CN109909511B

CN109909511B - Preparation method and application of bismuth-based hollow nano material

Info

Publication number: CN109909511B
Application number: CN201910222755.9A
Authority: CN
Inventors: 张文华; 刘妍; 周斌
Original assignee: Institute of Chemical Material of CAEP
Current assignee: Institute of Chemical Material of CAEP
Priority date: 2019-03-22
Filing date: 2019-03-22
Publication date: 2022-05-03
Anticipated expiration: 2039-03-22
Also published as: CN109909511A

Abstract

The invention discloses a preparation method and application of a bismuth-based hollow nano material, wherein the preparation method comprises the following steps: dissolving copper nano material in solvent to obtain first solution, and adding BiI₃Dissolving the bismuth-based hollow nano material in a solvent to obtain a second solution, mixing the first solution and the second solution, and reacting for a period of time to obtain the bismuth-based hollow nano material, wherein the solvent is dimethyl sulfoxide or N, N-dimethyl propylene urea. The bismuth-based hollow nano material prepared by the method can be used as a negative electrode material to be applied to a sodium ion battery or a lithium ion battery, and has good rate capability, ultra-long cycle stability and higher specific capacity.

Description

Preparation method and application of bismuth-based hollow nano material

Technical Field

The invention relates to the technical field of sodium ion batteries, in particular to a preparation method and application of a bismuth-based hollow nano material.

Background

In recent years, sodium ion batteries have received extensive attention from both academic and industrial fields in the field of large-scale energy storage. Battery performance is strongly dependent on the positive electrode, negative electrode, electrolyte and compatibility between them. Wherein the negative electrode material is a key factor for the development of the sodium ion battery. Therefore, the development of high-performance anode materials for rechargeable sodium-ion batteries is urgent. The metal bismuth is one of sodium ion battery cathode materials with high potential, but the bismuth can generate serious volume expansion after sodium storage, so that the material pulverization is caused, and the stability of the battery is seriously influenced.

Disclosure of Invention

In order to overcome the technical defects, the invention provides a preparation method and application of a bismuth-based hollow nano material, and the bismuth-based hollow nano material prepared by the method can be used as a negative electrode material to be applied to a sodium ion battery or a lithium ion battery, and has good rate capability, overlong cycle stability and higher specific capacity.

In order to achieve the technical effect, the invention provides a preparation method of a bismuth-based hollow nano material, which comprises the following steps: dissolving copper nano material in solvent to obtain first solution, and adding BiI₃Dissolving the bismuth-based hollow nano material in a solvent to obtain a second solution, mixing the first solution and the second solution, and reacting for a period of time to obtain the bismuth-based hollow nano material, wherein the solvent is dimethyl sulfoxide or N, N-dimethyl propylene urea.

The further technical scheme is that the shape of the copper nano material is any one of copper nano particles, copper nano wires, copper nano tubes, copper nano cones or copper nano cubic blocks.

The further technical proposal is that the diameter of the copper nano-particles is 2-500nm, the width of the copper nano-wires is 2-500nm, and the length is 1-1000 μm; the diameter of the copper nano tube is 10-100nm, and the length is as follows: 1-1000 μm; the diameter of the bottom of the copper nano cone is 50-150nm, and the diameter of the tip is as follows: 10-45nm and 1-10 μm in length; the diameter of the copper nano cube is 10-200 nm.

The further technical proposal is that the concentration of the first solution is 0.01-500 mg/mL.

The further technical proposal is that the preparation method of the second solution is to mix BiI₃Dissolving the mixture in dimethyl sulfoxide or N, N-dimethyl propylene urea, and adding 0-1mol/L tetrabutylammonium tetrafluoroborate to obtain a second solution, wherein the concentration of the second solution is 0.001-5 mol/L.

The further technical scheme is that the molar ratio of copper to bismuth in the hollow nano material is 1: 0.5-5.

The further technical scheme is that the reaction time of the first solution and the second solution is longer than five minutes.

The invention also provides an application of the bismuth-based hollow nano material, and the bismuth-based hollow nano material is used as a negative electrode material of a sodium ion battery or a lithium ion battery.

