CN114927690B - Nitrogen-doped carbon-coated nano antimony bismuth alloy material and preparation method and application thereof - Google Patents

Nitrogen-doped carbon-coated nano antimony bismuth alloy material and preparation method and application thereof Download PDF

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CN114927690B
CN114927690B CN202210485581.7A CN202210485581A CN114927690B CN 114927690 B CN114927690 B CN 114927690B CN 202210485581 A CN202210485581 A CN 202210485581A CN 114927690 B CN114927690 B CN 114927690B
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唐磊
杨建广
张洋
王西晓
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Shiny Materials Science & Technology Inc
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Abstract

The application discloses a nitrogen-doped carbon-coated nano antimony-bismuth alloy material, a preparation method and application thereof. The application firstly adopts the shearing emulsification technology to carry out Bi (OH) at a specific rotating speed 3 、Sb(OH) 3 The co-precipitated starch is prepared to obtain nano-grade antimony bismuth oxide composite powder with uniform particle size and good dispersibility, and then the nitrogen-doped carbon layer is coated on the basis of the nano-grade antimony bismuth oxide composite powder, so that the nitrogen-doped carbon layer with excellent coating effect can be obtained, and the nitrogen-doped carbon-coated nano-antimony bismuth alloy material provided by the application has excellent electrochemical performance under the synergistic effect of the nitrogen-doped carbon layer and alloying.

Description

Nitrogen-doped carbon-coated nano antimony bismuth alloy material and preparation method and application thereof
Technical Field
The application belongs to the technical field of negative electrode materials of sodium ion batteries, and particularly relates to a nitrogen-doped carbon-coated nano antimony-bismuth alloy material, and a preparation method and application thereof.
Background
Sodium has abundant reserves in the crust, has similar chemical properties to lithium and has great potential in the energy storage field. However, due to the influence of the radius of sodium ions, conventional graphite is difficult to be directly used as a negative electrode material of a sodium battery, and therefore, development of an electrochemically stable negative electrode material has become a problem to be solved in the development of sodium ion batteries.
Among the negative electrode materials, the antimony-based negative electrode material shows high specific capacity of 660mAh/g and a proper discharge platform through alloying reaction with sodium, and is a sodium ion battery negative electrode material with great potential. However, antimony is often accompanied by significant volume expansion during alloying with sodium, resulting in pulverization of the antimony anode active material, reduced electrochemical performance, failure of the battery, and severely limited application of antimony-based anode materials.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide a nitrogen-doped carbon-coated nano antimony-bismuth alloy material, and a preparation method and application thereof.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the application relates to a nitrogen-doped carbon-coated nano antimony-bismuth alloy material, which consists of nano antimony-bismuth alloy and a nitrogen-doped carbon layer coated on the surface of the nano antimony-bismuth alloy.
According to the nitrogen-doped carbon-coated nano antimony-bismuth alloy material provided by the application, the core material is nano antimony-bismuth alloy, the inventor discovers that bismuth is added into the antimony anode material as an alloy element, and can be mutually buffered in the alloying process of antimony and sodium, so that the volume expansion is greatly reduced, the pulverization of an antimony anode active substance is avoided, and the nitrogen-doped carbon is adopted as a coating layer, so that on one hand, the carbon coating is utilized to treat the nano antimony-bismuth alloy, the side reaction of the antimony-bismuth alloy and an electrolyte interface is reduced, the electrochemical stability of the anode material is improved, and on the other hand, through nitrogen doping, the electroneutrality of the carbon material is effectively destroyed, the band gap of the carbon material is opened, and the electrochemical activity and conductivity of a carbon coating structure are improved.
For alloying with antimony, the inventors have also tried other elements such as tin, nickel, zinc, copper, etc. during experimental exploration, and as a result, found that alloying with antimony only by bismuth resulted in the material having the best properties.
In a preferred scheme, in the nano antimony bismuth alloy, according to the mole ratio, sb: bi=0.5 to 2.
In a preferred scheme, the grain diameter of the nitrogen-doped carbon-coated nano antimony bismuth alloy material is 30-100 nm, and the thickness of the nitrogen-doped carbon layer is 5-10 nm.
