CN114420924A - Bismuth telluride-based composite negative electrode material of sodium/potassium ion battery and preparation method thereof - Google Patents
Bismuth telluride-based composite negative electrode material of sodium/potassium ion battery and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 28
- 239000011734 sodium Substances 0.000 title claims abstract description 27
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 25
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 18
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 14
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
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- 239000010405 anode material Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 8
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 8
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 229910003251 Na K Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention relates to a preparation method of a bismuth telluride-based composite negative electrode material of a sodium/potassium ion battery, which comprises the following steps: dissolving sodium tellurite and bismuth salt in ethylene glycol according to a certain proportion, adding sodium hydroxide and polyvinylpyrrolidone to prepare a uniform solution, carrying out hydrothermal reaction at a certain temperature, further washing for multiple times, drying to obtain an original material, and then sequentially coating graphene and a carbon nano layer on the material under a certain condition to obtain the composite negative electrode material. The material prepared by the invention is composed of nanosheets uniformly coated by graphene and carbon layers, so that the composite material has high specific capacity, excellent cycling stability and excellent rate capability when being used as a sodium/potassium ion battery cathode material; in addition, the preparation process is simple and easy to operate, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of sodium and potassium ion batteries, and particularly relates to a bismuth telluride-based composite negative electrode material and a preparation method thereof.
Background
At present, China has become the largest energy producing country and consuming country in the world, the main energy supply still mainly comprises coal, petroleum and natural gas, but a series of outstanding problems are caused, which mainly reflect the aspects of the challenge of energy supply safety, the increase of ecological environment pressure, the outstanding pollution emission problem, the low energy science and technology level, the fierce international competition and the like, and the problems in the energy field are more outstanding and severe by the targets of carbon peak reaching and carbon neutralization provided by China. Is limited by the characteristics of energy resources in China, and chemical basic raw materials are difficult to provide in petrochemical industry and coal chemical industry; the solar energy and wind energy power generation grid-connected rate is low, the water energy and nuclear energy are relatively excessive, and the fuel ethanol has the risk of competing for grains with people. Therefore, while the method is dedicated to the coordinated development of an isolated energy subsystem, the improvement of scientific technology is expected to develop clean energy. The lithium ion battery is applied to the fields of portable electronic equipment, electric automobiles and the like on a large scale due to high energy density, but the price is increased due to low lithium resource storage, and the lithium ion battery faces serious lithium dendrite and development bottleneck problems, so that the further application of the lithium ion battery is limited, and therefore, the development of a novel rechargeable battery with low cost, rich natural resources, high energy density and high power density as a substitute of the lithium ion battery is very urgent.
Novel secondary batteries such as sodium and potassium ion batteries have attracted much attention because they have similar electrochemical principles to lithium ion batteries. The Na + and K + are close to the standard oxidation-reduction potential of Li/Li +, so that the Na-K ion battery can present high energy density. The current negative electrode materials mainly comprise three major types of mechanism electrodes of insertion type, conversion reaction and alloying mechanism. The slow diffusion kinetics of the insertion type negative electrode material in the diffusion process causes poor rate capability, so that the specific capacity is limited; in contrast, higher specific capacities can be achieved with the conversion reaction materials, but the operating voltages are higher; the specific capacity of the alloying mechanism material is higher and the working voltage is lower. However, the conversion/alloying materials undergo a large volume change during cycling, which results in electrode rupture and gradual deactivation during cycling. Therefore, the development of the material with the conversion-alloying dual mechanism is expected to ensure that the electrode keeps low working voltage and high specific capacity, and meanwhile, the method of coating the graphene and the carbon layer can further inhibit large volume expansion in the charging and discharging process, so that the cycle life of the negative electrode material is prolonged.
As shown in the invention, the chemical formula of the cathode material is Bi2Te3@ rGO @ NC, when used as the cathode material of a sodium/potassium ion battery, undergoes conversion reaction and alloying reaction in the discharging process, and the final product is Na3Bi/K3Bi undergoes a corresponding reversible process in the charging process, and finally Bi is generated2Te3. During the reaction, the graphene and carbon layer reacts with Bi2Te3The nano-sheet is tightly combined with Bi2Te3The shape of the nano-sheet, thereby improving the cycling stability. In view of the above characteristics, the material is very suitable for a sodium/potassium ion battery anode material.
