CN114725334B - Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof - Google Patents
Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof Download PDFInfo
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Abstract
本发明提供了一种花状硒化锌‑锰/炭复合材料及其制备方法和应用，花状硒化锌‑锰/炭复合材料包括由2D多孔炭纳米片组装而成的花状结构，2D多孔炭纳米片上负载有硒化锌‑锰颗粒，化学通式为Zn(1‑x)MnxSe，0.2≤x≤0.4；制备方法包括以下步骤：(1)将硝酸锌、硝酸锰、聚乙烯吡咯烷酮和均苯三甲酸溶于溶剂中，得混合液；(2)将混合液进行溶剂热反应，结束后自然冷却至室温，离心洗涤、烘干，得花状前驱体；(3)将花状前驱体与硒粉在氩气气氛下煅烧，冷却后碾磨过筛。该复合材料具有良好的导电网络，为材料的体积膨胀提供了缓冲空间，可减少离子的迁移距离从而提高材料整体的离子迁移效率，提高了材料的比容量和电化学稳定性。
The invention provides a flower-shaped zinc selenide-manganese/carbon composite material and its preparation method and application. The flower-shaped zinc selenide-manganese/carbon composite material includes a flower-like structure assembled from 2D porous carbon nanosheets, 2D The porous carbon nanosheets are loaded with zinc-manganese particles, the general chemical formula is Zn (1-x) Mn x Se, 0.2≤x≤0.4; the preparation method includes the following steps: (1) combine zinc nitrate, manganese nitrate, poly Vinylpyrrolidone and trimesic acid are dissolved in a solvent to obtain a mixed solution; (2) The mixed solution is subjected to a solvothermal reaction, and after completion, it is naturally cooled to room temperature, centrifuged, washed, and dried to obtain a flower-like precursor; (3) The flower-like precursor and selenium powder are calcined in an argon atmosphere, cooled and then ground and sieved. The composite material has a good conductive network, which provides a buffer space for the volume expansion of the material, reduces the migration distance of ions, thereby improving the overall ion migration efficiency of the material, and improves the specific capacity and electrochemical stability of the material.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a flower-like zinc selenide-manganese/carbon composite material, and a preparation method and application thereof.
Background
The sodium ion battery has the advantages of low cost, high raw material abundance and the like. However, the current sodium ion battery cathode material has low mass specific capacity, and dendrite sodium is easy to generate in the process of high-current charge and discharge to cause safety problems, so that the large-scale commercial application of the material is severely restricted, and therefore, the research and development of the sodium ion battery cathode material with good performance and high mass specific capacity is urgently needed. The zinc selenide can simultaneously perform conversion reaction and alloying reaction, so that the zinc selenide has better theoretical capacity advantage than other selenides, has a lower discharge platform of zinc selenide, is environment-friendly and low in cost, and is always considered as one of potential candidates of the negative electrode of the sodium ion battery. However, zinc selenide, like other metal compounds, belongs to semiconductors, resulting in poor conductivity and sodium ion diffusion efficiency of zinc selenide, and severely limiting the specific capacity of zinc selenide in the sodium storage process. In addition, the simple zinc selenide electrode tends to have extremely large volume expansion in the charge and discharge process, so that a stable solid interface plasma film cannot be formed, and finally, the electrode material is continuously pulverized, and the capacity is rapidly reduced. These problems directly limit the commercial use of zinc selenide based sodium ion anode materials. Therefore, aiming at the defects, the transformation and modification of the zinc selenide material are carried out to improve the overall electrochemical performance of the material, and the method has very important significance for the research and development and design of zinc selenide-based material and even sodium ion battery cathode material.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects in the background art, and provides a flower-like zinc selenide-manganese/carbon composite material, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the flower-shaped zinc selenide-manganese/carbon composite material comprises a flower-shaped structure assembled by 2D porous carbon nano sheets, wherein zinc selenide-manganese particles are loaded on the 2D porous carbon nano sheets, and the chemical formula of the zinc selenide-manganese is Zn (1-x) Mn x Se, wherein 0.2≤x≤0.4。
Preferably, the carbon content of the flower-like zinc selenide-manganese/carbon composite material is 40-50%. The carbon content is controlled within the range, the volume expansion buffering effect of the carbon material in the circulation process is not influenced, and the higher specific capacity can be considered.