The inventor discovers that controlling the grain size and the coating layer of the nitrogen-doped carbon-coated nano antimony bismuth alloy material within the above ranges, the electrochemical performance of the final nitrogen-doped carbon-coated nano antimony bismuth alloy material is most excellent, if the grain size is too large, the volume expansion in the alloying process is still greatly affected, and the electrochemical performance of the cathode material is reduced.
The application relates to a preparation method of a nitrogen-doped carbon-coated nano antimony bismuth alloy material, which comprises the steps of SbCl 3 With BiCl 3 Dissolving in hydrochloric acid to obtain Sb-containing solution 3+ 、Bi 3+ Then adding Sb to the solution 3+ 、Bi 3+ The solution of (2) and ammonia water are simultaneously dripped into water to obtain reaction liquid, and the coprecipitation reaction is carried out under stirring to obtain Bi (OH) -containing solution 3 、Sb(OH) 3 And (2) carrying out heat treatment on the coprecipitated starch to obtain antimony bismuth oxide composite powder, adding the antimony bismuth oxide composite powder into an acid solution containing aniline to obtain a mixed solution, adding an ammonium persulfate solution into the mixed solution, carrying out polymerization reaction, carrying out solid-liquid separation to obtain polyaniline coated antimony bismuth oxide composite powder, and carrying out heat treatment on the polyaniline coated antimony bismuth oxide composite powder in a protective atmosphere to obtain the nitrogen-doped carbon-coated nano antimony bismuth alloy material.
Preferred embodiments, the SbCl 3 With BiCl 3 The molar ratio of (2) is 0.5-2.
Preferably, the concentration of the hydrochloric acid is 2-5 mol/L.
Preferred embodiments, the SbCl 3 With hydrochloric acidThe solid-liquid mass volume ratio is 2.5-25 g:1L.
Preferred embodiments will contain Sb 3+ 、Bi 3+ The solution of (2) and ammonia water are simultaneously dripped into water to obtain a reaction solution, the pH value of the reaction solution is controlled to be 2.5-4 in the dripping process, and the coprecipitation reaction is carried out under stirring to obtain the Bi (OH) containing solution 3 、Sb(OH) 3 Is a co-precipitated starch; the stirring mode is shearing stirring, and the stirring speed is 3000-9000 rpm.
The inventor discovers that the stirring process has great influence on the morphology of the preparation of the antimony bismuth oxide composite powder, the nano-grade antimony bismuth oxide composite powder with uniform particle size and good dispersibility can be obtained by adopting a dripping mode and shearing and stirring and controlling the rotating speed within the range, and the antimony bismuth oxide composite powder can lead the aniline to have a better nitrogen-doped carbon layer
In a preferred scheme, the temperature of the heat treatment of the coprecipitated starch is 450-600 ℃, and the time of the heat treatment of the coprecipitated starch is 40-120 min.
Preferably, the pH of the aniline-containing acid solution is 1-2.5.
Preferably, the aniline-containing acid solution is obtained by adding an acid solution to aniline, and the acid solution is selected from hydrochloric acid solution and/or sulfuric acid solution.
In a preferred scheme, the solid-liquid mass volume ratio of the antimony oxide bismuth composite powder to the aniline-containing acid solution is 1 g:50-200 mL.
In a preferred scheme, the solid-liquid mass volume ratio of the antimony oxide bismuth composite powder to the aniline is 1g: 500-1500 mu L.
In the application, the material ratio of the aniline and the antimony bismuth oxide composite powder is controlled within the range, and the thickness of the nitrogen-doped carbon layer of the finally obtained material is 5-10 nm, so that the electrochemical performance of the nitrogen-doped carbon-coated nano antimony bismuth alloy material is optimal, and if the aniline is excessively added, the generated carbon coating layer is too thick, the antimony content in the active substance is lower, and the specific capacity of the anode material is reduced; meanwhile, the active material cannot be dissolved in DMF (dimethyl formamide) which is a solvent for preparing the anode material, and the slurry prepared by the active material is difficult to uniformly coat on a copper current collector.
Preferably, the concentration of the ammonium persulfate solution is 20-50 g/L; the solid-liquid mass volume ratio of ammonium persulfate to aniline is 1 g:500-1000 mu L.
In a preferred embodiment, the ammonium persulfate solution is added to the mixed solution at a flow rate of 1 to 5 mL/min.
The inventor discovers that the flow rate of the ammonium persulfate solution needs to be effectively controlled, if the ammonium persulfate is added dropwise too fast, the yield of the polyaniline product is reduced, and if the ammonium persulfate is added too slowly, the active reaction centers generated by the system are too few, the induction period is too long, and the generated polyaniline coating has poor conductive effect.
