CN115072777B - Method for preparing hollow bismuth sulfide through co-regulation of cobalt doping and solvent and potassium ion battery cathode material prepared by same - Google Patents
Method for preparing hollow bismuth sulfide through co-regulation of cobalt doping and solvent and potassium ion battery cathode material prepared by same Download PDFInfo
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Abstract
The invention discloses a method for preparing hollow bismuth sulfide through cobalt doping and solvent cooperative regulation and control and a potassium ion battery cathode material prepared by the method, wherein the preparation method comprises the steps of adding bismuth inorganic strong acid salt and cobalt inorganic strong acid salt into a mixed solution of isopropanol and other polyhydric alcohols according to a certain proportion, carrying out solvothermal synthesis, and regulating and controlling the shape of a bismuth sulfide material precursor through the cobalt doping amount and the solvent cooperative action; and calcining the precursor powder of the bismuth sulfide material and sulfur powder/thiourea in an argon atmosphere to obtain the cobalt-doped hollow bismuth sulfide. The cobalt-doped hollow bismuth sulfide electrode material provided by the invention can provide a larger interlayer spacing to accommodate potassium ions with larger radius, and the cobalt-doped hollow bismuth sulfide electrode material is used as a negative electrode material to be applied to a potassium ion battery to show excellent cycle performance, and the cobalt-doped hollow bismuth sulfide electrode material is 100mA g ‑1 The reversible specific capacity can still be maintained at 212.3mAh g after 200 cycles under the current density ‑1 。
Description
Technical Field
The invention relates to a preparation method of a potassium ion battery electrode material, in particular to a method for preparing hollow bismuth sulfide through the cooperative regulation and control of cobalt doping and a solvent and a potassium ion battery cathode material prepared by the method.
Background
With the increase of national demand for energy, the problem of energy supply becomes a focus of national concern. The electric power industry is a main department of electric energy supply in China and is also a main department of carbon emission. In order to alleviate the global greenhouse effect problem, china puts forward a double-carbon target, so that the reduction of carbon emission also becomes another problem faced by China. In order to solve the problem of energy supply and demand balance, china vigorously develops energy storage projects. Therefore, the improvement of the performance of the energy storage material becomes a focus of research. The potassium ion battery has a similar working mechanism with the lithium ion battery, and the potassium element is abundant in the earth crust and is widely distributed, and the oxidation-reduction potential is low. The advantages of the above potassium ion battery have attracted attention of researchers.
Bismuth sulfide (Bi) 2 S 3 ) Occurring as electrode material is an alloy and a conversion mechanism, the theoretical specific capacity of the material is high (625 mAh g) -1 ). The bismuth sulfide is accompanied by large volume expansion in the alloying reaction process, and the cycling stability of the material is reduced. In addition, repeated desorption/intercalation of potassium ions during charging and discharging causes pulverization of the electrode material. Therefore, it is critical to alleviate the problem of material swelling through the control of the material structure.
In the prior art method, a hard template method or a soft template method is generally adopted to prepare the material with the hollow structure. The disadvantages of the method are as follows: in order to obtain the final hollow material, a template removing process is required, and a solvent dissolving or etching method is usually adopted to remove the template, so that the process flow is complicated.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a method for preparing hollow bismuth sulfide by co-regulation of cobalt doping and a solvent and a potassium ion battery anode material prepared by the method. According to the method, the material structure is cooperatively regulated and controlled through the metal element doping and the solvent, the electrode material pulverization can be effectively inhibited, and the prepared micro-nano bismuth sulfide material with the hollow structure provides an effective accommodating space for volume expansion in the circulation process, so that the circulation stability of the electrode material is optimized.
In order to solve the technical problem, the method of the invention comprises the following steps:
(1) Mixing bismuth inorganic strong acid salt and cobalt inorganic strong acid salt according to a molar ratio of 10:1 to 1:3 adding the mixture into a mixed solution of isopropanol and other polyols to carry out a solvothermal synthesis reaction; the method comprises the following steps of preparing and forming a hollow bismuth sulfide material precursor through the regulation and control of the amount of cobalt doping and the synergistic effect of a solvent, and then washing and centrifugally collecting to obtain a product, namely bismuth sulfide material precursor powder; the volume ratio of the isopropanol to other polyols is 1:1 to 1:5 forming a mixed solution;
(2) And (2) calcining the precursor powder of the bismuth sulfide material obtained in the step (1) and sulfur powder or thiourea in an argon atmosphere to form the cobalt-doped hollow bismuth sulfide.
Further, in the step (1): the bismuth inorganic strong acid salt comprises one of bismuth nitrate and bismuth chloride; the cobalt inorganic strong acid salt comprises one of cobalt nitrate and cobalt chloride; other polyols include ethylene glycol or glycerol; the temperature of the solvothermal synthesis reaction is 150-190 ℃; the solvothermal synthesis reaction time is 8-12 h.
