CN114975933A - Hierarchical slice MnO 2 @Co 3 O 4 @ C flexible composite electrode and preparation method and application thereof - Google Patents

Hierarchical slice MnO 2 @Co 3 O 4 @ C flexible composite electrode and preparation method and application thereof Download PDF

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CN114975933A
CN114975933A CN202210619826.0A CN202210619826A CN114975933A CN 114975933 A CN114975933 A CN 114975933A CN 202210619826 A CN202210619826 A CN 202210619826A CN 114975933 A CN114975933 A CN 114975933A
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张九如
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Abstract

Hierarchical slice MnO 2 @Co 3 O 4 The @ C flexible composite electrode and the preparation method and the application thereof comprise the following steps: placing the carbon cloth in a potassium permanganate solution, and sequentially performing ultrasonic treatment, cleaning and drying; respectively dissolving cobalt nitrate hexahydrate and dimethyl imidazole into deionized water to form solutionsPutting the pretreated carbon cloth into the solution B for ultrasonic treatment, then pouring the solution A into the solution B for standing, taking out the carbon cloth for washing, drying, putting into a tubular furnace, and sequentially carrying out annealing carbonization and oxidation to obtain Co 3 O 4 @ C nanoplatelet arrays; dissolving potassium permanganate into deionized water, pouring into a high-pressure reaction kettle, and adding Co 3 O 4 And (3) the @ C nano flaky array is insulated, the contents in the high-pressure reaction kettle are taken out, cooled, washed and dried to obtain the composite electrode. The method is simple, the synthesis conditions are mild and easy to control, the obtained electrode has high electrochemical capacity, and the electrode can show excellent electrochemical performance when being used as an ZIB electrode.

Description

Hierarchical slice MnO 2 @Co 3 O 4 @ C flexible composite electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of flexible electrode materials and preparation, and particularly relates to graded flaky MnO 2 @Co 3 O 4 @ C flexible composite electrode and preparation method and application thereof.
Background
The rechargeable Zinc Ion Battery (ZIB) has the advantages of low cost, abundant materials, high safety, acceptable energy density, environmental friendliness and the like, and has wide application prospects in large-scale energy storage and portable electronic applications. It is well known that the electrode material is one of the main factors determining the electrochemical performance of zinc ion batteries. Currently, research on positive electrode materials of aqueous zinc ion batteries has mainly focused on transition metal oxides. Among them, manganese oxide materials have been widely studied for their advantages of diversified crystal structures, high specific capacity, non-toxicity, low cost, and the like. However, when the manganese oxide material is used as a cathode material of an aqueous zinc ion battery, the problems of structural collapse, byproduct derivation, electrode material dissolution and the like exist in the charging and discharging processes, and the cycling stability of the manganese oxide material is directly influenced.
There are two general methods for improving the performance of the material, the first method is to introduce various defects, such as oxygen defect, manganese defect, etc., but the method also has various defects, such as over-high cost, uncontrollable reaction, etc.; the second method is to compound various carbon materials, such as graphene, redox graphene, etc., and this method also has the disadvantages of high cost and complicated steps.
Disclosure of Invention
The invention aims to provide hierarchical flaky MnO 2 @Co 3 O 4 The method is simple, the synthesis condition is mild and easy to control, the cost is low, the electrochemical capacity of the prepared product is high, and the prepared product can show excellent electrochemical performance when being used as a rechargeable zinc ion battery electrode.