In a preferred scheme, the temperature of the polymerization reaction is 20-40 ℃, and the time of the polymerization reaction is 1-4 h.
Preferably, the protective atmosphere is selected from N 2 And/or Ar 2 。
In a preferred scheme, the heating rate of the polyaniline-coated antimony oxide bismuth composite powder is 2-10 ℃/min in the heat treatment under the protective atmosphere, the heat treatment temperature is 650-800 ℃, and the heat treatment time is 30-120 min. And naturally cooling to room temperature after the heat preservation is finished.
In the application, the temperature of the heat treatment is controlled within the range, so that the carbon reduction temperature of antimony and bismuth can be reached, and finally the nitrogen-doped carbon-coated nano antimony-bismuth alloy material with excellent electrochemical performance is formed.
The application also provides application of the nitrogen-doped carbon-coated nano antimony-bismuth alloy material, and the nitrogen-doped carbon-coated nano antimony-bismuth alloy material is used as a negative electrode material in a sodium ion battery.
Principle and advantages
The application provides a nitrogen-doped carbon-coated nano antimony-bismuth alloy material, wherein a core material is nano antimony-bismuth alloy, the inventor finds that bismuth is added into an antimony negative electrode material as an alloy element, and can buffer each other in the alloying process of antimony and sodium, so that volume expansion is greatly reduced, pulverization of an antimony negative electrode active substance is avoided, and nitrogen-doped carbon is adopted as a coating layer, on one hand, the carbon coating is utilized to treat the nano antimony-bismuth alloy, side reaction of an interface between the antimony-bismuth alloy and an electrolyte is reduced, electrochemical stability of the negative electrode material is improved, on the other hand, through nitrogen doping, the electric neutrality of the carbon material is effectively destroyed, the band gap of the carbon material is opened, and electrochemical activity and conductivity of a carbon coating structure are improved.
The preparation method of the application firstly adopts the shearing emulsification technology to carry out Bi (OH) at a specific rotating speed 3 、Sb(OH) 3 The preparation of coprecipitation powder can obtain nano-grade antimony bismuth oxide composite powder with uniform particle size and good dispersibility, and then the coating of the nitrogen-doped carbon layer is carried out on the basis of the nano-grade antimony bismuth oxide composite powder, so that the nitrogen-doped carbon layer with excellent coating effect can be obtained, and the nitrogen-doped carbon-coated nano-antimony bismuth alloy material provided by the application has excellent electrochemical performance under the synergistic effect of the nitrogen-doped carbon layer and alloying.
The negative electrode active material prepared by the application can effectively relieve the volume expansion effect of antimony in the charge and discharge process, and the obtained negative electrode material has good cycle performance and excellent multiplying power performance;
the method provided by the application has the advantages of simple process flow, easy operation and easy realization of industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of the nitrogen-doped carbon-coated nano antimony bismuth alloy prepared in example 1.
FIG. 2 is a graph showing the voltage-capacity curve of the nitrogen-doped carbon-coated nano-antimony-bismuth alloy prepared in example 1 in a sodium-ion half-cell test;
FIG. 3 is a graph showing the cycle performance of the nitrogen-doped carbon-coated nano-antimony bismuth alloy prepared in example 1 in a sodium-ion half-cell test;
fig. 4 is a graph showing the rate performance of the nitrogen-doped carbon-coated nano antimony bismuth alloy prepared in example 1 in a sodium-ion half cell test.
Detailed Description
The present application will be described in further detail with reference to the following examples. The application is not limited to the following specific embodiments.
