CN113263184B - Selenium-doped nano antimony, preparation method and application thereof - Google Patents
Selenium-doped nano antimony, preparation method and application thereof Download PDFInfo
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 58
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 133
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011669 selenium Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 20
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 20
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 238000012512 characterization method Methods 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- 235000019441 ethanol Nutrition 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 10
- -1 centrifuging Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006104 solid solution Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 63
- 239000007789 gas Substances 0.000 description 7
- 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 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/0003—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses selenium-doped nano antimony, a preparation method and application thereof, wherein anhydrous ethanol is used as a solvent, selenium powder is used as a selenium source, antimony trichloride is used as an antimony source, sodium borohydride is used as a reducing agent, a solvothermal method is utilized to obtain nano particles with uniform size distribution and 30-50nm, and phase characterization shows that the nano particles are pure phases. The doped product provided by the invention has no impure phase antimony selenide, and the obtained product has small particle size and uniform appearance. In addition, sb of the present invention 1‑x Se x The material used as the cathode material of the sodium ion battery is 0.5A g ‑1 Shows 462.5mAh g at the current density of ‑1 The first cycle of the battery has specific charge capacity, and the residual capacity after 100 cycles is 481.5mAh g ‑1 . The solid solution of selenium in the crystal lattice of the nano antimony is beneficial to the rapid diffusion of sodium ions to synthesize the product Sb 1‑x Se x Has good electrochemical performance and can be used in the technical fields of energy material application and the like.
Description
Technical Field
The invention relates to a preparation method and application of a selenium-doped nano antimony material, belonging to the technical field of energy material application.
Background
In recent years, due to environmental problems, fuel vehicle sale prohibition schedules are established in various countries around the world, new clean energy sources are sought, and the dependence on fossil energy sources is reduced. The use of secondary ion batteries for energy storage is an important channel for obtaining clean energy. In the field of secondary ion batteries, secondary sodium ion batteries have been gradually emerging in recent years because of abundant sodium reserves, wide distribution, simple extraction, and low price. The sodium ion battery has wide application prospect in occasions requiring large-scale energy storage, such as the load for balancing a power grid and the like. The metal antimony can perform alloying reaction with sodium, is used for a sodium ion battery cathode, and has higher capacity. The main problem existing at present is that the alloying reaction of antimony and sodium can bring about large volume change, and in the circulating process, pulverization occurs and the antimony and the sodium fall off from the surface of a pole piece, so that the rapid capacity attenuation is caused. Therefore, a new preparation method is needed to be developed to optimize antimony and achieve the effect of improving the electrochemical performance of antimony.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide the selenium-doped nano antimony, the preparation method and the application thereof. The invention dopes and modifies antimony to improve the electrochemical performance of the antimony, and can be used in the technical fields of energy material application and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of selenium-doped nano-antimony adopts a solvothermal method, takes absolute ethyl alcohol as a solvent, selenium powder as a selenium source, antimony trichloride as an antimony source and sodium borohydride as a reducing agent to carry out hydrothermal reaction, and Sb with the maximum particle diameter of 20-50nm and uniform size distribution is obtained 1-x Se x Nanoparticles, wherein 0 < x < 1, phase characterization shows pure phase.
Preferably, the preparation method of the selenium-doped nano antimony comprises the following steps:
a. preparing a reducing solution containing sodium hydroselenide:
weighing 10-60mg of selenium powder and 0.6-1.6g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 30-100mL of ethanol, and stirring to fully react to obtain a reducing solution containing sodium selenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 0.8-2.6g of antimony trichloride into 15-50mL of ethanol, and stirring to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. preparation of Sb 1-x Se x Precursor solution of material:
dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and stirring for 20-60 minutes until no gas is generated to obtain a precursor solution;
transferring the precursor solution into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 50-70%, reacting for 10-20 hours in a hydrothermal reaction kettle closed system at 100-130 ℃, and after the reaction is finished, centrifuging and washing the product solution to obtain a reaction product, namely selenium-doped nano antimony particles.