Further, in the step (2), the mass ratio of the bismuth sulfide material precursor powder to the sulfur powder or thiourea is 1:1 to 1:6; the calcining temperature is 400-600 ℃; the calcination time is 2-5 h.
The potassium ion battery cathode material is prepared by applying the method.
According to the potassium ion battery, the cathode material is the cobalt-doped hollow bismuth sulfide electrode material prepared by the method.
The invention has the beneficial effects that:
by adopting the method, the bismuth sulfide precursor is cooperatively regulated and controlled by the cobalt doping and the solvent to form the hollow structure, a hard template, a soft template and the like are not needed, the step of removing the template is omitted, and the synthesis process of the hollow material is simplified. The preparation method has the advantages of simple preparation process, high yield and industrial prospect. The invention adopts the solvent thermal synthesis method and the calcination process to prepare the hollow bismuth sulfide material with uniform particle size distribution and good dispersibility, and the particle size is intensively distributed at 3-5 mu m.
When the cobalt-doped hollow bismuth sulfide prepared by the invention is used as a micro-nano composite material and used as a negative electrode material of a potassium ion battery, experiments show that the following beneficial effects exist: firstly, cobalt doping cavity bismuth sulfide has great interlamellar spacing and hollow structure, can effectively hold the electrode material volume expansion that arouses when the great potassium ion of radius is repeated to take off/inlay to promote the cycle stability of material. And secondly, the cobalt-doped hollow bismuth sulfide hollow structure has a large specific surface area, so that more active sites can be introduced into the material, and the defect generated by doping other atoms can provide a large number of potassium storage sites, so that the electrochemical performance of the battery is improved. The material is applied to a potassium ion battery at 100mA g -1 The specific capacity can still be maintained at 212.3mAh g after 200 cycles under the current density -1 。
Drawings
FIG. 1 is an SEM image of the precursor material obtained in example 1 under an electron microscope with a magnification of 678 times;
FIG. 2 is an SEM topography of the precursor material obtained in example 1 at a magnification of 7400 times;
FIG. 3 is an SEM topography of the precursor material obtained in example 1 at a magnification of 21000 times;
FIG. 4 is an SEM topography of the cobalt-doped hollow bismuth sulfide micro-nano composite material prepared in example 1;
FIG. 5 is an XRD diffraction pattern of the cobalt-doped hollow bismuth sulfide micro-nano composite material obtained in example 1;
FIG. 6 is an SEM topography of a part of the surface of the cobalt-doped hollow bismuth sulfide micro-nano composite material obtained in example 1;
FIG. 7 is a TEM morphology of the cobalt-doped hollow bismuth sulfide micro-nano composite material obtained in example 1;
FIG. 8 is an element distribution diagram of the cobalt-doped hollow bismuth sulfide micro-nano composite material obtained in example 1;
FIG. 9 is a long cycle performance diagram of a cobalt-doped hollow bismuth sulfide micro-nano composite material as a battery cathode material applied to a potassium ion battery.
Detailed Description
The present invention will be described in further detail with reference to examples. The drawings and examples are only for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Example 1:
the method for preparing the hollow bismuth sulfide through the coordinated regulation and control of cobalt doping and a solvent comprises the following steps:
(1) Stirring 6ml of ethylene glycol and 30ml of isopropanol for 10min to mix uniformly; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 7:1, stirring until the metal salt is completely dissolved; transferring all dissolved solution into a 50mL polytetrafluoroethylene autoclave, sealing the autoclave in a stainless steel autoclave, putting the stainless steel autoclave into an oven, carrying out solvothermal synthesis reaction for 10 hours at 180 ℃, washing, centrifuging and collecting to obtain a precursor powder of the bismuth sulfide material;
(2) Mixing precursor powder and sulfur powder according to a mass ratio of 1:6, placing the mixture in a tubular furnace, calcining the mixture for 4 hours at 500 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Scanning Electron Microscope (SEM) analysis was performed on the bismuth sulfide material precursor powder obtained in example 1, and the cobalt-doped bismuth sulfide precursor obtained in this example was observed under electron microscope magnification of 678 and 7400 as shown in fig. 1 and 2, and the surface of the material was observed under high magnification of 21000 as shown in fig. 3. The cobalt-doped hollow bismuth sulfide micro-nano composite material calcined in the sulfur atmosphere is shown in fig. 4, an XRD diffraction test is carried out on the cobalt-doped hollow bismuth sulfide material, and the synthesis of a pure-phase material is verified in fig. 5. It can be clearly observed from fig. 6 that the cobalt-doped hollow bismuth sulfide is a hollow microsphere composed of a combination of nanorods and nanoparticles. Further observing the hollow structure of the material by a Transmission Electron Microscope (TEM), the material can be clearly seen to be in a hollow state, as shown in FIG. 7. The distribution of Bi, co and S elements in the finally obtained material is shown in FIG. 8.