In order to achieve the purpose, the invention adopts the technical scheme that: hierarchical slice MnO 2 @Co 3 O 4 A preparation method of a @ C flexible composite electrode,the method comprises the following steps:
(1) placing the carbon cloth in a potassium permanganate solution for ultrasonic treatment, repeatedly and sequentially cleaning the carbon cloth by using deionized water and absolute ethyl alcohol, and drying the carbon cloth to obtain a pretreated carbon cloth;
(2) respectively dissolving cobalt nitrate hexahydrate and dimethyl imidazole into deionized water, and stirring to form a homogeneous solution A and a homogeneous solution B; putting the pretreated carbon cloth into the solution B for ultrasonic treatment, then pouring the solution A into the solution B to form a purple solution I, standing for a period of time, taking out the carbon cloth, washing with deionized water, and drying to obtain a CC/ZIF67 precursor; placing the CC/ZIF67 precursor in a tube furnace, annealing and carbonizing under the argon atmosphere, and oxidizing in the air to obtain Co growing on carbon cloth 3 O 4 @ C nanoplatelet arrays;
(3) dissolving potassium permanganate into deionized water, stirring to form a purple solution II, pouring the purple solution II into a high-pressure reaction kettle, and adding the Co growing on the carbon cloth prepared in the step (2) 3 O 4 The @ C nano flaky array is prepared by putting a high-pressure reaction kettle into a drying oven for heat preservation for a period of time, taking out the contents in the high-pressure reaction kettle, washing the contents with deionized water after cooling, and drying to obtain hierarchical flaky MnO 2 @Co 3 O 4 @ C Flexible composite electrode.
Preferably, in the step (1), the concentration of potassium permanganate is 0.3-1mol/L, and the ultrasonic time is 10-20 min; the size of the carbon cloth is 1-5cm 2 And repeatedly and sequentially cleaning the mixture for 3 times by using deionized water and absolute ethyl alcohol.
Preferably, in the step (2), the concentration of the solution A is 0.01-0.1mol/L, the concentration of the solution B is 0.2-0.6mol/L, the carbon cloth is put into the solution B for ultrasonic treatment for 5-20min, and the volume ratio of the solution A to the solution B is 1: (1-2).
Preferably, in the step (2), the homogeneous solution A and the homogeneous solution B are respectively formed by stirring for 5-20min through a magnetic stirrer; the standing temperature of the mixed solution A and the mixed solution B is 25 ℃, and the standing time is 4-24 h.
Preferably, in the step (2), the temperature of the annealing carbonization heat treatment in the argon atmosphere is 400-; the heat treatment temperature for oxidation in the air is 300-500 ℃, the time is 1-4h, and the heating rate is 2-10 ℃/min.
Preferably, in the step (3), the concentration of potassium permanganate in the purple solution II is 0.001-0.01 mol/L; the temperature of the drying box is set to be 120-170 ℃, and the heat preservation time in the drying box is 0.5-4 h.
Preferably, in the step (3), a purple solution II is formed after magnetic stirring; the high-pressure reaction kettle is a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining.
Preferably, in steps (1) to (3), the drying conditions are all as follows: the drying temperature is 60-80 ℃, and the drying time is 6-24 h.
The invention also provides a hierarchical flaky MnO 2 @Co 3 O 4 The @ C flexible composite electrode is prepared by the preparation method.
The invention also provides the hierarchical flaky MnO 2 @Co 3 O 4 The application of the @ C flexible composite electrode as the positive electrode of the zinc ion battery.
Compared with the prior art, the invention has the following advantages:
according to the invention, the flaky cobaltosic oxide nano array derived from ZIF67 is compounded with manganese dioxide, so that the electrochemical performance of the material is effectively improved. The cobaltosic oxide (flaky nano array) with structural stability and controllable morphology is prepared on the carbon cloth, and the cobaltosic oxide nano sheet array keeps a nano porous structure with excellent conductivity, so that the cobaltosic oxide nano sheet array can be used for preparing a high-performance composite material to improve the performance of manganese oxide. The preparation method has the advantages of mild preparation conditions, simple process, controllable operation and lower cost; the obtained hierarchical flaky MnO 2 @Co 3 O 4 @ C flexible composite electrode as anode, zinc foil as cathode and ZnSO with concentration of 2mol/L 4 +0.1mol/L MnSO 4 The aqueous solution is used as electrolyte and assembled into a button cell for electrochemical test, and the result shows that the hierarchical flaky MnO is 2 @Co 3 O 4 The @ C flexible composite electrode shows high specific capacity of 250mAh/g at 0.1A/g, and the capacity is kept at 70% after the flexible composite electrode is cycled for 1000 times under the current density of 1A/g, so that the flexible composite electrode showsExcellent electrochemical performance.