Compared with the prior art, the invention has the following beneficial effects: according to the invention, the first solution and the second solution are mixed to generate a displacement reaction, and meanwhile, the outward diffusion speed of copper species is faster than the inward diffusion speed of bismuth, so that a tubular structure is formed, namely the Kirkendall effect. The prepared hollow structure nano material can effectively buffer the volume expansion of the material, thereby improving the performance of the battery, and the bismuth-based hollow nano material is applied to a sodium ion battery or a lithium ion battery as a negative electrode material, and has good rate capability, overlong cycle stability and higher specific capacity when being used as the negative electrode material of the sodium ion battery or the lithium ion battery.

Drawings

FIG. 1 is an X-ray diffraction pattern of a bismuth nanotube;

FIG. 2 is a transmission electron microscope image of a bismuth nanotube;

FIG. 3 is a schematic diagram of the rate capability of a bismuth nanotube negative sodium ion battery;

fig. 4 is a schematic diagram of the cycling stability of a bismuth nanotube negative sodium ion battery.

Detailed Description

The following examples further illustrate the invention but are not intended to limit the invention thereto.

Example 1

Copper nanoparticles having a particle size of 2nm were prepared into a 10mg/mL Dimethylsulfoxide (DMSO) solution (first solution). Then 0.01mol/L BiI containing 0.01mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO solution with a copper/bismuth molar ratio of 1:1.5 (second solution). The first solution and the second solution were mixed on a magnetic stirrer and stirred at a speed of 100 rpm for 0.5 hour. Washing the product with ethanol, centrifuging, and drying in vacuum to obtain the hollow bismuth nanoparticles. Mixing the hollow nano particles, the carbon black and sodium carboxymethyl cellulose (CMC) according to the mass ratio: 7: 2: 1 preparing slurry to be coated on copper foil, assembling the slurry and a sodium metal sheet into a half cell, wherein a diaphragm is glass fiber, and electrolyte is 1M NaPF₆The electrochemical performance of the battery was examined in the diglyme solution of100mA g^-1At current density, the capacity is 375mA h g^-1。

Example 2

Copper nanoparticles having a particle size of 100nm were prepared into a 20mg/mL N, N-Dimethylpropyleneurea (DMPU) solution (first solution). Then 0.01mol/L BiI is prepared₃DMPU solution (second solution). The first solution and the second solution were mixed at a copper/bismuth molar ratio of 1:2 and reacted for 72 hours. Washing the product with ethanol, centrifuging, and drying in vacuum to obtain the hollow bismuth nanoparticles. Mixing hollow bismuth nanoparticles, carbon black and CMC in a mass ratio of 8: 1:1 preparing slurry to be coated on copper foil and assembling the slurry and sodium metal sheets into a half cell, wherein a diaphragm is glass fiber, and electrolyte is 1M NaPF₆The electrochemical performance of the cell was tested at 200mA g^-1At a current density, the capacity is 321mA h g^-1。

Example 3

Copper nanoparticles with a particle size of 300nm were formulated into 10mg/mL DMSO (first solution). Then preparing BiI₃DMSO solution (second solution), the first solution, the second solution, the copper/bismuth molar ratio of 1:3, reaction for 0.5 hours. Washing the product with ethanol, centrifuging, and drying in vacuum to obtain the hollow bismuth nanoparticles. Mixing the hollow bismuth nanoparticles, the carbon black and the CMC in a mass ratio of: 8: 1:1 preparing slurry to be coated on copper foil, assembling the slurry and a sodium metal sheet into a half cell, wherein a diaphragm is glass fiber, and electrolyte is 1M NaPF₆The electrochemical performance of the cell was tested at 1000mA g^-1At a current density, the capacity is 287mA h g^-1。

Example 4

Copper nanoparticles 500nm in diameter were formulated into 20mg/mL DMSO (first solution). Then 0.01mol/L BiI containing 0.1mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO (second solution). And mixing the first solution and the second solution on a magnetic stirrer, stirring at the speed of 300 revolutions per minute and the molar ratio of copper to bismuth being 1:2, and reacting for 1 hour. Washing the product with ethanol, centrifuging, and drying in vacuum to obtain the hollow bismuth nanoparticles. Mixing hollow bismuth nanoparticles, carbon black and CMC, according to mass ratio: 8: 1:1 preparing slurry to be coated on copper foil, assembling the slurry and a sodium metal sheet into a symmetrical battery, wherein a diaphragm is made of glass fiber, and electrolyte is 1M NaPF₆The electrochemical performance of the cell was tested in a dimethyl ether (DME) solution at 1000mA g^-1At a current density of 295mA hr g^-1。

