CN112490422B - Rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material and preparation method and application thereof - Google Patents

Rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material and preparation method and application thereof Download PDF

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CN112490422B
CN112490422B CN202011244167.4A CN202011244167A CN112490422B CN 112490422 B CN112490422 B CN 112490422B CN 202011244167 A CN202011244167 A CN 202011244167A CN 112490422 B CN112490422 B CN 112490422B
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manganese dioxide
methanol
nanotube
methylimidazole
cobaltosic oxide
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CN112490422A (en
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曹志桄
苏梓学
丘勇才
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South China University of Technology SCUT
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract

The invention discloses a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material and a preparation method and application thereof, belonging to the field of lithium ion battery materials. The method comprises the following steps: (1) carrying out hydrothermal reaction on potassium permanganate and concentrated hydrochloric acid to obtain nanotube manganese dioxide; (2) adding nanotube manganese dioxide into methanol to obtain a manganese dioxide methanol solution, adding the manganese dioxide methanol solution into a 2-methylimidazole methanol solution, adding into a cobalt nitrate hexahydrate methanol solution, and standing to obtain an organic metal framework/manganese dioxide compound; (3) and (3) calcining the organic metal framework/manganese dioxide compound obtained in the step (2) at high temperature to obtain the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material. The metal oxide compound with the rod-shaped porous hollow structure can relieve the problem of volume expansion of materials in the charge and discharge processes, and has a good application prospect in the field of lithium ion batteries.

Description

Rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material as well as a preparation method and application thereof.
Background
Along with energy problems and environmental problems, the demand of human beings on high-specific-capacity lithium ion batteries is more and more urgent. How to achieve high capacity, high power and long life of lithium ion batteries depends onWherein the structural design and performance of each core component is enhanced. At present, the lithium ion battery cathode materials generally applied in the market are mainly graphite-carbon cathode materials, and are divided into several forms such as graphite, hard carbon and soft carbon materials. Transition metal oxides have been one of the hot spots of research due to their wide variety of alternatives and small volume effect. The transition metal oxides have the following advantages: (1) the theoretical specific capacity is higher; the theoretical specific capacity of the transition metal oxide is far higher than that of the current commercial carbon material (372mAh/g), such as MnO2Is 1232mAh/g, Fe2O3Is 1007mAh/g and Fe3O4Is 924mAh/g, Co3O4890mAh/g, 673mAh/g CuO and the like; (2) manganese dioxide and cobaltosic oxide have low discharge plateaus of about 0.4V and 0.6V; the voltage of the two transition metal oxides is obviously lower than the voltage platform of other transition metal oxide cathode materials, such as Fe2O30.7-0.9V, CuO about 0.9V; (3) manganese dioxide has various crystal structures (such as alpha phase, beta phase and gamma phase and the like); (4) manganese dioxide also has the advantages of abundant natural reserves, low price, less environmental pollution and the like; (5) the transition metal oxide hybrid structure can retain the advantages of each component, and simultaneously provide synergistic effect to improve physical and chemical properties such as electrochemical reactivity and mechanical stability. However, transition metal oxides as negative electrode materials for lithium ion batteries have a number of disadvantages: (1) the transition metal oxide has poor conductivity and is not beneficial to charge transfer in the charge and discharge process; (2) in the process of charging and discharging, the transition metal oxide is easy to generate obvious volume change, so that electrode materials are pulverized, the connection among the transition metal oxide and the electrode materials is reduced, and the system resistance is increased; or fall off the surface of the current collector, resulting in loss of active material.
To solve the above problems, many methods have been adopted, such as synthesizing iron oxide/cobalt oxide hybrid materials such as Fe2O3@Co3O4@ C composite nanomaterial, Fe2O3@Co3O4Nanowire, Co3O4@Fe2O3A core-shell acicular nanostructure. In addition to this, the present invention is,the layered hollow nanostructure is an effective method to mitigate volume changes during charging and discharging. The porous structure can not only reduce the diffusion path of lithium ions, but also has larger specific surface area to be fully contacted with the electrolyte. Therefore, the cobaltosic oxide/manganese dioxide hybrid material with the rod-shaped porous nano structure can effectively improve the lithium storage performance of the battery.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide negative electrode material.
The invention also aims to provide the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide negative electrode material prepared by the method.