Preferably, when the reducing solution containing sodium hydrogen selenide is prepared in the step a, 10-30mg of selenium powder and 0.6-0.8g of sodium borohydride are weighed and placed into a flask, 30-50mL of ethanol is added, and stirring is carried out for at least 20min, so that reactants are fully reacted, and the reducing solution containing sodium hydrogen selenide is obtained.
Preferably, in the preparation of the ethanol solution of antimony trichloride in the step b, 0.8 to 1.3g of antimony trichloride is dissolved in 15 to 25mL of ethanol, and at least 20nim is stirred to be completely dissolved.
Preferably, in the step c, the product solution after the reaction is finished is centrifuged and washed, and the rotation speed of the centrifugation is not lower than 8000rpm; after the solution after the reaction is centrifuged, an absolute ethyl alcohol solvent is used for cleaning, and one centrifugation and washing process is completed; repeating the centrifuging and washing processes at least 2 times; then, washing by using deionized water, centrifuging, and finishing a subsequent centrifuging and washing process; repeating the subsequent centrifugation and washing processes at least 2 times; and finally, washing by using an absolute ethyl alcohol solvent, centrifuging, collecting the obtained product, and drying in an oven at 50-70 ℃ to obtain pure and dry selenium-doped nano antimony particles.
Preferably, the method of the invention obtains Sb with the maximum particle diameter of 20-50nm and uniform size distribution by hydrothermal reaction 1-x Se x Particles of a nanomaterial.
The invention relates to selenium-doped nano antimony, which is prepared by the preparation method of the selenium-doped nano antimony.
The application of the selenium-doped nano antimony is characterized in that: the selenium-doped nano antimony is used as an active substance component in an electrode material component in a sodium ion battery to prepare an electrode component.
Compared with the prior art, the invention has the following obvious substantive characteristics and remarkable advantages:
1. the doped product prepared by the method is pure phase and does not contain second phase antimony selenide, the particle size of the obtained doped product is small, the appearance is uniform, and the prepared selenium-doped nano antimony has good quality and excellent performance;
2. sb of the invention 1-x Se x The composite material is used as a negative electrode material of a sodium ion battery, and shows outstanding specific charge capacity, the solid solution of selenium in the crystal lattice of nano antimony is beneficial to the rapid diffusion of sodium ions, and the synthesized product has good electrochemical performance and can be used in the technical fields of energy material application and the like;
3. the method is simple, easy to realize and low in cost.
Drawings
FIG. 1 Sb prepared according to example two of the present invention 1-x Se x XRD pattern of (a).
FIG. 2 Sb prepared according to example two of the present invention 1-x Se x XPS plot of (A).
FIG. 3 Sb prepared according to example two of the present invention 1-x Se x SEM images at different magnifications.
FIG. 4 Sb prepared according to example two of the present invention 1-x Se x At 0.5A g -1 Cycle plot of sodium ion battery at current density.
Detailed Description
The above-described embodiments are further illustrated below with reference to specific examples, in which preferred embodiments of the invention are detailed below:
the first embodiment is as follows:
in this embodiment, a method for preparing selenium-doped nano antimony includes the following steps:
a. preparing a reducing solution containing sodium hydroselenide:
weighing 30mg of selenium powder and 1.6g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 100mL of ethanol, and stirring to fully react to obtain a reducing solution containing sodium hydroselenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 2.6g of antimony trichloride into 50mL of ethanol, and stirring to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and then stirring for 30 minutes until no gas is generated, so as to obtain a precursor solution;
and then transferring the precursor solution into 2 polytetrafluoroethylene hydrothermal kettles with the capacity of 100mL, enabling the filling degree of the hydrothermal kettles to be 50-70%, reacting for 10 hours in a hydrothermal reaction kettle closed system at 130 ℃, and after the reaction is finished, centrifuging and washing the product solution to obtain a reaction product, namely the selenium-doped nano antimony particles.