As a general inventive concept, the invention provides a preparation method of the flower-shaped zinc selenide-manganese/carbon composite material, which comprises the following steps:
(1) Zinc nitrate, manganese nitrate, polyvinylpyrrolidone and trimesic acid are dissolved in a solvent to obtain a mixed solution;
(2) Carrying out solvothermal reaction on the mixed solution, naturally cooling to room temperature after the reaction is finished, centrifugally washing and drying the obtained material to obtain a flower-shaped precursor;
(3) And respectively placing the flower-shaped precursor and the selenium powder into two reaction porcelain boats, placing into a tube furnace, calcining under an argon atmosphere, cooling, grinding and sieving to obtain the flower-shaped zinc selenide-manganese/carbon composite energy storage material.
When the flower-shaped zinc selenide-manganese/carbon composite material is prepared by the method, when zinc nitrate and manganese nitrate are replaced by other zinc salts and manganese salts, a flower-shaped precursor is difficult to prepare, and if zinc nitrate is singly used, the prepared energy storage material has a rod-shaped structure; if the manganese nitrate is singly used, the prepared energy storage material has a spherical structure; and then the flower-shaped zinc selenide-manganese/carbon composite energy storage material cannot be prepared. The flower-shaped precursor consists of a 2D sheet structure with the thickness smaller than 100nm, and the structure can improve the contact area between the energy storage material obtained later and the electrolyte and provide a buffer space for volume expansion in the charge and discharge process.
Preferably, in the step (1), the molar ratio of the zinc nitrate to the manganese nitrate is 1 (0.2-0.8), and the molar ratio of the total molar amount of the zinc nitrate and the manganese nitrate to the trimesic acid is 1-1.8:2-2.5. The invention can make the prepared flower-shaped precursor structure better by reasonably controlling parameters such as the total molar quantity of zinc nitrate and manganese nitrate, the molar ratio of trimesic acid and the like.
Preferably, in the step (1), the molar ratio of the total molar amount of the zinc nitrate and the manganese nitrate to the polyvinylpyrrolidone is (1-1.8) mmol (2.5-3.5) g. In the present invention, the number average molecular weight of polyvinylpyrrolidone may be 30k.
Preferably, in the step (1), the solvent is formed by mixing N, N-dimethylformamide and ethanol, and the volume ratio of the N, N-dimethylformamide to the ethanol is 1 (0.5-2). Further preferably, the volume ratio of the N, N-dimethylformamide to the ethanol is 1:1. In the present invention, if other solvents such as water are added to the solvent used, it is difficult to obtain a flower-like precursor.
Preferably, in the step (1), the concentration of zinc nitrate in the mixed solution is 2-15mmol/L.
Preferably, in the step (2), the solvothermal reaction temperature is 120-200 ℃ and the reaction time is 4-8h.
Preferably, in the step (3), the mass ratio of the flower-shaped precursor to the selenium powder is 1 (1-3); the calcining temperature is 400-750 ℃, the heating rate is 2-5 ℃/min, and the calcining time is 45-180min. The proper mass ratio of the flower-shaped precursor and the selenium powder is combined with the calcination process, so that the obtained product can keep a unique flower-shaped structure perfectly.