The invention aims to provide application of the rod-shaped porous cobaltosic oxide/manganese dioxide negative electrode material in the fields of lithium ion batteries and the like.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide negative electrode material comprises the following steps:
(1) adding the manganese dioxide dispersion liquid into a 2-methylimidazole methanol solution for ultrasonic dispersion to obtain manganese dioxide/2-methylimidazole dispersion liquid;
(2) adding the manganese dioxide/2-methylimidazole dispersion liquid obtained in the step (1) into cobalt nitrate methanol hexahydrate dispersion liquid, standing for reaction, and centrifugally separating the reacted solution to obtain an organic metal framework/manganese dioxide compound;
(3) and (3) calcining the organic metal framework/manganese dioxide compound obtained in the step (2) at high temperature to obtain the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material.
Preferably, in the step (1), the preparation of the manganese dioxide dispersion comprises the steps of:
stirring potassium permanganate and water, adding concentrated hydrochloric acid for reaction, and filtering the solution after the reaction to obtain nanotube manganese dioxide; then adding the nanotube manganese dioxide into methanol for ultrasonic dispersion to obtain manganese dioxide dispersion liquid;
the content of the potassium permanganate in the water is 0.625-1 wt%; the volume ratio of the added concentrated hydrochloric acid to the water is 0.0125: 1-0.035: 1; the concentration of the concentrated hydrochloric acid is 35-37 wt%; the reaction temperature is 140-160 ℃, and the reaction time is 4-6 h.
Preferably, the potassium permanganate is added by adopting stirring treatment, the stirring treatment temperature is 20-25 ℃, and the stirring time is 5-10 min; the reaction temperature is 140-160 ℃, and the reaction time is 4-6 h.
Preferably, the resulting complex is preferably isolated, washed and dried. The separation can adopt vacuum filtration; the cleaning can be carried out by washing with water for multiple times; the drying is preferably carried out at 70-80 ℃ for 10-12 h.
Preferably, the length of the manganese dioxide in the manganese dioxide dispersion of step (1) is 1 to 2 μm, more preferably 1.5 μm; the manganese dioxide tube has a diameter of 50 to 150nm, more preferably 100 nm.
Preferably, the concentration of the methanol is 99.99 percent.
Preferably, the nanotube manganese dioxide is added and then stirred for reaction; the stirring reaction temperature is 20-25 ℃, and the ultrasonic time is 5-10 min.
Preferably, the nanotube manganese dioxide is present in the methanol in an amount of 0.125 to 0.25 wt%.
Preferably, in the step (1), the content of the 2-methylimidazole in the methanol is 0.5-0.8 wt%.
Preferably, in the step (2), the manganese dioxide dispersion may be subjected to ultrasonic treatment after adding 2-methylimidazole. The ultrasonic temperature is 20-25 ℃, and the ultrasonic time is 5-10 min.
Preferably, in the step (2), the manganese dioxide/2-methylimidazole dispersion liquid is added with a cobalt nitrate hexahydrate methanol solution and then is kept stand for 2-6 hours.
Preferably, in the step (2), the content of the cobalt nitrate hexahydrate in the methanol is 0.5-0.8 wt%; the standing time is 4-6 h.
Preferably, in step (2), the molar ratio of Mn to Co in the manganese dioxide/2-methylimidazole dispersion to cobalt nitrate hexahydrate methanol dispersion is 0.58: 1-0.77: 1.
preferably, in the step (2), the obtained complex is preferably separated, washed and dried. The separation can adopt centrifugal separation and the like; the cleaning can be carried out by respectively washing with methanol and water for multiple times; the drying is preferably carried out at 70-80 ℃ for 10-12 h.
Preferably, in the step (3), the calcination temperature is 400-450 ℃, and the calcination time is 2-4 h.
Preferably, in the step (3), the calcining atmosphere is an air atmosphere.
The porous cobaltosic oxide/nanotube manganese dioxide cathode material obtained by the preparation method is a cathode material which is formed by combining an organic metal framework and nanotube manganese dioxide and calcining the combination to generate a double transition metal oxide hybrid. The material is added with the nanotube manganese dioxide in the self-assembly process of the organic metal framework, and is calcined to form the rodlike porous cobaltosic oxide/nanotube manganese dioxide, the structure can effectively relieve the volume expansion problem of two transition metal oxides in the circulation process, simultaneously provides a more effective lithium ion transmission channel, improves the stress property of the material, and can improve the circulation capacity and the circulation performance of the lithium ion battery, so the material has good application prospect in the fields of the lithium ion battery and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, after the nanotube manganese dioxide is synthesized, the novel rod-shaped morphology structure can be uniformly formed in the self-assembly process by adjusting the use amounts of Mn and Co, the structural stability of the material is improved, and the morphology of the nanotube manganese dioxide is maintained.
