecting 20mL of ethanol solution dispersed with 100mg of two-dimensional leafy ZIF-L (CuCo) into 300mL of ethanol/water mixed solution (the volume concentration of ethanol is 30%) dissolved with 300mg of tannic acid, stirring for 15 minutes at room temperature, centrifugally washing the precipitate with ethanol, and drying in an oven at 60 ℃ to obtain a tawny product, namely the two-dimensional leafy hollow structure tannic acid-CuCo.
3. Preparation of CuCo @ carbon composite material by carbothermic reduction
Placing tannic acid-CuCo with two-dimensional leaf-shaped hollow structure in a porcelain boat, and heating at 1 deg.C for min in argon atmosphere of a tube furnace-1The temperature is raised to 200 ℃ at the temperature raising rate, the temperature is kept for 0.5 hour to stabilize the basic skeleton of the material, and then the temperature is raised for 1 min-1The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 1 hour, the conversion from cobalt ions to metal cobalt in the tannic acid-CuCo, from copper ions to metal copper and from tannic acid to carbon is completed, and the CuCo @ carbon composite material, namely the two-dimensional leaf-shaped hollow carbon confinement CuCo composite material, is obtained.
4. Preparation of CuO-Co by low-temperature oxidation3O4@ carbon composite material
Placing the CuCo @ carbon composite material in a porcelain boat, and heating for 10 min in a tube furnace air atmosphere-1The temperature rise rate is increased to 200 ℃ and the temperature is kept for 6 hours, the conversion from metal to metal oxide in the CuCo @ carbon composite material is completed on the premise of ensuring that the carbon skeleton is not oxidized, and the CuO-Co is obtained3O4@ carbon composite material (noted as CuO-Co)3O4and/C), namely a two-dimensional hollow carbon-limited metal oxide composite material.
To demonstrate the beneficial effects of the present invention, the two-dimensional hollow carbon-confined metallic cobalt oxide composite (Co) prepared in example 1 was used3O4/C) coated on copper foil as anode (area 1.13 cm)2The loading amount is 1mg cm-2) The button cell is assembled in a glove box by adopting a lithium sheet as a counter electrode to construct a two-electrode half-cell system (Co)3O4a/C | | lithium plate). And then, carrying out charge and discharge performance test on the assembled button cell on a Xinwei cell test system: the current density is controlled at 200mAg in the battery cycle test-1The results are shown in FIG. 7; the current density was gradually changed to 200, 400, 800, 1600, 3200, 6400mAg in the battery rate test-1The results are shown in FIG. 8. As can be seen from FIG. 7, the specific capacity of the prepared battery is maintained at 805.6mAh g after 200 times of cyclic charge and discharge-1Far higher than the specific capacity (372.0 mAhg) of commercial graphite anode-1). As can be seen from FIG. 8, the prepared battery also exhibited rate testsExcellent performance at 6400mA g-1275.6mAhg at current density-1Specific capacity, in particular current density, of 6400mA g-1Return to 200mA g-1And then, the specific capacity is quickly recovered, and the new requirements of the current society on energy storage devices can be well met.
Claims (8)
1. A preparation method of a two-dimensional hollow carbon confinement transition metal oxide composite material for a lithium ion battery anode is characterized by comprising the following steps:
(1) preparation of two-dimensional foliated ZIF-L (M)
Quickly injecting deionized water dissolved with 2-methylimidazole into deionized water dissolved with transition metal salt, stirring at room temperature for 3-6 hours, centrifugally washing the precipitate with deionized water, and drying to obtain purple two-dimensional leafy ZIF-L (M); wherein, the transition metal salt is cobalt nitrate or the combination of cobalt nitrate and zinc nitrate or nickel nitrate or copper nitrate, and M represents any one of Co, ZnCo, NiCo and CuCo;
(2) tannic acid coordination etch ZIF-L (M)
Injecting the ethanol solution dispersed with the two-dimensional leafy ZIF-L (M) into an ethanol/water mixed solution dissolved with tannic acid, stirring at room temperature for 10-30 minutes, centrifugally washing the precipitate with ethanol, and drying to obtain tan two-dimensional leafy hollow-structure tannic acid-M;
(3) preparation of transition metal @ carbon composite material by carbothermic reduction
Placing tannic acid-M with a two-dimensional leaf-shaped hollow structure in a porcelain boat, and carrying out high-temperature heat treatment in a tube furnace under the atmosphere of inert gas to obtain a transition metal @ carbon composite material;
(4) preparation of transition metal oxide @ carbon composite material by low-temperature oxidation
The transition metal @ carbon composite material is placed in a porcelain boat, low-temperature oxidation treatment is carried out in a tubular furnace in the air atmosphere, and the transition from metal to metal oxide in the transition metal @ carbon composite material is completed on the premise that the carbon skeleton is not oxidized, so that the transition metal oxide @ carbon composite material, namely the two-dimensional hollow carbon confinement transition metal oxide composite material, is obtained.