Example 5

Copper nanowires 45nm in diameter were prepared as a 5mg/mL solution in dimethyl sulfoxide (DMSO) (first solution). Then 0.1mol/L BiI containing 0.1mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO solution (second solution). And mixing the first solution and the second solution on a magnetic stirrer, stirring at a copper/bismuth molar ratio of 1:2 and a stirring speed of 300 revolutions per minute, and reacting for 2 hours. Washing the product with ethanol, centrifuging, and vacuum drying to obtain bismuth nanotube with crystal structure shown in figure 1, pure bismuth, no diffraction peak of other substances, tubular shape shown in figure 2, and diameter of about 50 nm. Mixing bismuth nanotubes, carbon black and CMC in a mass ratio of 7: 2: 1 preparing slurry to be coated on copper foil, assembling the slurry and a sodium metal sheet into a half cell, wherein a diaphragm is glass fiber, and electrolyte is 1M NaPF₆The electrochemical performance of the cell was tested in DME solution. Fig. 3 is a graph of rate performance of the cell at different current densities: at 100mA g^-1、200mA g^-1、600mA g^-1、1000mA g^-1、2000mA g^-1、6000mA g^-1And 10000mA g^-1The specific capacity under the current density is 350mA h g^-1、328mA h g^-1、309mA h g^-1、285mA h g^-1、244mA h g^-1、160mA h g^-1And 95mA h g^-1It can be seen from the figure that when the current density returns to 100mA g^-1The reversible capacity is restored to 350mAh g at the initial current density^-1The battery is proved to have good rate capability. FIG. 4 is a graph of the cycling stability of a battery at 1A g^-1After 1500 cycles under the high current density, the capacity of the battery still keeps 198mAh g^-1And the battery is proved to have ultra-long cycle stability.

Example 6

Copper nanowires with a diameter of 100nm were formulated into 15mg/mL DMSO (first solution). Then 0.2mol/L BiI containing 0.5mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO (second solution). Mixing the first solution and the second solution on a magnetic stirrer, and stirring, wherein the molar ratio of copper to bismuth is 1:2, the stirring speed is 600 rpm, and the reaction is carried out for 72 hours. Washing the product with ethanol, centrifuging, and drying in vacuum to obtain the bismuth nanotube. Mixing the bismuth nanotube, the carbon black and the CMC in a mass ratio of: 7: 1.5: 1.5 coating the slurry on copper foil, assembling with sodium metal sheet to obtain a half-cell, wherein the diaphragm is glass fiber, and the electrolyte is 1M NaPF₆The electrochemical performance of the cell was tested at 200mA g^-1At a current density, the capacity is 330mA h g^-1。

Example 7

Copper nano-cubes with a diameter of 100nm were formulated into a 10mg/mL DMSO solution (first solution). Then 0.01mol/L BiI containing 0.1mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO solution (second solution). And (3) mixing the first solution and the second solution on a magnetic stirrer, and stirring at a stirring speed of 450 revolutions per minute in a copper/bismuth molar ratio of 1: 2.5, reacting for 2 hours. The product was washed with ethanol, centrifuged, and vacuum dried to obtain hollow bismuth nano-cubes. Mixing hollow bismuth nano-cubic blocks, carbon black and CMC in a mass ratio: 7: 2: 1 preparing slurry to be coated on copper foil, assembling the slurry and a sodium metal sheet into a symmetrical battery, wherein a diaphragm is made of glass fiber, and electrolyte is 1M NaPF₆The electrochemical performance of the cell was tested at 1000mA g^-1At a current density, the capacity was 275mA h g^-1。