Example 1
Step one, 11.5g SbCl 3 And 13g BiCl 3 Dissolved in 1L of hydrochloric acid with a concentration of 2.5mol/L to obtain solution 1. Dropping the solution 1 and 1.5mol/L ammonia water into a beaker containing deionized water simultaneously for coprecipitation reaction, stirring by adopting an L-80 shearing emulsifying machine during the reaction, controlling the shearing rate to be 3500 revolutions per minute, and controlling the pH value to be 3 during the dropping process to obtain Bi (OH) 3 And Sb (OH) 3 Co-precipitating powder;
step two, placing the coprecipitated powder prepared in the step one into a crucible, heating to 550 ℃ at a heating rate of 8 ℃/min, and preserving heat for 90min to prepare antimony bismuth oxide composite powder;
and thirdly, weighing 1g of the antimony bismuth oxide composite powder obtained in the second step, adding the antimony bismuth oxide composite powder into 100mL of sulfuric acid solution with the pH of 1, and adding 1000 mu L of aniline into the sulfuric acid solution to prepare solution 2. Adding 25mL of ammonium persulfate solution with the concentration of 40g/L into the solution 2 at the flow rate of 2mL/min to prepare polyaniline-coated antimony oxide bismuth composite powder;
and step four, placing the polyaniline-coated antimony bismuth oxide composite powder obtained in the step three into a crucible, heating to 700 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 60min, and cooling to room temperature along with a furnace after the heat preservation is finished, so as to finally obtain the nitrogen-doped carbon-coated antimony bismuth alloy anode material.
FIG. 1 is a scanning electron microscope image of the nitrogen-doped carbon-coated nano antimony bismuth alloy prepared in example 1, from which it can be seen that the average particle size of the nitrogen-doped carbon-coated nano antimony bismuth alloy is 45nm; the thickness of the nitrogen-doped carbon layer was also measured to be 5 to 10nm.
Mixing the obtained nitrogen-doped carbon-coated antimony bismuth alloy anode material with acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1, adding the mixture into N, N-dimethylamide, stirring for 8 hours, coating the mixture on a copper current collector, and finally drying the mixture in a vacuum drying oven at 80 ℃ for 12 hours. The active material coated on the copper current collector was used as a battery anode material.
Electrochemical tests show that under the current density of 0.1C, the first discharge capacity of the obtained anode material is 571.60mAh/g, the discharge capacity of the anode material after 50 charge-discharge cycles is 397.68mAh/g, and the capacity retention rate of the anode material is 69.57%.
Example 2
Step one, 23g SbCl 3 And 26g BiCl 3 Dissolved in 1L of hydrochloric acid with a concentration of 4mol/L to obtain a solution 1. Dropping the solution 1 and 2mol/L ammonia water into a new beaker containing deionized water simultaneously for coprecipitation reaction, stirring by adopting an L-300 shearing emulsifying machine during the reaction, controlling the shearing rate to 6500 revolutions per minute, and controlling the pH value in the dropping process to be 2.5 to obtain Bi (OH) 3 And Sb (OH) 3 Co-precipitating powder;
step two, placing the coprecipitated powder prepared in the step one into a crucible, heating to 600 ℃ at a heating rate of 10 ℃/min, and preserving heat for 60min to prepare antimony bismuth oxide composite powder;
and thirdly, weighing 10g of the antimony bismuth oxide composite powder obtained in the second step, adding the antimony bismuth oxide composite powder into 1500mL of sulfuric acid with the pH of 1.5, and adding 5000 mu L of aniline into the sulfuric acid to prepare a solution 2. Adding 100mL of ammonium persulfate solution with the concentration of 50g/L into the solution 2 at the flow rate of 5mL/min to prepare polyaniline-coated antimony oxide bismuth composite powder;
and fourthly, placing the polyaniline-coated antimony bismuth oxide composite powder obtained in the third step into a crucible, heating to 650 ℃ at a heating rate of 8 ℃/min under argon atmosphere, preserving heat for 120min, and cooling to room temperature along with a furnace after the heat preservation is finished, so as to finally obtain the nitrogen-doped carbon-coated antimony bismuth alloy negative electrode material.
Electrochemical tests show that under the current density of 1C, the first discharge capacity of the obtained anode material is 495.36mAh/g, the discharge capacity of the anode material after 50 charge-discharge cycles is 267.41mAh/g, and the capacity retention rate of the anode material is 53.98%.