As a general inventive concept, the invention provides an application of the flower-shaped zinc selenide-manganese/carbon composite material or the flower-shaped zinc selenide-manganese/carbon composite material prepared by the preparation method in a sodium ion battery anode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The flower-like zinc selenide-manganese/carbon composite material prepared by the method keeps a unique flower-like structure well, zinc selenide-manganese crystals are generated and anchored on the 2D porous carbon nano-sheet, the 2D structure has good structural stability and flexibility, and good conductive network is provided for the material by connection; the large number of cavity structures also provides buffer space for the volumetric expansion of the material. The porous structure can fully infiltrate the electrode material and the electrolyte, and reduce the migration distance of ions, so that the ion migration efficiency of the whole material is improved. In addition, zinc, manganese and carbon materials play a synergistic effect, so that the resistance of the materials is reduced, and meanwhile, a strong pseudocapacitance effect is generated. Thereby improving the specific capacity and electrochemical stability of the material.
(2) The sodium storage material prepared by the method has lower production cost, and has much higher capacity and rate capability than those of monobasic metal selenide, and has good application prospect in the aspect of sodium ion battery cathode materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of the flower-like zinc selenide-manganese/carbon composite material prepared in example 1;
FIG. 2 is a scanning electron micrograph of a flower-like precursor prepared in example 1;
FIG. 3 is a scanning electron micrograph of the flower-like zinc selenide-manganese/carbon composite prepared in example 1;
FIG. 4 is a thermogravimetric analysis of the flower-like zinc selenide-manganese/carbon composite material prepared in example 1;
FIG. 5 is a scanning electron micrograph of the composite energy storage material prepared in comparative example 1;
FIG. 6 is a scanning electron micrograph of the composite energy storage material prepared in comparative example 2;
FIG. 7 is a graph of specific capacity versus efficiency for sodium cells assembled from the flower-like zinc selenide-manganese/carbon composite of example 1 at different currents;
fig. 8 is a graph showing the specific discharge capacity and efficiency of the sodium battery assembled from the flower-like zinc selenide-manganese/carbon composite material obtained in example 1, as a function of the number of cycles.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
the preparation method of the flower-like zinc selenide-manganese/carbon composite material comprises the following steps:
(1) 1mmol of zinc nitrate, 0.5mmol of manganese nitrate, 2mmol of trimesic acid and 3g of polyvinylpyrrolidone (number average molecular weight: 30 k) were dissolved in 80mL of solvent to obtain a mixed solution; wherein the solvent consists of N, N-dimethylformamide and ethanol according to the volume ratio of 1:1;
(2) Transferring the mixed solution into a polytetrafluoroethylene-stainless steel reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 160 ℃, the reaction time is 6 hours, naturally cooling to room temperature after the reaction is finished, centrifugally washing the obtained material for 3 times, and drying to obtain a flower-shaped precursor;
(3) Respectively placing the flower-like precursor and the selenium powder in two reaction porcelain boats, wherein the mass ratio of the flower-like precursor to the selenium powder is 1:2, then placing the mixture in a tube furnace, heating to 600 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, maintaining the temperature at 600 ℃ and calcining for 120min, cooling, grinding and sieving to obtain the flower-like zinc selenide-manganese/carbon composite material.
Wherein, fig. 1 is an X-ray diffraction diagram of the flower-shaped zinc selenide-manganese/carbon composite material obtained in example 1, and it can be seen from fig. 1 that the flower-shaped zinc selenide-manganese/carbon composite material contains two zinc selenide-manganese phases, and no obvious other phases are generated in the reaction process. Fig. 2 is a scanning electron micrograph of the precursor material obtained in example 1, and it can be seen from fig. 2 that the precursor material obtained has a 2D nanoplatelet composition resembling a flower shape. Fig. 3 is a scanning electron micrograph of the flower-shaped zinc selenide-manganese/carbon composite material obtained in example 1, and it can be seen from fig. 3 (a) that the prepared composite material is flower-like, zinc selenide-manganese particles are randomly embedded on a 2D porous carbon nano sheet, and from fig. 3 (b), a large number of pore structures are formed inside the nano sheet. FIG. 4 is a thermogravimetric analysis of the flower-like zinc selenide-manganese/carbon composite material prepared in example 1.