Disclosure of Invention
Technical problem to be solved
The invention provides a bismuth telluride-based composite negative electrode material of a sodium/potassium ion battery and a preparation method thereof, aiming at developing a sodium/potassium ion battery negative electrode material with low cost, high capacity, long service life and high power density.
Technical scheme
A bismuth telluride-based composite cathode material for sodium/potassium ion batteries is characterized in that the chemical formula of the cathode material is Bi2Te3@rGO@NC。
A preparation method of a bismuth telluride-based composite negative electrode material of a sodium/potassium ion battery is characterized by comprising the following steps:
step 1: weighing sodium tellurite and bismuth salt according to a stoichiometric ratio, dispersing the sodium tellurite and bismuth salt in ethylene glycol, adding sodium hydroxide and polyvinylpyrrolidone, stirring to form a uniform solution, then adding a certain amount of graphene, and stirring and performing ultrasonic treatment to obtain a well-dispersed solution; the stirring temperature is 25-50 ℃, and the stirring time is 2-4 h;
step 2: transferring the solution obtained in the step 1 into a reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at a certain temperature and time;
and step 3: precipitating the product obtained in the step 2 by centrifugation or filtration, washing with water and ethanol for multiple times, and finally freeze-drying the resultant powder to obtain Bi2Te3@rGO；
And 4, step 4: dissolving tris (hydroxymethyl) aminomethane in a certain amount of deionized water, adding a small amount of concentrated hydrochloric acid to adjust the pH value of the solution, and stirring to form a uniform solution; weighing a certain amount of dopamine hydrochloride as a carbon and nitrogen source, completely dissolving the dopamine hydrochloride into the solution, and weighing a certain amount of Bi2Te3@ rGO is uniformly dispersed in the solution under the ultrasonic action, and is stirred for a certain time; washing with water and ethanol, freeze-drying, carbonizing in argon atmosphere, and naturally cooling to obtain the target product Bi2Te3@rGO@NC。
The further technical scheme of the invention is as follows: the bismuth salt in the step 1 can be one or more of bismuth chloride, bismuth nitrate and bismuth sulfate.
The further technical scheme of the invention is as follows: the molar ratio of the sodium tellurite to the bismuth salt in the step 1 is 2.9-3.1: 1.9-2.1.
The further technical scheme of the invention is as follows: the mass ratio of the bismuth antimonide to the graphene in the step 1 is 1.0-5.0.
The further technical scheme of the invention is as follows: the hydrothermal reaction temperature in the step 2 is 150-200 ℃, and the heat preservation time is 20-40 h.
The further technical scheme of the invention is as follows: the vacuum degree of the freeze drying in the step 3 and the step 4 is more than or equal to 10MPa, the temperature is-40 to-50 ℃, and the time is 10 to 24 hours.
The further technical scheme of the invention is as follows: the pH range of the solution in the step 4 is 6.8-8.0.
The further technical scheme of the invention is as follows: dopamine hydrochloride and Bi in step 42Te3The mass ratio of @ rGO is 1.0-2.0.
The further technical scheme of the invention is as follows: in the step 4, the carbonization temperature is 450-600 ℃, and the carbonization time is 1-3 h.
Advantageous effects
Compared with the prior art, the bismuth telluride-based composite negative electrode material for the sodium/potassium ion battery and the preparation method thereof have the following advantages:
(1) the cathode material prepared by the invention has a multilayer three-dimensional structure, can contain large-size sodium and potassium ions, and can maintain a stable structure in the charging and discharging process.
(2) The negative electrode material prepared by the invention keeps excellent structural stability and electrochemical dynamics behavior in the charge-discharge cycle process under the synergistic action of the graphene and the carbon layer, thereby presenting high discharge specific capacity, long cycle life and high power density.