(2) After the invention is calcined, the organic metal framework is converted into porous cobaltosic oxide and is combined with the nanotube manganese dioxide to form the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide double transition metal oxide hybrid anode material. The porous nano cobaltosic oxide and the nano hollow manganese dioxide have larger specific surface areas, can provide larger contact areas of electrodes and electrolyte, increase active sites of reaction, provide more effective lithium ion transmission channels, simultaneously relieve the problem of volume expansion of the cobaltosic oxide and the manganese dioxide in the circulating process by utilizing a porous and hollow structure, and can effectively improve the stress property of materials, thereby improving the circulating capacity and the circulating stability of the lithium ion battery.
(3) The invention adopts the solution method to prepare the porous cobaltosic oxide/nanotube manganese dioxide cathode material, has simple process and low equipment requirement, and is suitable for large-scale production.
Drawings
FIG. 1 is an SEM image of porous cobaltosic oxide and rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared in example 1 of the present invention.
FIG. 2 is a TEM image of a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared in example 1 of the present invention.
FIG. 3 is an XRD pattern of porous cobaltosic oxide, nanotube manganese dioxide and rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared in example 1 of the present invention.
FIG. 4 is a graph showing the results of electrochemical performance tests of the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared in example 1 of the present invention as a negative electrode material of a lithium ion battery.
FIG. 5 shows the high current of 1A g for the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared in example 1 of the present invention-1A cycle chart of time.
FIG. 6 shows that the molar ratio of Mn to Co in example 13 of the present invention is 1: TEM image of rod-like porous cobaltosic oxide/nanotube manganese dioxide prepared at 1 hour.
FIG. 7 shows that the molar ratio of Mn to Co in example 13 of the present invention is 0.58: TEM image of rod-like porous cobaltosic oxide/nanotube manganese dioxide prepared at 1 hour.
FIG. 8 is a TEM image of a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared at a calcination temperature of 400 ℃ in example 14 of the present invention.
FIG. 9 is an SEM image of a simple mixture of porous cobaltosic oxide/nanotube manganese dioxide prepared according to comparative example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto. All the raw materials and reagents used in the present invention are commercially available raw materials and reagents, unless otherwise specified.
Example 1: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of 37wt% concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) And (3) adding 75mL of manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding 50mL of 2-methylimidazole methanol dispersion into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) respectively placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
To examine the performance of the negative electrode material prepared in this example, a lithium ion battery was prepared using the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide obtained in this example as negative electrode materials, respectively. Wherein the mass ratio of the negative electrode material, the conductive acetylene black and the PVDF thickening agent is 7: 2: 1, the mixed slurry is coated on a copper foil and dried in a vacuum drying oven for 12 hours to prepare a negative electrode sheet, the negative electrode sheet and a lithium sheet form a lithium ion half battery, and the electrolyte is 1mol/L LiPF6/(EC + DME), the membrane was Celgard2400 membrane.
SEM images of porous cobaltosic oxide and rod-shaped porous cobaltosic oxide/nanotube manganese dioxide prepared in this example are shown in FIG. 1. It can be seen from A and B in FIG. 1 that porous cobaltosic oxide with a size of about 500nm is obtained by the method of the present invention, and from C and D in FIG. 1 that rod-like porous cobaltosic oxide/nanotube manganese dioxide with a size distribution similar to A and B in FIG. 1 is obtained by the method of the present invention, and a new structure similar to a lollipop is formed.
TEM images of the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide negative electrode material prepared in this example are shown in a and B of fig. 2. It can be seen that the porous cobaltosic oxide is combined with the nanotubes to form a lollipop-like hybrid structure, the size of the porous cobaltosic oxide is 500nm, and the diameter of the nanotubes is 100 nm.
The XRD patterns of the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide, porous cobaltosic oxide and nanotube manganese dioxide cathode material prepared in this example are shown in fig. 3, which shows that the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide has characteristic peaks of both porous cobaltosic oxide and nanotube manganese dioxide, which indicates that the crystal form of nanotube manganese dioxide is kept good after high-temperature calcination.