Example 3
Step one, 14g SbCl 3 And 15.5g BiCl 3 Dissolved in 1L of hydrochloric acid with a concentration of 3.5mol/L to obtain solution 1. Dropping the solution 1 and 4mol/L ammonia water into a beaker containing deionized water to perform coprecipitation reaction, stirring by adopting an L-120 shearing emulsifying machine during the reaction, controlling the shearing rate to be 5000 revolutions per minute, and controlling the pH value to be 4 during the dropping process to obtain Bi (OH) 3 And Sb (OH) 3 Co-precipitating powder;
step two, placing the coprecipitated powder prepared in the step one into a crucible, heating to 500 ℃ at a heating rate of 5 ℃/min, and preserving heat for 120min to prepare antimony bismuth oxide composite powder;
and thirdly, weighing 5g of the antimony bismuth oxide composite powder obtained in the second step in 1000mL of hydrochloric acid with the pH of 2, and adding 7500 mu L of aniline into the solution to prepare a solution 2. Adding 150mL of an acidic ammonium persulfate solution with the concentration of 50g/L into the solution 2 at the flow rate of 5mL/min to prepare polyaniline-coated antimony oxide bismuth powder;
and step four, placing the polyaniline-coated antimony bismuth oxide composite powder obtained in the step three into a crucible, heating to 750 ℃ at a heating rate of 10 ℃/min under argon atmosphere, preserving heat for 45min, and cooling to room temperature along with a furnace after the heat preservation is finished, so as to finally obtain the nitrogen-doped carbon-coated antimony bismuth alloy anode material.
Electrochemical tests show that under the current density of 2C, the first discharge capacity of the obtained anode material is 421.84mAh/g, the discharge capacity of the anode material after 50 charge-discharge cycles is 281.05mAh/g, and the capacity retention rate of the anode material is 66.62%.
Example 4
Step one, 9g SbCl 3 And 10.5g BiCl 3 Dissolved in 1L of hydrochloric acid solution with the concentration of 3mol/L to obtain solution 1. Dropping the solution 1 and 1mol/L ammonia water into a beaker containing deionized water simultaneously for coprecipitation reaction, stirring by adopting an L-120 shearing emulsifying machine during the reaction, controlling the shearing rate to be 5000 revolutions per minute, and controlling the pH value to be 3 during the dropping process to obtain Bi (OH) 3 And Sb (OH) 3 Co-precipitating powder;
step two, placing the coprecipitated powder prepared in the step one into a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90min to prepare antimony bismuth oxide composite powder;
step three, weighing 10g of the antimony bismuth oxide composite powder obtained in the step two, adding the antimony bismuth oxide composite powder into 500mL of sulfuric acid with pH of 2, and adding 7500 mu L of aniline into the sulfuric acid to prepare solution 2. Adding 250mL of an acidic ammonium persulfate solution with the concentration of 60g/L into the solution 2 at the flow rate of 5mL/min to prepare polyaniline-coated antimony oxide bismuth composite powder;
and fourthly, placing the polyaniline-coated antimony bismuth oxide composite powder obtained in the third step into a crucible, heating to 650 ℃ at a heating rate of 8 ℃/min under argon atmosphere, preserving heat for 120min, and cooling to room temperature along with a furnace after the heat preservation is finished, so as to finally obtain the nitrogen-doped carbon-coated antimony bismuth alloy negative electrode material.
Electrochemical tests show that under the current density of 0.1C, the first discharge capacity of the obtained anode material is 620.41mAh/g, the discharge capacity of the anode material after 50 charge-discharge cycles is 407.91mAh/g, and the capacity retention rate of the anode material is 65.75%.
The above embodiments are merely for illustrating technical features of the present application, and should not be used to limit the scope of the present application. All equivalent changes or modifications made on the basis of the technical proposal of the application should be covered in the protection scope of the application.
Comparative example 1 (Co-precipitation without shearing)
The other conditions were the same as in example 1 above, except that Bi (OH) was prepared 3 And Sb (OH) 3 The common spiral stirring treatment is adopted during coprecipitation of powder, and the stirring treatment by a shearing emulsifying machine is not adopted. SEM (scanning electron microscope) detection shows that the particle size and morphology of the obtained antimony bismuth oxide composite powder are not uniform, the agglomeration phenomenon is serious, and the particle size D50 is 97 mu m. Electrochemical tests prove that under the current density of 0.1 ℃, the first discharge capacity of the obtained anode material is 314.60mAh/g, the discharge capacity of the anode material after 50 charge-discharge cycles is 107.55mAh/g, and the capacity retention rate of the anode material is 34.18%.
Comparative example 2 (without nitrogen coating)
Other conditions are the same as those of the above embodiment 1, except that the prepared antimony bismuth oxide composite powder is not subjected to nitrogen coating treatment, and electrochemical tests prove that under the current density of 0.1C, the obtained anode material has a first discharge capacity of 302.35mAh/g, the anode material has a discharge capacity of 102.45mAh/g after 50 charge-discharge cycles, and the capacity retention rate of the anode material is 33.88%.