(3) The preparation process is simple and easy to operate, has low equipment requirement, is environment-friendly and is suitable for large-scale commercial production.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 shows Bi prepared in example 1 of the present invention2Te3，Bi2Te3@rGO，Bi2Te3X-ray diffraction (XRD) pattern of @ rGO @ NC negative electrode material;
FIG. 2 shows Bi prepared in example 1 of the present invention2Te3The first charge-discharge curve of the @ rGO @ NC negative electrode material with the current density of 50mA/g in a sodium ion battery;
FIG. 3 shows Bi prepared in example 1 of the present invention2Te3A cycle performance diagram of @ rGO @ NC negative electrode material in a sodium ion battery with current density of 200 mA/g;
FIG. 4 shows Bi prepared in example 1 of the present invention2Te3A cycle performance diagram of the @ rGO @ NC negative electrode material in a sodium ion battery with the current density of 500 mA/g;
FIG. 5 shows Bi prepared in example 1 of the present invention2Te3@ rGO @ NC negative electrodeThe material is in a cycle performance diagram of a sodium ion battery under the current density of 1000 mA/g;
FIG. 6 shows Bi prepared in example 1 of the present invention2Te3The @ rGO @ NC negative electrode material has a first charge-discharge curve with the current density of 50mA/g in a potassium ion battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
(1) Weighing sodium tellurite and bismuth trichloride according to a molar ratio of 3:2, dispersing the sodium tellurite and bismuth trichloride in 50mL of ethylene glycol, stirring the mixture for 2 hours at 30 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium hydroxide and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 5.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining, sealing the lining in a reaction kettle, and reacting at 180 ℃ for 36 h;
(3) precipitating the product obtained in the step (2) by a high-speed centrifuge, washing with deionized water for more than 3 times, freezing the generated powder, and drying at-40 ℃ for 12h under a vacuum condition (the vacuum degree is 20MPa) to obtain Bi2Te3@ rGO negative electrode material.
(4) Dissolving trihydroxymethyl aminomethane in 100mL of deionized water, adding concentrated hydrochloric acid by using a liquid transfer gun, and stirring to form a uniform solution with the pH value of 8.0; dopamine hydrochloride and Bi2Te3Respectively and completely dissolving and dispersing the @ rGO in the solution in a mass ratio of 1:1, stirring for a period of time, washing with water and ethanol, freeze-drying for 24 hours, keeping the temperature for 3 hours at 500 ℃ under the argon atmosphere, and naturally cooling to obtain a target product Bi2Te3@rGO@NC。
Bi prepared in this example2Te3The active material @ rGO @ NC is mixed with an acetylene black conductive agent and a PVDF (polyvinylidene fluoride) binder in a mass ratio of 8: 1:1 is dissolved in NMP (N-methyl pyrrolidone), mixed into uniform slurry and coated on a copper foil current collector, dried at 80 ℃ for 12h and then cut into a negative plate with the diameter of 12 mm. Sodium and potassium metal are used as a negative plate, a glass fiber membrane is used as a diaphragm, and 1M NaPF6Or KPF6The solution is used as electrolyte, a CR2025 half cell is assembled in a glove box filled with argon, and constant-current charge and discharge tests are carried out within a voltage window of 0-3.0V.
FIG. 1 shows Bi prepared in this example2Te3X-ray diffraction (XRD) pattern of @ rGO @ NC negative electrode material, and Bi prepared in this example simultaneously2Te3The comparison of the materials proves that the Bi of the composite material is not changed after the graphene and the carbon coating layer are added2Te3The structure of (1).
FIG. 2 shows the first charge-discharge curve of sodium ion battery at 50mA/g current density, the first charge specific capacity reaches 457.2mAh/g, and the charge-discharge efficiency reaches 67.7%.
FIG. 3 shows a cycle performance diagram of the material under a current density of 200mA/g, the first charging specific capacity is 239.1mAh/g, the charging and discharging efficiency is as high as 55.3%, and the second charging specific capacity of the material is 122.8mAh/g after cycle 2000.
FIG. 4 shows a cycle performance diagram of the material under the current density of 500mA/g, the first charging specific capacity is 204.3mAh/g, and the cycle 3500 charging specific capacity is 100.1 mAh/g.