The flower-shaped zinc selenide-manganese/carbon composite material prepared in the embodiment comprises a flower-shaped structure assembled by 2D porous carbon nano sheets, wherein zinc selenide-manganese particles are loaded on the 2D porous carbon nano sheets, and the zinc selenide-manganese particles are formed by Zn 0.697 Mn 0.303 Se and Zn 0.71 Mn 0.29 Se composition. The carbon content of the flower-like zinc selenide-manganese/carbon composite material is 46.8%.
Example 2:
the preparation method of the flower-like zinc selenide-manganese/carbon composite material comprises the following steps:
(1) 1mmol of zinc nitrate, 0.5mmol of manganese nitrate, 2mmol of trimesic acid and 3g of polyvinylpyrrolidone (number average molecular weight: 30 k) were dissolved in 80mL of solvent to obtain a mixed solution; wherein the solvent is prepared from N, N-dimethylformamide and ethanol according to the volume ratio of 1:1, the composition is as follows;
(2) Transferring the mixed solution into a polytetrafluoroethylene-stainless steel reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 160 ℃, the reaction time is 6 hours, naturally cooling to room temperature after the reaction is finished, centrifugally washing the obtained material for 3 times, and drying to obtain a flower-shaped precursor;
(3) Respectively placing the flower-like precursor and the selenium powder in two reaction porcelain boats, wherein the mass ratio of the flower-like precursor to the selenium powder is 1:2, then placing the mixture in a tube furnace, heating to 600 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, maintaining the temperature at 600 ℃ and calcining for 120min, cooling, grinding and sieving to obtain the flower-like zinc selenide-manganese/carbon composite material.
Example 3:
the preparation method of the flower-like zinc selenide-manganese/carbon composite material comprises the following steps:
(1) 1mmol of zinc nitrate, 0.5mmol of manganese nitrate, 2mmol of trimesic acid and 3g of polyvinylpyrrolidone (number average molecular weight: 30 k) were dissolved in 80mL of solvent to obtain a mixed solution; wherein the solvent consists of N, N-dimethylformamide and ethanol according to the volume ratio of 1:1;
(2) Transferring the mixed solution into a polytetrafluoroethylene-stainless steel reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 120 ℃, the reaction time is 4 hours, naturally cooling to room temperature after the reaction is finished, centrifugally washing the obtained material for 3 times, and drying to obtain a flower-shaped precursor;
(3) Respectively placing the flower-like precursor and the selenium powder in two reaction porcelain boats, wherein the mass ratio of the flower-like precursor to the selenium powder is 1:2, then placing the mixture in a tube furnace, heating to 600 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, maintaining the temperature at 600 ℃ and calcining for 120min, cooling, grinding and sieving to obtain the flower-like zinc selenide-manganese/carbon composite material.
Example 4:
the preparation method of the flower-like zinc selenide-manganese/carbon composite material comprises the following steps:
(1) 1mmol of zinc nitrate, 0.5mmol of manganese nitrate, 2mmol of trimesic acid and 3g of polyvinylpyrrolidone (number average molecular weight: 30 k) were dissolved in 80mL of solvent to obtain a mixed solution; wherein the solvent consists of N, N-dimethylformamide and ethanol according to the volume ratio of 1:1;
(2) Transferring the mixed solution into a polytetrafluoroethylene-stainless steel reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 160 ℃, the reaction time is 6 hours, naturally cooling to room temperature after the reaction is finished, centrifugally washing the obtained material for 3 times, and drying to obtain a flower-shaped precursor;
(3) Respectively placing the flower-like precursor and the selenium powder in two reaction porcelain boats, wherein the mass ratio of the flower-like precursor to the selenium powder is 1:2, then placing the mixture in a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under argon atmosphere, maintaining the temperature at 700 ℃ and calcining for 180min, cooling, grinding and sieving to obtain the flower-like zinc selenide-manganese/carbon composite material.