Comparative example 3 (alloying with tin)
Other conditions were the same as in example 1 above, except that SnCl was used 4 And SbCl 3 The coprecipitation is carried out to prepare nitrogen-doped carbon-coated tin-antimony alloy powder, and electrochemical tests show that under the current density of 0.1C, the first discharge capacity of the obtained anode material is 561.44mAh/g, the discharge capacity of the anode material after 5 charge-discharge cycles is 163.18mAh/g, and the capacity retention rate of the anode material is 29.06%.
Comparative example 4 (alloying with Zinc)
Other conditions were the same as in example 1 above, except that CuCl was used 2 And SbCl 3 The coprecipitation is carried out to prepare nitrogen-doped carbon-coated tin-antimony alloy powder, and electrochemical tests show that under the current density of 0.1C, the first discharge capacity of the obtained anode material is 417.60mAh/g, the discharge capacity of the anode material after 5 charge-discharge cycles is 64.91mAh/g, and the capacity retention rate of the anode material is 15.54%.

Claims (8)

1. A nitrogen-doped carbon-coated nano antimony bismuth alloy material is characterized in that: consists of a nano antimony-bismuth alloy and a nitrogen-doped carbon layer coated on the surface of the nano antimony-bismuth alloy;
in the nano antimony bismuth alloy, according to the mole ratio, sb: bi=0.5 to 2;
the grain diameter of the nitrogen-doped carbon-coated nano antimony bismuth alloy material is 30-100 nm, and the thickness of the nitrogen-doped carbon layer is 5-10 nm;
the preparation method of the nitrogen-doped carbon-coated nano antimony bismuth alloy material comprises the following steps:
will SbCl 3 With BiCl 3 Dissolving in hydrochloric acid to obtain Sb-containing solution 3+ 、Bi 3+ Then adding Sb to the solution 3+ 、Bi 3+ The solution of (2) and ammonia water are simultaneously dripped into water to obtain a reaction solution, the pH value of the reaction solution is controlled to be 2.5-4 in the dripping process, and the coprecipitation reaction is carried out under stirring to obtain the Bi (OH) containing solution 3 、Sb(OH) 3 Is a co-precipitated starch; carrying out heat treatment on coprecipitated starch to obtain antimony bismuth oxide composite powder, adding the antimony bismuth oxide composite powder into an acid solution containing aniline,obtaining a mixed solution, adding ammonium persulfate solution into the mixed solution, carrying out polymerization reaction, carrying out solid-liquid separation to obtain polyaniline-coated antimony oxide bismuth composite powder, and carrying out heat treatment on the polyaniline-coated antimony oxide bismuth composite powder under a protective atmosphere to obtain the nitrogen-doped carbon-coated nano antimony bismuth alloy material; the stirring mode is shearing stirring, and the stirring speed is 3000-9000 rpm.
2. The method for preparing the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 1, which is characterized by comprising the following steps: will SbCl 3 With BiCl 3 Dissolving in hydrochloric acid to obtain Sb-containing solution 3+ 、Bi 3+ Then adding Sb to the solution 3+ 、Bi 3+ The solution of (2) and ammonia water are simultaneously dripped into water to obtain a reaction solution, the pH value of the reaction solution is controlled to be 2.5-4 in the dripping process, and the coprecipitation reaction is carried out under stirring to obtain the Bi (OH) containing solution 3 、Sb(OH) 3 Is a co-precipitated starch; performing heat treatment on coprecipitated starch to obtain antimony bismuth oxide composite powder, adding the antimony bismuth oxide composite powder into an acid solution containing aniline to obtain a mixed solution, adding an ammonium persulfate solution into the mixed solution, performing polymerization reaction and solid-liquid separation to obtain polyaniline coated antimony bismuth oxide composite powder, and performing heat treatment on the polyaniline coated antimony bismuth oxide composite powder in a protective atmosphere to obtain the nitrogen-doped carbon-coated nano antimony bismuth alloy material; the stirring mode is shearing stirring, and the stirring speed is 3000-9000 rpm.
3. The method for preparing the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 2, which is characterized by comprising the following steps: the SbCl 3 With BiCl 3 The molar ratio of (2) is 0.5-2; the concentration of the hydrochloric acid is 2-5 mol/L; the SbCl 3 The solid-liquid mass volume ratio of the aqueous solution to hydrochloric acid is 2.5-25 g:1L.