FIG. 5 shows a cycle performance diagram of the material under the current density of 1000mA/g, the first charging specific capacity is 163.6mAh/g, and the cycle 3500 charging specific capacity is 92.8 mAh/g.
FIG. 6 shows the first charge-discharge curve of potassium ion battery at 50mA/g current density, the first charge specific capacity is 322.7mAh/g, and the charge-discharge efficiency is as high as 47.9%.
Example 2
(1) Weighing sodium tellurite and bismuth sulfate according to a molar ratio of 2.9:2.1, dispersing the sodium tellurite and the bismuth sulfate in 50mL of ethylene glycol, stirring the mixture for 1h at 40 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium tellurite and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 3.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining, sealing the lining in a reaction kettle, and reacting at 180 ℃ for 36 h;
(3) precipitating the product obtained in the step (2) by a high-speed centrifuge, washing with deionized water for more than 3 times, freezing the generated powder, and drying at-40 ℃ for 12h under a vacuum condition (the vacuum degree is 20MPa) to obtain Bi2Te3@ rGO negative electrode material.
(4) Dissolving trihydroxymethyl aminomethane in 100mL of deionized water, adding concentrated hydrochloric acid by using a liquid transfer gun, and stirring to form a uniform solution with the pH value of 8.0; dopamine hydrochloride and Bi2Te3Respectively and completely dissolving and dispersing the @ rGO in the solution in a mass ratio of 1:1, stirring for a period of time, washing with water and ethanol, freeze-drying for 24 hours, keeping the temperature for 3 hours at 500 ℃ under the argon atmosphere, and naturally cooling to obtain a target product Bi2Te3@rGO@NC。
Example 3
(1) Weighing sodium tellurite and bismuth sulfate according to a molar ratio of 2.9:2.1, dispersing the sodium tellurite and the bismuth sulfate in 50mL of ethylene glycol, stirring the mixture for 1h at 40 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium tellurite and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 3.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining, sealing the lining in a reaction kettle, and reacting for 20h at 200 ℃;
(3) precipitating the product obtained in the step (2) by a high-speed centrifuge, washing with deionized water for more than 3 times, freezing the generated powder, and drying at-50 ℃ for 24h under a vacuum condition (vacuum degree of 20MPa) to obtain Bi2Te3@ rGO negative electrode material.
(4) Dissolving tris (hydroxymethyl) aminomethane in 100mL of deionized water, adding concentrated hydrochloric acid with a pipette, and stirring to give a pH of 8.0To obtain a homogeneous solution; dopamine hydrochloride and Bi2Te3Respectively and completely dissolving and dispersing the @ rGO in the solution in a mass ratio of 1:1, stirring for a period of time, washing with water and ethanol, freeze-drying for 24 hours, keeping the temperature for 2 hours at 450 ℃ under the argon atmosphere, and naturally cooling to obtain a target product Bi2Te3@rGO@NC。
Example 4
(1) Weighing sodium tellurite and bismuth nitrate according to a molar ratio of 2.9:2.1, dispersing the sodium tellurite and the bismuth nitrate into 50mL of ethylene glycol, stirring the mixture for 1h at 40 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium tellurite and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 3.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining and sealing
Reacting for 20 hours at 200 ℃ in a reaction kettle;
(3) precipitating the product obtained in step (2) by a high-speed centrifuge, and cleaning with deionized water
Washing for more than 3 times, finally freezing the generated powder, and drying at-50 ℃ for 24h under the vacuum condition (the vacuum degree is 20MPa) to obtain the Bi2Te3@ rGO negative electrode material.
(4) Dissolving tris (hydroxymethyl) aminomethane in 100mL of deionized water, and adding with a pipette
Concentrated hydrochloric acid, forming a homogeneous solution with a pH of 7.5 by stirring; the dopamine hydrochloride and Bi2Te3@ rGO are completely dissolved and dispersed in the solution respectively according to the mass ratio of 2:1, stirred for a period of time, washed by water and ethanol, freeze-dried for 24 hours, kept at 500 ℃ for 3 hours in an argon atmosphere, and naturally cooled to obtain a target product Bi2Te3@ rGO @ NC.