Preparing a cobalt-doped hollow bismuth potassium sulfide battery cathode and analyzing electrochemical properties: the cobalt-doped bismuth sulfide material prepared in example 1, conductive carbon black Super P, and binder CMC were mixed in the following ratio of 7:2:1, adding deionized water, mixing, grinding to prepare slurry, coating the slurry on a current collector copper foil, drying at 60 ℃ to prepare a negative plate, taking a metal potassium plate as a positive electrode, taking glass fiber as a diaphragm, taking KFSI (potassium bifluoride sulfimide) as a potassium salt and taking diethylene glycol dimethyl ether as solvents, and assembling in an argon glove box to obtain the CR2032 type button experiment battery. The cycle curve of the potassium ion battery is shown in FIG. 9, and when the material is used as the negative electrode material of the potassium ion battery, the current is 100mA g at room temperature -1 The reversible specific capacity can still be maintained at 212.3mAh g after 200 cycles under the current density -1 The electrochemical material has good cycling stability and shows excellent electrochemical performance.
Example 2:
(1) Stirring 18ml of ethylene glycol and 18ml of isopropanol for 10min to mix uniformly; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 5:3, stirring until the metal salt is completely dissolved; transferring all the dissolved solution into a 50mL polytetrafluoroethylene high-pressure autoclave, sealing the high-pressure autoclave in a stainless steel high-pressure autoclave, putting the high-pressure autoclave into an oven, carrying out solvothermal synthesis reaction for 8 hours at 190 ℃, washing, centrifuging and collecting to obtain a product, namely bismuth sulfide material precursor powder;
(2) Mixing precursor powder and sulfur powder according to the mass ratio of 1:1, placing the mixture in a tubular furnace, calcining the mixture for 2 hours at the temperature of 600 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Example 3:
(1) Stirring 12ml of ethylene glycol and 24ml of isopropanol for 10min to mix uniformly; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 5:1, stirring until the metal salt is completely dissolved; transferring all the dissolved solution into a 50mL polytetrafluoroethylene high-pressure autoclave, sealing the high-pressure autoclave in a stainless steel high-pressure autoclave, putting the high-pressure autoclave into an oven, carrying out solvothermal synthesis reaction for 8 hours at 190 ℃, washing, centrifuging and collecting to obtain a product, namely bismuth sulfide material precursor powder;
(2) Mixing precursor powder and sulfur powder according to the proportion of 1:3, placing the mixture in a tubular furnace, calcining the mixture for 5 hours at the temperature of 400 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Example 4:
(1) Stirring 6ml of ethylene glycol and 30ml of isopropanol for 10min to mix uniformly; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 10:1, stirring until the metal salt is completely dissolved; transferring all the dissolved solution into a 50mL polytetrafluoroethylene high-pressure autoclave, sealing the high-pressure autoclave in a stainless steel high-pressure autoclave, putting the high-pressure autoclave into an oven, carrying out solvothermal synthesis reaction for 8 hours at 190 ℃, washing, centrifuging and collecting to obtain a product, namely bismuth sulfide material precursor powder;
(2) Mixing precursor powder and sulfur powder according to a mass ratio of 1:1, placing the mixture in a tubular furnace, calcining the mixture for 5 hours at the temperature of 400 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Example 5:
(1) Mixing glycerol 6ml and isopropanol 30ml under stirring for 10 min; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 10:1, stirring until the metal salt is completely dissolved; transferring all the dissolved solution into a 50mL polytetrafluoroethylene high-pressure autoclave, sealing the high-pressure autoclave in a stainless steel high-pressure autoclave, putting the high-pressure autoclave into an oven, carrying out solvothermal synthesis reaction for 8 hours at 190 ℃, washing, centrifuging and collecting to obtain a product, namely bismuth sulfide material precursor powder;
(2) Mixing precursor powder and sulfur powder according to a mass ratio of 1:3, placing the mixture in a tubular furnace after mixing, calcining the mixture for 4 hours at 500 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Example 6:
(1) Mixing 18ml of glycerol and 18ml of isopropanol uniformly by stirring for 10 min; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 5:1, stirring until the metal salt is completely dissolved; transferring all dissolved solution into a 50mL polytetrafluoroethylene autoclave, sealing the autoclave in a stainless steel autoclave, putting the stainless steel autoclave into an oven, carrying out solvothermal synthesis reaction for 10 hours at 180 ℃, washing, centrifuging and collecting to obtain a precursor powder of the bismuth sulfide material;