The cycle performance test results of the lithium ion battery assembled in this example are shown in fig. 4. As can be seen from A in FIG. 4, the rate capability of porous cobaltosic oxide is better than that of rod-shaped porous cobaltosic oxide/nanotube manganese dioxide at low current, and when the current intensity is higher than 1000mAg-1When the temperature of the water is higher than the set temperature,the rodlike porous cobaltosic oxide/nanotube manganese dioxide is superior to the porous cobaltosic oxide, and the current is 4000mAg-1When the capacity of the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide is kept at 290mA h g-1While the capacity of the porous cobaltosic oxide is only 120mA h g-1. As can be seen from B in FIG. 4, at 300mAg-1After 160 cycles of circulation, the capacity of the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide reaches 1100mA h g-1Close to the theoretical specific capacity of manganese dioxide (1232mA h g)-1) The capacity of the porous cobaltosic oxide is only 410mA h g-1The capacity is far lower than the capacity obtained by rodlike porous cobaltosic oxide/nanotube manganese dioxide and also far lower than the theoretical specific capacity (890mA h g) of the cobaltosic oxide-1). FIG. 5 shows the application of a bar-shaped porous cobaltosic oxide/nanotube manganese dioxide in high current of 1Ag-1The cycle chart shows that after 210 cycles, the capacity reaches 687mA g-1The coulombic efficiency is kept stable, which shows that the hybridized double transition metal oxide not only has the characteristics of two metal oxides, but also has synergistic effect and shows good multiplying power and cycle performance.
The SEM images, TEM images, XRD images and electrochemical performance test results of the materials obtained in the following examples 2-12 are similar to those in example 1.
Example 2: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.6g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 3: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 140 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 4: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 4 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 5: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.06g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 6: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 30mL of methanol, and performing ultrasonic dispersion for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 7: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 30mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 8: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 4h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 9: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of manganese dioxide dispersion liquid obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.006: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.006: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 10: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.006: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.006: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 11: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.007: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.005: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 400 ℃, calcining for 2h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 12: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding the manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) Adding the 2-methylimidazole methanol dispersion liquid into cobalt nitrate hexahydrate methanol dispersion liquid, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(6) And (3) placing the organic metal framework/manganese dioxide compound and the organic metal framework obtained in the steps (4) and (5) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 4h, and cooling to room temperature to obtain rod-shaped porous cobaltosic oxide/nanotube manganese dioxide and porous cobaltosic oxide.
Example 13: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of 37wt% concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) The manganese dioxide dispersion obtained in step (2) was added to 50mL of a 2-methylimidazole methanol dispersion in an amount shown in table 1, wherein the mass ratio of 2-methylimidazole to methanol was 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) Adding 85mL of manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) And (4) placing the organic metal framework/manganese dioxide compound obtained in the step (4) in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 2h, and cooling to room temperature to obtain the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide.
TABLE 1
Figure BDA0002769415420000161
It can be seen from FIG. 6 that the Mn: co is 1: 1, the resulting porous cobaltosic oxide/manganese dioxide material is not uniform and does not form a rod-like structure.
It can be seen from FIG. 7 that the Mn: co is 0.58: 1, the structure of the rod-shaped porous cobaltosic oxide/manganese dioxide material can be still synthesized.
Example 15: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of 37wt% concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) And (2) dissolving 0.05g of nanotube manganese dioxide obtained in the step (1) in 35mL of methanol, and ultrasonically dispersing for 5min to obtain a manganese dioxide dispersion liquid.
(3) Adding 25mL of the manganese dioxide dispersion obtained in the step (2) into 50mL of 2-methylimidazole methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, carrying out ultrasonic dispersion for 5 minutes to obtain a manganese dioxide/2-methylimidazole dispersion liquid.
(4) And (3) adding 75mL of manganese dioxide/2-methylimidazole dispersion obtained in the step (3) into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, finally performing centrifugal separation, washing for 3 times by using methanol, and drying for 12h at 80 ℃ to obtain the organic metal framework/manganese dioxide compound.
(5) And (4) placing the organic metal framework/manganese dioxide compound obtained in the step (4) in a muffle furnace in an air atmosphere, heating to 400 ℃, calcining for 2h, and cooling to room temperature to obtain the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide.
It can be seen from figure 8 that the structure of the rod-shaped porous cobaltosic oxide/manganese dioxide material remains intact when the temperature is reduced to 400 c.