Drawings
FIG. 1 is a hierarchical sheet MnO prepared in accordance with an embodiment of the present invention 2 @Co 3 O 4 SEM image of @ C flexible composite electrode;
FIG. 2 is a hierarchical sheet MnO prepared in accordance with an embodiment of the present invention 2 @Co 3 O 4 XRD pattern of @ C flexible composite electrode.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example one
Hierarchical flaky MnO 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode comprises the following steps:
(1) pretreatment of carbon cloth
Placing a carbon cloth (1cm multiplied by 2cm) in a 0.5mol/L potassium permanganate solution for ultrasonic treatment for 15min, repeatedly and sequentially cleaning for 3 times by deionized water and absolute ethyl alcohol, and drying in a drying oven at 70 ℃ for 12h to obtain the pretreated carbon cloth;
(2) preparation of Co grown on carbon cloth 3 O 4 @ C nanosheet array
Respectively dissolving 2mmol of cobalt nitrate hexahydrate and 16mmol of dimethyl imidazole into 40mL of deionized water, and magnetically stirring for 10min to form a homogeneous solution A and a homogeneous solution B; putting the pretreated carbon cloth into the solution B for ultrasonic treatment for 10min, then pouring the solution A into the solution B to form a purple solution I, standing for 6h at 25 ℃, taking out the carbon cloth, washing with deionized water, and drying in an oven at 70 ℃ for 12h to obtain a CC/ZIF67 precursor; placing the CC/ZIF67 precursor in a tube furnace, firstly annealing and carbonizing in an argon atmosphere, and carrying out heat treatment at 500 ℃ for 2h at the heating rate of 3 ℃/min; finally oxidizing in air, and carrying out heat treatment at 350 ℃ for 1h at the heating rate of 3 ℃/min to obtain Co grown on the carbon cloth 3 O 4 @ C nanoplatelet arrays;
(3) preparation of hierarchical flaky MnO 2 @Co 3 O 4 @ C flexible composite electrode
0.057mmol higherDissolving potassium manganate into 36mL deionized water, forming a purple solution II through magnetic stirring, pouring the purple solution II into 50mL stainless steel high-pressure reaction kettle containing a polytetrafluoroethylene lining, and adding the Co growing on the carbon cloth prepared in the step (2) 3 O 4 @ C nanometer flake array, placing the high-pressure reaction kettle into a drying box, setting the temperature of the drying box to be 150 ℃, preserving heat for 1h, taking out the contents in the high-pressure reaction kettle, washing the contents with deionized water after cooling, and drying the contents in the drying box at 70 ℃ for 12h to obtain hierarchical flake MnO 2 @Co 3 O 4 @ C Flexible composite electrode.
This example also provides a hierarchical sheet MnO 2 @Co 3 O 4 The @ C flexible composite electrode is prepared by the preparation method. The SEM is shown in FIG. 1, and it can be seen that the synthesized composite material is a cross-linked hierarchical sheet structure, and the bulk sheet structure is Co 3 O 4 And a carbon skeleton with a thickness of 100-300nm and a small-scale grid-like sheet structure MnO 2 And the size is 40-60 nm. As can be seen from FIG. 2, the main phase is MnO 2 Or Co 3 O 4 Four diffraction peaks at 36.9, 44.8, 59.4 and 65.3 deg. other than the two diffraction peaks of the carbon cloth belong to Co 3 O 4 The diffraction peaks of the (511) and (440) crystal faces of (1) and (440) are JCPDS No.02-0422 corresponding to PDF card, and the two diffraction peaks at 37.2 degrees and 65.5 degrees respectively belong to MnO 2 The diffraction peaks of the (311) and (312) crystal planes of the film are corresponding to the PDF cards JCPDS No.80-1098, and no other crystal phases are detected, which indicates that MnO is prepared 2 @Co 3 O 4 The @ C flexible composite electrode has good purity.