Example 5
(1) Weighing sodium tellurite and bismuth nitrate according to a molar ratio of 3.05:2, dispersing the sodium tellurite and the bismuth nitrate into 50mL of ethylene glycol, stirring the mixture for 1 hour at 50 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium hydroxide and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 1.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining and sealing
Reacting for 40 hours at 150 ℃ in a reaction kettle;
(3) precipitating the product obtained in step (2) by a high-speed centrifuge, and cleaning with deionized water
Washing for more than 3 times, finally freezing the generated powder, and drying at-40 ℃ for 24h under the vacuum condition (the vacuum degree is 20MPa) to obtain the Bi2Te3@ rGO negative electrode material.
(4) Dissolving tris (hydroxymethyl) aminomethane in 100mL of deionized water, and adding with a pipette
Concentrated hydrochloric acid, forming a homogeneous solution with a pH of 6.8 by stirring; the dopamine hydrochloride and Bi2Te3@ rGO are completely dissolved and dispersed in the solution respectively according to the mass ratio of 2:1, stirred for a period of time, washed by water and ethanol, freeze-dried for 24 hours, kept at 600 ℃ for 1 hour under the argon atmosphere, and naturally cooled to obtain a target product Bi2Te3@ rGO @ NC.
Example 6
(1) Weighing sodium tellurite and bismuth chloride according to a molar ratio of 3:2.1, dispersing the sodium tellurite and the bismuth chloride in 50mL of ethylene glycol, stirring the mixture at 35 ℃ for 4 hours to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium hydroxide and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 2.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining and sealing
Reacting for 38 hours at 160 ℃ in a reaction kettle;
(3) precipitating the product obtained in step (2) by a high-speed centrifuge, and cleaning with deionized water
Washing for more than 3 times, finally freezing the generated powder, and drying at-45 ℃ for 18h under the vacuum condition (the vacuum degree is 20MPa) to obtain the Bi2Te3@ rGO negative electrode material.
(4) Dissolving tris (hydroxymethyl) aminomethane in 100mL of deionized water, and adding with a pipette
Concentrated hydrochloric acid, forming a homogeneous solution with a pH of 7.6 by stirring; the dopamine hydrochloride and Bi2Te3@ rGO are completely dissolved and dispersed in the solution respectively according to the mass ratio of 1.5:1, stirred for a period of time, washed by water and ethanol, freeze-dried for 18 hours, kept at 580 ℃ for 1.5 hours under the argon atmosphere, and naturally cooled to obtain a target product Bi2Te3@ rGO @ NC.
Example 7
(1) Weighing sodium tellurite and bismuth chloride according to a molar ratio of 3:2, dispersing the sodium tellurite and the bismuth chloride in 50mL of ethylene glycol, stirring the mixture for 3 hours at 35 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium hydroxide and the PVP are completely dissolved, adding graphene according to a mass ratio of the bismuth antimonide to the graphene of 2.5, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining and sealing
Reacting for 30 hours at 170 ℃ in a reaction kettle;
(3) precipitating the product obtained in step (2) by a high-speed centrifuge, and cleaning with deionized water
Washing for more than 3 times, finally freezing the generated powder, and drying at-45 ℃ for 18h under the vacuum condition (the vacuum degree is 20MPa) to obtain the Bi2Te3@ rGO negative electrode material.
(4) Dissolving tris (hydroxymethyl) aminomethane in 100mL of deionized water, and adding with a pipette
Concentrated hydrochloric acid, forming a homogeneous solution with a pH of 7.9 by stirring; the dopamine hydrochloride and Bi2Te3@ rGO are completely dissolved and dispersed in the solution respectively according to the mass ratio of 1.5:1, stirred for a period of time, washed by water and ethanol, freeze-dried for 18 hours, kept at 520 ℃ for 3 hours in an argon atmosphere, and naturally cooled to obtain a target product Bi2Te3@ rGO @ NC.