Comparative example 1:
a preparation method of a composite energy storage material comprises the following steps:
(1) 1mmol of zinc nitrate, 2mmol of trimesic acid and 3g of polyvinylpyrrolidone (number average molecular weight: 30 k) are dissolved in 80mL of solvent to obtain a mixed solution; wherein the solvent consists of N, N-dimethylformamide and ethanol according to the volume ratio of 1:1;
(2) Transferring the mixed solution into a polytetrafluoroethylene-stainless steel reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 160 ℃, the reaction time is 6 hours, naturally cooling to room temperature after the reaction is finished, centrifugally washing the obtained material for 3 times, and drying to obtain a flower-shaped precursor;
(3) And respectively placing the flower-shaped precursor and the selenium powder in two reaction porcelain boats, placing the flower-shaped precursor and the selenium powder in a tubular furnace according to the mass ratio of 1:2, heating to 600 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, maintaining the temperature at 600 ℃ and calcining for 120min, cooling, grinding and sieving to obtain the composite energy storage material. Fig. 5 is a scanning electron micrograph of the composite energy storage material prepared in comparative example 1, and it is understood that the method in comparative example 1 cannot prepare a flower-shaped composite energy storage material.
Comparative example 2:
a preparation method of a composite energy storage material comprises the following steps:
(1) 1mmol of manganese nitrate, 2mmol of trimesic acid and 3g of polyvinylpyrrolidone (number average molecular weight: 30K) are dissolved in 80mL of solvent to obtain a mixed solution; wherein the solvent consists of N, N-dimethylformamide and ethanol according to the volume ratio of 1:1;
(2) Transferring the mixed solution into a polytetrafluoroethylene-stainless steel reaction kettle for solvothermal reaction, wherein the solvothermal reaction temperature is 160 ℃, the reaction time is 6 hours, naturally cooling to room temperature after the reaction is finished, centrifugally washing the obtained material for 3 times, and drying to obtain a flower-shaped precursor;
(3) And respectively placing the flower-shaped precursor and the selenium powder in two reaction porcelain boats, placing the flower-shaped precursor and the selenium powder in a tubular furnace according to the mass ratio of 1:2, heating to 600 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, maintaining the temperature at 600 ℃ and calcining for 120min, cooling, grinding and sieving to obtain the composite energy storage material. Fig. 6 is a scanning electron micrograph of the composite energy storage material prepared in comparative example 2, and it is understood that the method in comparative example 2 cannot prepare a flower-shaped composite energy storage material.
In order to test that the flower-like zinc selenide-manganese/carbon composite material provided by the invention has energy storage characteristics and can be used for a negative electrode material of a sodium ion battery, the flower-like zinc selenide-manganese/carbon composite material in example 1 and the energy storage materials obtained in comparative examples 1-2 are used as the negative electrode materials to prepare the sodium ion battery, and then the test of items such as a discharge curve is carried out, and the test results are shown in fig. 7-8.
The preparation method of the sodium ion battery comprises the following steps: dissolving 10wt% of adhesive (CMC), 10wt% of conductive agent (carbon black) and 80wt% of active substance in a mixed solvent of deionized water and ethanol (volume ratio: deionized water: ethanol=3:2), uniformly stirring, coating on a copper foil, and drying in a forced air drying oven at 80 ℃ for 12 hours; and (3) drying, and punching the electrode into a pole piece (phi 12 mm) by using a punch to obtain the required electrode. The loading capacity of active substances on the pole piece is 0.6-1.2mg/cm 2 . The metal sodium block was flattened and cut into a sheet shape as a counter electrode, a glass fiber filter membrane as a membrane, 1mol/L sodium triflate solution (1 mol/L concentration) dissolved in diglyme as an electrolyte, and a button cell was assembled in a glove box filled with argon gas.