This example also provides the above-described hierarchical sheet MnO 2 @Co 3 O 4 The application of the @ C flexible composite electrode as the positive electrode of the zinc ion battery is as follows: to grade the sheet MnO 2 @Co 3 O 4 @ C flexible composite electrode as anode, zinc foil as cathode and ZnSO with concentration of 2mol/L 4 +0.1mol/L MnSO 4 The aqueous solution is used as electrolyte and assembled into a button cell for electrochemical test, and the result shows that the graded sheet isMnO 2 @Co 3 O 4 The @ C flexible composite electrode shows high specific capacity of 250mAh/g at 0.1A/g, the capacity is kept at 70% after the flexible composite electrode is cycled for 1000 times at the current density of 1A/g, and excellent electrochemical performance is shown.
Example two
Hierarchical slice MnO 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode comprises the following steps:
(1) pretreatment of carbon cloth
Placing a carbon cloth (2cm multiplied by 2cm) in a 0.3mol/L potassium permanganate solution for ultrasonic treatment for 10min, repeatedly and sequentially cleaning for 3 times by using deionized water and absolute ethyl alcohol, and drying in an oven at 70 ℃ for 12h to obtain a pretreated carbon cloth;
(2) preparation of Co grown on carbon cloth 3 O 4 @ C nanosheet array
Respectively dissolving 1mmol of cobalt nitrate hexahydrate and 16mmol of dimethyl imidazole into 80mL of deionized water, and magnetically stirring for 5min to form a homogeneous solution A and a homogeneous solution B; putting the pretreated carbon cloth into the solution B for ultrasonic treatment for 5min, then pouring the solution A into the solution B to form a purple solution I, standing for 4h at 25 ℃, taking out the carbon cloth, washing with deionized water, and drying in an oven at 70 ℃ for 12h to obtain a CC/ZIF67 precursor; placing the CC/ZIF67 precursor in a tube furnace, firstly annealing and carbonizing in an argon atmosphere, and carrying out heat treatment at 400 ℃ for 3h at the heating rate of 2 ℃/min; finally oxidizing in air, heat treating at 300 deg.C for 2h with a heating rate of 2 deg.C/min to obtain Co grown on carbon cloth 3 O 4 @ C nanoplatelet arrays;
(3) preparation of hierarchical flaky MnO 2 @Co 3 O 4 @ C flexible composite electrode
Dissolving 0.036mmol of potassium permanganate into 36mL of deionized water, magnetically stirring to form a purple solution II, pouring the purple solution II into 50mL of stainless steel high-pressure reaction kettle containing a polytetrafluoroethylene lining, and adding the Co growing on the carbon cloth prepared in the step (2) 3 O 4 The @ C nano flaky array is prepared by placing a high-pressure reaction kettle into a drying oven, setting the temperature of the drying oven to be 120 ℃, and preserving heatTaking out the contents of the high-pressure reaction kettle after 0.5h, cooling, washing with deionized water, and drying in a 70 ℃ oven for 12h to obtain hierarchical flaky MnO 2 @Co 3 O 4 @ C Flexible composite electrode.
This example also provides a hierarchical sheet MnO 2 @Co 3 O 4 The @ C flexible composite electrode is prepared by the preparation method.
This example also provides the above-described hierarchical sheet MnO 2 @Co 3 O 4 The application of the @ C flexible composite electrode as the positive electrode of the zinc ion battery is as follows: to grade the sheet MnO 2 @Co 3 O 4 @ C flexible composite electrode as anode, zinc foil as cathode and ZnSO with concentration of 2mol/L 4 +0.1mol/L MnSO 4 The aqueous solution is used as electrolyte and assembled into a button cell for electrochemical test, and the result shows that the hierarchical flaky MnO is 2 @Co 3 O 4 The @ C flexible composite electrode shows high specific capacity of 200mAh/g at 0.1A/g, capacity is kept at 60% after the flexible composite electrode is cycled for 1000 times at current density as high as 1A/g, and excellent electrochemical performance is shown.