Comparative example 1: preparation of porous cobaltosic oxide/nanotube manganese dioxide cathode material
(1) 0.5g of potassium permanganate is firstly added into 60mL of water, stirred for 5min, then 1mL of 37wt% concentrated hydrochloric acid is added, and the mixed solution is poured into a reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 5 h. And (3) carrying out vacuum filtration on the substance obtained by the reaction, washing with water for 3 times, and drying at 80 ℃ for 12h to obtain the nanotube manganese dioxide.
(2) Adding 50mL of 2-methylimidazole methanol dispersion into 30mL of cobalt nitrate hexahydrate methanol dispersion, wherein the mass ratio of 2-methylimidazole to methanol is 0.005: 1, the mass ratio of the cobalt nitrate hexahydrate to the methanol is 0.007: 1, standing for 5h, then performing centrifugal separation, washing with methanol for 3 times, and drying at 80 ℃ for 12h to obtain the organic metal framework.
(3) And (3) mixing the nanotube manganese dioxide obtained in the step (1) and the step (2) with an organic metal framework, placing the mixture in a muffle furnace in an air atmosphere, heating to 450 ℃, calcining for 5 hours, and cooling to room temperature to obtain a porous cobaltosic oxide/nanotube manganese dioxide mixture.
The porous cobaltosic oxide/nanotube manganese dioxide mixture prepared in this comparative example was compared with example 1, the nanotube manganese dioxide and porous cobaltosic oxide were not uniformly distributed, and the nanotube manganese dioxide was agglomerated without forming rod-shaped porous cobaltosic oxide/nanotube manganese dioxide (see fig. 9).
The above embodiments are the best mode for carrying out the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and are included in the scope of the present invention.

Claims (8)

1. A preparation method of a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material is characterized by comprising the following steps:
(1) adding the manganese dioxide dispersion liquid into a 2-methylimidazole methanol solution for ultrasonic dispersion to obtain manganese dioxide/2-methylimidazole dispersion liquid;
(2) adding the manganese dioxide/2-methylimidazole dispersion liquid obtained in the step (1) into cobalt nitrate methanol hexahydrate dispersion liquid, standing for reaction, and centrifugally separating the reacted solution to obtain an organic metal framework/manganese dioxide compound;
(3) calcining the organic metal frame/manganese dioxide compound obtained in the step (2) at high temperature to obtain a rod-shaped porous cobaltosic oxide/nanotube manganese dioxide cathode material;
in the step (1), the preparation of the manganese dioxide dispersion liquid comprises the following steps:
stirring potassium permanganate and water, adding concentrated hydrochloric acid for reaction, and filtering the solution after the reaction to obtain nanotube manganese dioxide; then adding the nanotube manganese dioxide into methanol for ultrasonic dispersion to obtain manganese dioxide dispersion liquid;
the content of the potassium permanganate in the water is 0.625-1 wt%; the volume ratio of the added concentrated hydrochloric acid to the water is 0.0125: 1-0.035: 1; the concentration of the concentrated hydrochloric acid is 35-37 wt%; the reaction temperature is 140-160 ℃, and the reaction time is 4-6 h;
in the step (2), the molar ratio of Mn to Co in the manganese dioxide/2-methylimidazole dispersion and the cobalt nitrate hexahydrate methanol dispersion is 0.58: 1-0.77: 1.
2. the method according to claim 1, wherein the manganese dioxide dispersion liquid of step (1) contains 0.125 to 0.25wt% of manganese dioxide.
3. The method according to claim 1, wherein the manganese dioxide in the manganese dioxide dispersion liquid of step (1) has a length of 1 to 2 μm and a diameter of 50 to 150 nm.
4. The method according to claim 1, wherein the 2-methylimidazole methanol solution of step (1) contains 2-methylimidazole in methanol in an amount of 0.5 to 0.8 wt%.
5. The method according to claim 1, wherein in the cobalt nitrate hexahydrate methanol dispersion liquid in the step (2), the content of cobalt nitrate hexahydrate in methanol is 0.5-0.8 wt%; the standing time is 4-6 h.
6. The preparation method as claimed in claim 1, wherein in the step (3), the calcination temperature is 400-450 ℃ and the calcination time is 2-4 h.
7. A rod-shaped porous cobaltosic oxide/nanotube manganese dioxide negative electrode material, characterized in that it is prepared by the method of any one of claims 1 to 6.
8. The use of the rod-shaped porous cobaltosic oxide/nanotube manganese dioxide negative electrode material of claim 7 in the preparation of lithium ion batteries.
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