FIG. 7 is a graph showing specific capacities versus efficiencies obtained at different current densities when the materials obtained in example 1, comparative example 1 and comparative example 2 were used as negative electrode materials for sodium ion batteries, wherein the specific discharge capacities of example 1 were 360.0, 348.5, 346.9, 329.3, 321.4, 310.7, 306.7, 301.3 and 294.4mAh/g at current densities of 0.1, 0.2, 0.5, 1, 1.5, 2, 3, 5 and 10A/g, respectively, and there was a specific discharge capacity of 481.7mAh/g after the current density was restored to 0.1A/g.
Fig. 8 is a graph of specific capacity versus cycle number at different currents, which is obtained by testing the energy storage material obtained in example 1 when the energy storage material is used as a negative electrode material of a sodium ion battery, and it can be seen from the graph that the specific capacity and the cycle stability of the flower-like zinc selenide-manganese/carbon composite material of example 1 are extremely high, and the specific discharge capacity of the energy storage material obtained in example 1 after 1000 cycles at a flow density of 2A/g is 369.6mAh/g.
Claims (8)
1. The preparation method of the flower-like zinc selenide-manganese/carbon composite material is characterized by comprising the following steps of:
(1) Zinc nitrate, manganese nitrate, polyvinylpyrrolidone and trimesic acid are dissolved in a solvent to obtain a mixed solution; the solvent is formed by mixing N, N-dimethylformamide and ethanol, and the volume ratio of the N, N-dimethylformamide to the ethanol is 1 (0.5-2);
(2) Carrying out solvothermal reaction on the mixed solution, naturally cooling to room temperature after the reaction is finished, centrifugally washing and drying the obtained material to obtain a flower-shaped precursor;
(3) Respectively placing the flower-shaped precursor and selenium powder into two reaction porcelain boats, placing the two reaction porcelain boats into a tube furnace, calcining the two reaction porcelain boats under the argon atmosphere, cooling the two reaction porcelain boats, grinding and sieving the two reaction porcelain boats to obtain the flower-shaped zinc selenide-manganese/carbon composite energy storage material;
the flower-shaped zinc selenide-manganese/carbon composite material comprises a flower-shaped structure assembled by 2D porous carbon nano sheets, wherein zinc selenide-manganese particles are loaded on the 2D porous carbon nano sheets, and the chemical general formula of the zinc selenide-manganese is Zn （1-x） Mn x Se, wherein x is more than or equal to 0.2 and less than or equal to 0.4.
2. The method for preparing a flower-like zinc selenide-manganese/carbon composite according to claim 1, wherein the carbon content of the flower-like zinc selenide-manganese/carbon composite is 40 to 50%.
3. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the zinc nitrate and the manganese nitrate in the mixed solution is 1 (0.2-0.8), and the molar ratio of the total molar amount of the zinc nitrate and the manganese nitrate to the trimesic acid is 1-1.8:2-2.5.
4. The process according to claim 1, wherein in the step (1), the molar ratio of the total molar amount of zinc nitrate and manganese nitrate to polyvinylpyrrolidone is (1-1.8) mmol (2-5) g.
5. The method according to claim 1, wherein in the step (1), the concentration of zinc nitrate in the mixed solution is 2 to 15mmol/L.
6. The process according to any one of claims 1 to 5, wherein in step (2), the solvothermal reaction is carried out at a temperature of 120 to 200 ℃ for a reaction time of 4 to 8 hours.
7. The preparation method according to any one of claims 1 to 5, wherein in the step (3), the mass ratio of the flower-like precursor to selenium powder is 1 (1-3); the calcining temperature is 400-750 ℃, the heating rate is 2-5 ℃/min, and the calcining time is 45-180min.
8. Use of a flower-like zinc selenide-manganese/carbon composite material prepared by the preparation method according to any one of claims 1 to 7 in a sodium ion battery anode material.
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