Example 8

Copper nanoparticles 50nm in diameter were formulated into a 5mg/mL DMSO solution (first solution). Then 0.01mol/L BiI containing 0.1mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO solution (second solution). And (3) mixing the first solution and the second solution on a magnetic stirrer, and stirring at the stirring speed of 300 revolutions per minute and the molar ratio of copper to bismuth of 1:2, reacting for 24 hours. Washing the product with ethanol, centrifuging, and vacuum drying to obtain hollow bismuth nanoparticlesAnd (4) granulating. Mixing the hollow bismuth nanoparticles, the carbon black and the CMC in a mass ratio of: 7: 2: 1 preparing slurry to be coated on copper foil, assembling the slurry and a lithium metal sheet into a symmetrical battery, wherein a diaphragm is glass fiber, and electrolyte is 1M LiPF₆The electrochemical performance of the cell was tested at 1000mA g^-1At a current density, the capacity was 282mA hr g^-1。

Example 9

Copper nanowires 50nm in diameter were formulated into 10mg/mL of DMPU (first solution). Then 0.01mol/L BiI containing 0.1mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMPU (second solution). And (3) mixing the first solution and the second solution on a magnetic stirrer, and stirring at a stirring speed of 500 revolutions per minute in a copper/bismuth molar ratio of 1:2, reacting for 50 hours. Washing the product with ethanol, centrifuging, and drying in vacuum to obtain the bismuth nanotube. Mixing the bismuth nanotube, the carbon black and the CMC in a mass ratio of: 8: 1:1 preparing slurry to be coated on copper foil, assembling the slurry and a lithium metal sheet into a symmetrical battery, wherein a diaphragm is glass fiber, and electrolyte is 1M LiPF₆The electrochemical performance of the cell was tested at 100mA g^-1Under the current density, the capacity is 383mA h g^-1。

Example 10

Copper nano-cubes with a diameter of 150nm were formulated into a 10mg/mL DMSO solution (first solution). Then 0.01mol/L BiI containing 0.1mol/L tetrabutylammonium tetrafluoroborate (TBABF4) is prepared₃DMSO solution (second solution). And (3) mixing the first solution and the second solution on a magnetic stirrer, and stirring at a stirring speed of 400 revolutions per minute in a copper/bismuth molar ratio of 1:3, reacting for 20 hours. The product was washed with ethanol, centrifuged, and vacuum dried to obtain hollow bismuth nano-cubes. Mixing hollow bismuth nano-cubic blocks, carbon black and CMC in a mass ratio: 7: 2: 1 preparing slurry to be coated on copper foil, assembling the slurry and a lithium metal sheet into a symmetrical battery, wherein a diaphragm is glass fiber, and electrolyte is 1M LiPF₆The electrochemical performance of the cell was tested at 200mA g^-1At a current density, the capacity is 330mA h g^-1。

Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.

Claims

1. The preparation method of the bismuth-based hollow nano material is characterized by comprising the following steps of: dissolving copper nano material in solvent to obtain first solution, and adding BiI₃Dissolving the bismuth-based hollow nano material in a solvent to obtain a second solution, mixing the first solution and the second solution, reacting for a period of time to obtain a bismuth-based hollow nano material, applying the bismuth-based hollow nano material to a cathode material of a sodium ion battery or a lithium ion battery, wherein the solvent is dimethyl sulfoxide or N, N-dimethyl propylene urea, the copper nano material is in any one of a copper nano particle, a copper nano wire, a copper nano tube, a copper nano cone or a copper nano cubic block, and the diameter of the copper nano particle is 2-500 nm; the width of the copper nanowire is 2-500nm, and the length of the copper nanowire is 1-1000 mu m; the diameter of the copper nano tube is 10-100nm, and the length is as follows: 1-1000 μm; the diameter of the bottom of the copper nano cone is 50-150nm, and the diameter of the tip is as follows: 10-45nm and 1-10 μm in length; the diameter of the copper nano cube is 10-200nm, and the preparation method of the second solution is to mix BiI₃Dissolving the hollow nano-material in dimethyl sulfoxide or N, N-dimethyl propylene urea, and then adding 0-1mol/L tetrabutyl ammonium tetrafluoroborate to obtain a second solution, wherein the concentration of the second solution is 0.001-5mol/L, the molar ratio of copper to bismuth in the hollow nano-material is 1:0.5-5, and the reaction time of the first solution and the second solution is longer than five minutes.

2. The method for preparing the bismuth-based hollow nanomaterial according to claim 1, wherein the concentration of the first solution is 0.01 to 500 mg/mL.