EXAMPLE III
Hierarchical slice MnO 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode comprises the following steps:
(1) pretreatment of carbon cloth
Placing a carbon cloth (2cm multiplied by 2.5cm) in a 1mol/L potassium permanganate solution for ultrasonic treatment for 20min, repeatedly and sequentially cleaning for 3 times by using deionized water and absolute ethyl alcohol, and drying in an oven at 70 ℃ for 12h to obtain a pretreated carbon cloth;
(2) preparation of Co grown on carbon cloth 3 O 4 @ C nanosheet array
Respectively dissolving 4mmol of cobalt nitrate hexahydrate and 24mmol of dimethyl imidazole into 40mL of deionized water, and magnetically stirring for 20min to form a homogeneous solution A and a homogeneous solution B; putting the pretreated carbon cloth into the solution B for ultrasonic treatment for 20min, then pouring the solution A into the solution B to form a purple solution I, standing for 24h at 25 ℃, taking out the carbon cloth, washing with deionized water, and thenDrying in an oven at 70 ℃ for 12h to obtain a CC/ZIF67 precursor; placing the CC/ZIF67 precursor in a tube furnace, firstly annealing and carbonizing in an argon atmosphere, and carrying out heat treatment at 700 ℃ for 4h at the heating rate of 10 ℃/min; finally oxidizing in air, heat treating at 500 deg.C for 4h with a heating rate of 10 deg.C/min to obtain Co grown on carbon cloth 3 O 4 @ C nanoplatelet arrays;
(3) preparation of hierarchical flaky MnO 2 @Co 3 O 4 @ C flexible composite electrode
Dissolving 0.36mmol of potassium permanganate into 36mL of deionized water, magnetically stirring to form a purple solution II, pouring the purple solution II into 50mL of stainless steel high-pressure reaction kettle containing a polytetrafluoroethylene lining, and adding the Co grown on the carbon cloth prepared in the step (2) 3 O 4 @ C nano flaky array, putting the high-pressure reaction kettle into a drying box, setting the temperature of the drying box to be 170 ℃, preserving heat for 4 hours, taking out the contents in the high-pressure reaction kettle, washing the contents with deionized water after cooling, and drying the contents in the drying box at 70 ℃ for 12 hours to obtain hierarchical flaky MnO 2 @Co 3 O 4 @ C Flexible composite electrode.
This example also provides a hierarchical sheet MnO 2 @Co 3 O 4 The @ C flexible composite electrode is prepared by the preparation method.
This example also provides the above-described hierarchical sheet MnO 2 @Co 3 O 4 The application of the @ C flexible composite electrode as the positive electrode of the zinc ion battery is as follows: to grade the sheet MnO 2 @Co 3 O 4 @ C flexible composite electrode as anode, zinc foil as cathode and ZnSO with concentration of 2mol/L 4 +0.1mol/L MnSO 4 The aqueous solution is used as electrolyte and assembled into a button cell for electrochemical test, and the result shows that the hierarchical flaky MnO is 2 @Co 3 O 4 The @ C flexible composite electrode shows high specific capacity of 180mAh/g at 0.1A/g, the capacity is kept 65% after the flexible composite electrode is cycled for 1000 times at the current density of 1A/g, and excellent electrochemical performance is shown.
The above results indicate that the hierarchical flaky MnO prepared by the present invention 2 @Co 3 O 4 The @ C flexible composite electrode can be used as a positive electrode material of a zinc ion battery.