(2) Mixing precursor powder and sulfur powder according to the mass ratio of 1:6, placing the mixture into a tubular furnace, calcining the mixture for 2 hours at the temperature of 600 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Example 7:
(1) Mixing 18ml of glycerol and 18ml of isopropanol uniformly by stirring for 10 min; adding bismuth chloride to the mixed solvent: cobalt chloride, the molar ratio of the two is as follows: 1:1, stirring until the metal salt is completely dissolved; transferring all dissolved solution into a 50mL polytetrafluoroethylene autoclave, sealing the autoclave in a stainless steel autoclave, putting the stainless steel autoclave into an oven, carrying out solvothermal synthesis reaction for 12 hours at 150 ℃, washing, centrifuging and collecting to obtain a precursor powder of the bismuth sulfide material;
(2) Mixing the precursor powder and thiourea according to the mass ratio of 1:6, placing the mixture in a tubular furnace, calcining the mixture for 5 hours at the temperature of 400 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
Example 8:
(1) 9ml of glycerol and 27ml of isopropanol are stirred for 10min to be uniformly mixed; adding bismuth nitrate into the mixed solvent: cobalt nitrate, the molar ratio of the two is as follows: 1:3, stirring until the metal salt is completely dissolved; transferring all dissolved solution into a 50mL polytetrafluoroethylene high-pressure autoclave, sealing the high-pressure autoclave in a stainless steel high-pressure autoclave, putting the high-pressure autoclave into an oven, carrying out solvothermal synthesis reaction for 9 hours at 190 ℃, washing, centrifuging and collecting to obtain a product, namely bismuth sulfide material precursor powder;
(2) Mixing precursor powder and sulfur powder according to a mass ratio of 1:3, placing the mixture in a tubular furnace, calcining the mixture for 2 hours at 500 ℃ in an argon atmosphere, and cooling the mixture to room temperature to obtain the cobalt-doped hollow bismuth sulfide micro-nano material.
TABLE 1 Capacity and coulombic efficiency after cycling for each example
From fig. 1, it can be visually observed that the particle size of the material precursor is uniform. As can be seen from FIG. 9 and Table 1, the negative electrode material of the potassium ion battery prepared by the invention is 100mA g -1 The circulation performance under the current density is excellent, and the coulombic efficiency after 200 cycles is 99.2%. It can be seen from fig. 9 that the material can still maintain stable cycle performance under deep charge and discharge, which illustrates that the material structure in the present invention is designed to provide an expansion space for repeated deintercalation of large-radius potassium ions during charge and discharge, and can effectively maintain the stability of the electrode material structure.
Claims (5)
1. A method for preparing hollow bismuth sulfide through cobalt doping and solvent cooperative regulation is characterized by comprising the following steps:
(1) Mixing bismuth inorganic strong acid salt and cobalt inorganic strong acid salt according to a molar ratio of 10:1 to 1:3, adding the mixture into a mixed solution of isopropanol and other polyols to perform solvothermal synthesis reaction; the method comprises the following steps of preparing and forming a hollow bismuth sulfide material precursor through the regulation and control of the amount of cobalt doping and the synergistic effect of a solvent, and then washing and centrifugally collecting to obtain a product bismuth sulfide material precursor powder; the volume ratio of the isopropanol to other polyols is 1:1 to 1:5 forming a mixed solution;
the bismuth inorganic strong acid salt comprises one of bismuth nitrate and bismuth chloride; the cobalt inorganic strong acid salt comprises one of cobalt nitrate and cobalt chloride; other polyols include ethylene glycol or glycerol;
(2) And (2) calcining the precursor powder of the bismuth sulfide material in the step (1) and sulfur powder or thiourea in an argon atmosphere to form the cobalt-doped hollow bismuth sulfide.
2. The method for preparing hollow bismuth sulfide through cobalt doping and solvent cooperative regulation and control as claimed in claim 1, wherein in the step (1), the solvothermal synthesis reaction temperature is 150-190 ℃; the time of the solvothermal synthesis reaction is 8-12 h.
3. The method for preparing hollow bismuth sulfide through cobalt doping and solvent synergistic regulation and control as claimed in claim 1, wherein in the step (2), the mass ratio of the bismuth sulfide material precursor powder to the sulfur powder or thiourea is 1:1 to 1:6; the calcining temperature is 400-600 ℃; the calcination time is 2-5 h.
4. A potassium ion battery negative electrode material, characterized by being prepared by the method of any one of claims 1 to 3.
5. A potassium ion battery, characterized in that the negative electrode material thereof is the negative electrode material of the potassium ion battery according to claim 4.
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