4. The method for preparing the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 2, which is characterized by comprising the following steps: the temperature of the heat treatment of the coprecipitated starch is 450-600 ℃, and the time of the heat treatment of the coprecipitated starch is 40-120 min.
5. The method for preparing the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 2, which is characterized by comprising the following steps: the pH value of the acid solution containing aniline is 1-2.5; the aniline-containing acid solution is obtained by adding an acid solution to aniline, and the acid solution is selected from hydrochloric acid solution and/or sulfuric acid solution; the solid-liquid mass volume ratio of the antimony oxide bismuth composite powder to the aniline-containing acid solution is 1 g:50-200 mL; the solid-liquid mass volume ratio of the antimony oxide bismuth composite powder to the aniline is 1g: 500-1500 mu L.
6. The method for preparing the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 2, which is characterized by comprising the following steps: the concentration of the ammonium persulfate solution is 20-50 g/L; the solid-liquid mass volume ratio of ammonium persulfate to aniline is 1 g:500-1000 mu L;
adding ammonium persulfate solution into the mixed solution at a flow rate of 1-5 mL/min;
the temperature of the polymerization reaction is 20-40 ℃, and the time of the polymerization reaction is 1-4 h.
7. The method for preparing the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 2, which is characterized by comprising the following steps: the heating rate of the polyaniline coated antimony oxide bismuth composite powder is 2-10 ℃/min in the heat treatment under the protective atmosphere, the heat treatment temperature is 650-800 ℃, and the heat treatment time is 30-120 min.
8. The application of the nitrogen-doped carbon-coated nano antimony bismuth alloy material according to claim 1, which is characterized in that: the nitrogen-doped carbon-coated nano antimony bismuth alloy material is used as a negative electrode material in a sodium ion battery.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013065787A1 (en) * 2011-11-02 2013-05-10 独立行政法人産業技術総合研究所 Negative electrode material for sodium secondary battery and method for producing same, negative electrode for sodium secondary battery, and sodium secondary battery
JP2016134376A (en) * 2015-01-22 2016-07-25 住友電気工業株式会社 Negative electrode for sodium ion secondary battery and sodium ion secondary battery
CN113571682A (en) * 2021-07-29 2021-10-29 广东工业大学 Bismuth/carbon composite material and preparation method and application thereof
CN113753876A (en) * 2021-07-20 2021-12-07 中南大学 Potassium ion battery negative electrode material and preparation method thereof
CN114094078A (en) * 2021-11-16 2022-02-25 中国科学院深圳先进技术研究院 Nitrogen-doped carbon-coated metal sulfide heterojunction material, preparation method and battery application
CN114256453A (en) * 2021-12-24 2022-03-29 永高股份有限公司 Antimony bismuth carbon nano composite material, preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107534137A (en) * 2015-02-05 2018-01-02 德克萨斯大学系统董事会 For lithium or the bismuth antimony anode of sodium-ion battery group

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013065787A1 (en) * 2011-11-02 2013-05-10 独立行政法人産業技術総合研究所 Negative electrode material for sodium secondary battery and method for producing same, negative electrode for sodium secondary battery, and sodium secondary battery
JP2016134376A (en) * 2015-01-22 2016-07-25 住友電気工業株式会社 Negative electrode for sodium ion secondary battery and sodium ion secondary battery
CN113753876A (en) * 2021-07-20 2021-12-07 中南大学 Potassium ion battery negative electrode material and preparation method thereof
CN113571682A (en) * 2021-07-29 2021-10-29 广东工业大学 Bismuth/carbon composite material and preparation method and application thereof
CN114094078A (en) * 2021-11-16 2022-02-25 中国科学院深圳先进技术研究院 Nitrogen-doped carbon-coated metal sulfide heterojunction material, preparation method and battery application
CN114256453A (en) * 2021-12-24 2022-03-29 永高股份有限公司 Antimony bismuth carbon nano composite material, preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Xiao-Dong He，etal..From nanomelting to nanobeads: nanostructured SbxBi1 x alloys anchored in three-dimensional carbon frameworks as a high-performance anode for potassium-ion batteries.《Journal of Materials Chemistry A》.2019,(第第7期期),27041–27047. *

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