Example 8
(1) Weighing sodium tellurite and bismuth sulfate according to a molar ratio of 3:2.1, dispersing the sodium tellurite and the bismuth sulfate in 50mL of ethylene glycol, stirring the mixture for 3 hours at 35 ℃ to form a uniform solution, adding sodium hydroxide and PVP, continuously stirring the mixture until the sodium hydroxide and the PVP are completely dissolved, adding graphene according to the mass ratio of the bismuth antimonide to the graphene of 4.0, and fully and uniformly stirring the mixture;
(2) transferring the solution obtained in the step (1) into a 100mL polytetrafluoroethylene lining and sealing
Reacting for 35 hours at 175 ℃ in a reaction kettle;
(3) precipitating the product obtained in step (2) by a high-speed centrifuge, and cleaning with deionized water
Washing for more than 3 times, finally freezing the generated powder, and drying at-40 ℃ for 24h under the vacuum condition (the vacuum degree is 20MPa) to obtain the Bi2Te3@ rGO negative electrode material.
(4) Dissolving tris (hydroxymethyl) aminomethane in 100mL of deionized water, and adding with a pipette
Concentrated hydrochloric acid, forming a homogeneous solution with a pH of 7.0 by stirring; the dopamine hydrochloride and Bi2Te3@ rGO are completely dissolved and dispersed in the solution respectively according to the mass ratio of 1:1, stirred for a period of time, washed by water and ethanol, freeze-dried for 24 hours, kept at 450 ℃ for 3 hours under the argon atmosphere, and naturally cooled to obtain a target product Bi2Te3@ rGO @ NC.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.
Claims (10)
1. A bismuth telluride-based composite cathode material for sodium/potassium ion batteries is characterized in that the chemical formula of the cathode material is Bi2Te3@rGO@NC。
2. The preparation method of the bismuth telluride-based composite negative electrode material of the sodium/potassium ion battery as defined in claim 1 is characterized by comprising the following steps:
step 1: weighing sodium tellurite and bismuth salt according to a stoichiometric ratio, dispersing the sodium tellurite and bismuth salt in ethylene glycol, adding sodium hydroxide and polyvinylpyrrolidone, stirring to form a uniform solution, then adding a certain amount of graphene, and stirring and performing ultrasonic treatment to obtain a well-dispersed solution; the stirring temperature is 25-50 ℃, and the stirring time is 2-4 h;
step 2: transferring the solution obtained in the step 1 into a reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at a certain temperature and time;
and step 3: precipitating the product obtained in the step 2 by centrifugation or filtration, washing with water and ethanol for multiple times, and finally freeze-drying the resultant powder to obtain Bi2Te3@rGO；
And 4, step 4: dissolving tris (hydroxymethyl) aminomethane in a certain amount of deionized water, adding a small amount of concentrated hydrochloric acid to adjust the pH value of the solution, and stirring to form a uniform solution; weighing a certain amount of dopamine hydrochloride as a carbon and nitrogen source, completely dissolving the dopamine hydrochloride into the solution, and weighing a certain amount of Bi2Te3@ rGO is uniformly dispersed in the solution under the ultrasonic action, and is stirred for a certain time; washing with water and ethanol, freeze-drying, carbonizing in argon atmosphere, and naturally cooling to obtain the target product Bi2Te3@rGO@NC。
3. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: the bismuth salt in the step 1 can be one or more of bismuth chloride, bismuth nitrate and bismuth sulfate.
4. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: the molar ratio of the sodium tellurite to the bismuth salt in the step 1 is 2.9-3.1: 1.9-2.1.
5. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: the mass ratio of the bismuth antimonide to the graphene in the step 1 is 1.0-5.0.
6. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: the hydrothermal reaction temperature in the step 2 is 150-200 ℃, and the heat preservation time is 20-40 h.
7. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: the vacuum degree of the freeze drying in the step 3 and the step 4 is more than or equal to 10MPa, the temperature is-40 to-50 ℃, and the time is 10 to 24 hours.
8. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: the pH range of the solution in the step 4 is 6.8-8.0.
9. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: dopamine hydrochloride and Bi in step 42Te3The mass ratio of @ rGO is 1.0-2.0.
10. The preparation method of the bismuth telluride-based composite anode material for the sodium/potassium ion battery according to claim 2, wherein the preparation method comprises the following steps: in the step 4, the carbonization temperature is 450-600 ℃, and the carbonization time is 1-3 h.
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