2. The method for preparing a two-dimensional hollow carbon-confined transition metal oxide composite material according to claim 1, wherein: in the step (1), the molar ratio of the 2-methylimidazole to the transition metal salt is 1: 6-8.
3. The method for preparing a two-dimensional hollow carbon-confined transition metal oxide composite material according to claim 1, wherein: in the step (2), the concentration of the tannic acid dissolved in the ethanol/water mixed solution is 0.5-1 mg mL-1The volume concentration of the ethanol in the ethanol/water mixed solution is 25 to 50 percent.
4. The method for preparing a two-dimensional hollow carbon-confined transition metal oxide composite material according to claim 1, wherein: in the step (2), the mass ratio of the two-dimensional leafy ZIF-L (M) to the tannic acid is 1: 2.5-4.
5. The method for preparing a two-dimensional hollow carbon-confined transition metal oxide composite material according to claim 1, wherein: in the step (3), the high-temperature heat treatment method comprises the following steps: the temperature is raised to 200-300 ℃ and kept for 0.5-1 hour, and then raised to 500-700 ℃ and kept for 1-2 hours.
6. The method for preparing a two-dimensional hollow carbon-confined transition metal oxide composite material according to claim 1, wherein: in the step (3), the heating rate of the high-temperature heat treatment is 1-2 ℃ min-1。
7. The method for preparing a two-dimensional hollow carbon-confined transition metal oxide composite material according to claim 1, wherein: in the step (4), the temperature of the low-temperature oxidation treatment is 180-240 ℃ and the time is 3-6 hours.
8. The method of preparing a two-dimensional hollow carbon-confined transition metal oxide composite material of claim 1, which isIs characterized in that: in the step (4), the heating rate of the low-temperature oxidation treatment is 5-10 ℃ min-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111203948.3A CN113948705B (en) | 2021-10-15 | 2021-10-15 | Preparation method of two-dimensional hollow carbon confinement transition metal oxide composite material for lithium ion battery anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111203948.3A CN113948705B (en) | 2021-10-15 | 2021-10-15 | Preparation method of two-dimensional hollow carbon confinement transition metal oxide composite material for lithium ion battery anode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113948705A true CN113948705A (en) | 2022-01-18 |
| CN113948705B CN113948705B (en) | 2023-03-31 |
Family
ID=79330636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111203948.3A Active CN113948705B (en) | 2021-10-15 | 2021-10-15 | Preparation method of two-dimensional hollow carbon confinement transition metal oxide composite material for lithium ion battery anode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113948705B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112678799A (en) * | 2021-01-26 | 2021-04-20 | 四川大学 | Carbon-coated silicon negative electrode material with hollow structure and preparation method thereof |
| CN117430824A (en) * | 2023-12-20 | 2024-01-23 | 成都大学 | Nitrogen-doped hollow MOF material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058174A (en) * | 2016-06-13 | 2016-10-26 | 大连理工大学 | Preparation method and application of flower-shaped composite material formed by carbon plates in which cobaltosic oxide is embedded in hollow nano sphere mode |
| CN109037617A (en) * | 2018-07-10 | 2018-12-18 | 厦门理工学院 | A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application |
| CN109728282A (en) * | 2018-12-30 | 2019-05-07 | 北京乐华锂能科技有限公司 | A kind of preparation method of Porous transition metal oxides/carbon composite |
| WO2020016067A1 (en) * | 2018-07-16 | 2020-01-23 | Freie Universität Berlin | Atomic metal- and n-doped open-mesoporous carbon nanofibers for efficient and bio-adaptable oxygen electrode in metal-air batteries |
| CN111463430A (en) * | 2020-04-09 | 2020-07-28 | 北京工业大学 | In-situ polymerization Co3O4Preparation method of/Co/N-C lithium ion battery cathode material |
| CN111916769A (en) * | 2020-08-20 | 2020-11-10 | 浙江工业大学 | Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery |
| CN112736259A (en) * | 2020-12-28 | 2021-04-30 | 陕西师范大学 | Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space |
| CN112751008A (en) * | 2021-02-09 | 2021-05-04 | 福州大学 | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof |
| CN113161538A (en) * | 2021-04-08 | 2021-07-23 | 中北大学 | Co embedded in carbon box mesoporous wall3O4Nanoparticle negative electrode material |
-
2021
- 2021-10-15 CN CN202111203948.3A patent/CN113948705B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058174A (en) * | 2016-06-13 | 2016-10-26 | 大连理工大学 | Preparation method and application of flower-shaped composite material formed by carbon plates in which cobaltosic oxide is embedded in hollow nano sphere mode |
| CN109037617A (en) * | 2018-07-10 | 2018-12-18 | 厦门理工学院 | A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application |