Claims (10)

1. Hierarchical flaky MnO 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized by comprising the following steps of:
(1) placing the carbon cloth in a potassium permanganate solution for ultrasonic treatment, repeatedly and sequentially cleaning the carbon cloth by using deionized water and absolute ethyl alcohol, and drying the carbon cloth to obtain a pretreated carbon cloth;
(2) respectively dissolving cobalt nitrate hexahydrate and dimethyl imidazole into deionized water, and stirring to form a homogeneous solution A and a homogeneous solution B; putting the pretreated carbon cloth into the solution B for ultrasonic treatment, then pouring the solution A into the solution B to form a purple solution I, standing for a period of time, taking out the carbon cloth, washing with deionized water, and drying to obtain a CC/ZIF67 precursor; placing the CC/ZIF67 precursor in a tube furnace, annealing and carbonizing under the argon atmosphere, and oxidizing in the air to obtain Co growing on carbon cloth 3 O 4 @ C nanoplatelet arrays;
(3) dissolving potassium permanganate into deionized water, stirring to form a purple solution II, pouring the purple solution II into a high-pressure reaction kettle, and adding the Co growing on the carbon cloth prepared in the step (2) 3 O 4 The @ C nano flaky array is prepared by putting a high-pressure reaction kettle into a drying oven for heat preservation for a period of time, taking out the contents in the high-pressure reaction kettle, washing the contents with deionized water after cooling, and drying to obtain hierarchical flaky MnO 2 @Co 3 O 4 @ C flexible composite electrode.
2. The graded, sheet-like MnO of claim 1 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the step (1), the concentration of potassium permanganate is 0.3-1mol/L, and the ultrasonic time is 10-20 min; the size of the carbon cloth is 1-5cm 2 And repeatedly and sequentially cleaning the mixture for 3 times by using deionized water and absolute ethyl alcohol.
3. A grading according to claim 1 or 2Sheet MnO 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the step (2), the concentration of the solution A is 0.01-0.1mol/L, the concentration of the solution B is 0.2-0.6mol/L, carbon cloth is placed in the solution B for ultrasonic treatment for 5-20min, and the volume ratio of the solution A to the solution B is 1: (1-2).
4. A graded sheet MnO according to claim 1 or 2 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the step (2), the homogeneous solution A and the homogeneous solution B are formed by stirring for 5-20min through a magnetic stirrer respectively; the standing temperature of the mixed solution A and the mixed solution B is 25 ℃, and the standing time is 4-24 h.
5. A graded sheet MnO according to claim 1 or 2 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the step (2), the temperature of annealing carbonization in the argon atmosphere is 400-700 ℃, the time is 2-4h, and the heating rate is 2-10 ℃/min; the heat treatment temperature for oxidation in the air is 300-500 ℃, the time is 1-4h, and the heating rate is 2-10 ℃/min.
6. A graded sheet MnO according to claim 1 or 2 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the step (3), the concentration of potassium permanganate in the purple solution II is 0.001-0.01 mol/L; the temperature of the drying box is set to be 120-170 ℃, and the heat preservation time in the drying box is 0.5-4 h.
7. A graded sheet MnO according to claim 1 or 2 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the step (3), a purple solution II is formed after magnetic stirring; the high-pressure reaction kettle is a stainless steel high-pressure reaction kettle containing a polytetrafluoroethylene lining.
8. A graded sheet MnO according to claim 1 or 2 2 @Co 3 O 4 The preparation method of the @ C flexible composite electrode is characterized in that in the steps (1) to (3), the drying conditions are as follows: the drying temperature is 60-80 ℃, and the drying time is 6-24 h.
9. Hierarchical slice MnO 2 @Co 3 O 4 A @ C flexible composite electrode, characterized by being produced by the production method according to any one of claims 1 to 8.
10. The hierarchical sheet MnO of claim 9 2 @Co 3 O 4 The application of the @ C flexible composite electrode as the positive electrode of the zinc ion battery.
CN202210619826.0A 2022-06-02 2022-06-02 Hierarchical slice MnO 2 @Co 3 O 4 @ C flexible composite electrode and preparation method and application thereof Withdrawn CN114975933A (en)

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CN116487576A (en) * 2023-06-20 2023-07-25 河南师范大学 Preparation method and application of flexible self-supporting ferro-manganese oxide positive electrode material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116487576A (en) * 2023-06-20 2023-07-25 河南师范大学 Preparation method and application of flexible self-supporting ferro-manganese oxide positive electrode material
CN116487576B (en) * 2023-06-20 2023-08-25 河南师范大学 Preparation method and application of flexible self-supporting ferro-manganese oxide positive electrode material

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