| WO2020016067A1 (en) * | 2018-07-16 | 2020-01-23 | Freie Universität Berlin | Atomic metal- and n-doped open-mesoporous carbon nanofibers for efficient and bio-adaptable oxygen electrode in metal-air batteries |
| CN109728282A (en) * | 2018-12-30 | 2019-05-07 | 北京乐华锂能科技有限公司 | A kind of preparation method of Porous transition metal oxides/carbon composite |
| CN111463430A (en) * | 2020-04-09 | 2020-07-28 | 北京工业大学 | In-situ polymerization Co3O4Preparation method of/Co/N-C lithium ion battery cathode material |
| CN111916769A (en) * | 2020-08-20 | 2020-11-10 | 浙江工业大学 | Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery |
| CN112736259A (en) * | 2020-12-28 | 2021-04-30 | 陕西师范大学 | Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space |
| CN112751008A (en) * | 2021-02-09 | 2021-05-04 | 福州大学 | Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof |
| CN113161538A (en) * | 2021-04-08 | 2021-07-23 | 中北大学 | Co embedded in carbon box mesoporous wall3O4Nanoparticle negative electrode material |
Non-Patent Citations (4)
| Title |
|---|
| JIAMING SHEN等: "Hollow ZIFs-derived nanoporous carbon for efficient capacitive deionization", 《ELECTROCHIMICA ACTA》 * |
| 王薪贺: "Zn/Co双金属有机框架衍生的空心结构Co/NC的合成及其催化性能研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
| 葛晓丽: "基于金属有机骨架化合物的电极材料及其电化学性能", 《中国博士学位论文全文数据（工程科技I辑）》 * |
| 黄启高等: "MOF衍生钴氧化物材料的制备及其电化学性能", 《陕西科技大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112678799A (en) * | 2021-01-26 | 2021-04-20 | 四川大学 | Carbon-coated silicon negative electrode material with hollow structure and preparation method thereof |
| CN117430824A (en) * | 2023-12-20 | 2024-01-23 | 成都大学 | Nitrogen-doped hollow MOF material and preparation method and application thereof |
| CN117430824B (en) * | 2023-12-20 | 2024-03-15 | 成都大学 | Nitrogen-doped hollow MOF material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113948705B (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108649190B (en) | Vertical graphene/titanium niobium oxide/sulfur carbon composite material with three-dimensional porous array structure and preparation method and application thereof | |
| CN103000864B (en) | A kind of sulphur composite positive pole and preparation method thereof | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN113948705B (en) | Preparation method of two-dimensional hollow carbon confinement transition metal oxide composite material for lithium ion battery anode | |
| CN111193014B (en) | Cobaltosic oxide-nitrogen doped carbon/carbon nanocage composite material with eggshell-yolk structure and preparation method and application thereof | |
| CN108598394B (en) | Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof | |
| CN111710860B (en) | Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof | |
| CN113745506B (en) | Method for preparing polyanion type sodium battery anode material based on organic acid dissolution method | |
| CN113161533A (en) | MOF-derived ZnO @ C composite material and application thereof | |
| CN114725366B (en) | Preparation method of niobium-titanium oxide negative electrode material for lithium ion battery | |
| CN110304658B (en) | Nb for lithium ion battery18W16O93Negative electrode material and preparation method thereof | |
| CN111933904A (en) | Bimetal sulfide and preparation method thereof, compound and preparation method thereof, lithium-sulfur positive electrode material and lithium-sulfur battery | |
| CN109560277B (en) | Preparation method of nanowire-shaped manganese selenide/carbon composite material | |
| CN108110231B (en) | Carbon-coated Fe4N nano composite material, preparation method and application thereof | |
| CN110311111A (en) | N adulterates CNT in-stiu coating Co nano particle composite material and preparation and application | |
| CN109167026B (en) | Silicon-cobalt composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN115188935A (en) | Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof | |
| CN114804039B (en) | Carbon matrix composite vanadium nitride nano array and preparation method and application thereof | |
| CN113725433B (en) | N-doped carbon Ni 0.6 Co 0.4 Se 2 Preparation method and application of @ rGO composite material | |
| CN110828819B (en) | Pyrrhotite type iron sulfide negative electrode material for potassium ion battery and preparation method thereof | |
| CN112531165A (en) | Alkali metal cathode composite protective film and preparation method thereof, alkali metal cathode and alkali metal secondary battery | |
| CN114094075B (en) | Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof | |
| CN114420916B (en) | Positive electrode material of lithium-sulfur battery, and preparation method and application thereof | |
| CN111384365A (en) | Preparation method of carbon-coated multilayer NiO hollow sphere composite material | |
| CN113130862B (en) | Three-dimensional graphene composite material and preparation method and application thereof |
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 |