The second embodiment:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for preparing selenium-doped nano antimony includes the following steps:
a. preparing a reducing solution containing sodium hydroselenide:
weighing 60mg of selenium powder and 1.6g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 100mL of ethanol, and stirring to fully react to obtain a reducing solution containing sodium hydroselenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 2.6g of antimony trichloride into 50mL of ethanol, and stirring to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and stirring for 20 minutes until no gas is generated to obtain a precursor solution;
transferring the precursor solution into 2 polytetrafluoroethylene hydrothermal kettles with the capacity of 75mL, enabling the filling degree of the hydrothermal kettles to be 50-70%, reacting for 10 hours in a hydrothermal reaction kettle closed system at 130 ℃, and centrifuging and washing the product solution after the reaction is finished to obtain the reaction product of selenium-doped nano antimony particles.
Experimental test analysis:
the structure of the product selenium-doped nano antimony prepared by the method of the second embodiment is shown in figure 1, and is pure antimony metalPhase JCPDS:85-1323. X-ray photoelectron spectroscopy analysis of the product selenium-doped nano-antimony prepared by the second method of example 2 is shown in FIG. 2, in which FIG. 2 (a) is an XPS line of Se element, and two peaks located at 54.13eV and 54.85eV respectively correspond to 3d of Se 5/2 And 3d 3/2 Energy levels, wherein FIG. 2 (b) is an XPS line of Sb element, peaks located in the vicinity of 528.4eV and 537.7eV respectively represent the 3d of elemental Sb 5/2 And 3d 3/2 Energy level. From fig. 2, the selenium-doped nano antimony product contains Se element. The morphology of the selenium-doped nano antimony product prepared by the second embodiment is shown in fig. 3, the particle size of the product is small, 20-40nm, and the particle size of the product is uniform.
The product selenium doped nanometer antimony Sb prepared by the second method of the embodiment 1-x Se x Application in sodium ion batteries:
a. preparing a working electrode piece:
a-1, preparing slurry:
sb 1-x Se x The product is taken as an active substance, the ketjen black is taken as conductive carbon black, the carboxymethyl cellulose (CMC) is taken as a binder, and the mass ratio of the conductive carbon black to the carboxymethyl cellulose is Sb 1-x Se x : keqin black: mixing CMC in a mass ratio of 7;
a-2, preparing a working electrode pole piece:
coating the prepared slurry on a copper foil by using a scraper, drying the copper foil by placing the copper foil in a drying oven at 70 ℃ for 3 hours, and then cutting the dried slurry into small round pieces with the diameter of 10 mm;
b. assembling the sodium-ion battery:
the sodium ion battery was assembled in a glove box filled with argon gas, and a metal sodium sheet having a diameter of 14mm was used as a counter electrode, and 1mol L of the counter electrode was used -1 The sodium perchlorate solution is used as electrolyte, and the solvent of the electrolyte is as follows: preparing a mixed solution according to the volume ratio of PC to EC to FEC of 47.5, assembling a CR2032 coin cell, and testing the electrochemical performance;
c. testing of electrochemical performance:
as shown in FIG. 4, the current density of the electrochemical test was measuredDegree of 0.5A g -1 The charging specific capacity of the first circle of the battery is 462.5mAh g -1 Then, the capacity slowly increased due to the activation process, and the remaining capacity after 100 cycles was 481.5mAh g -1 And the electrochemical performance is very good.
In the preparation method of selenium-doped nano antimony in the above embodiment, a solvothermal method is used, absolute ethyl alcohol is used as a solvent, selenium powder is used as a selenium source, antimony trichloride is used as an antimony source, and sodium borohydride is used as a reducing agent to perform a hydrothermal reaction, so that Sb with uniform size distribution is obtained 1-x Se x Particles of a nanomaterial. The phase characterization of the nano particles prepared by the embodiment shows that the nano particles are pure phases, impure phase antimony selenide is not generated, and the obtained product is small in particle size and uniform in appearance. In addition, the solid solution of selenium in the nano antimony crystal lattice in the embodiment is beneficial to the rapid diffusion of sodium ions, and the product Sb is synthesized 1-x Se x Has good electrochemical performance and can be used in the technical fields of energy material application and the like.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing selenium-doped nano antimony includes the following steps:
a. preparing a reducing solution containing sodium hydroselenide:
weighing 10mg of selenium powder and 0.6g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 30mL of ethanol, and stirring to fully react to obtain a reducing solution containing sodium hydroselenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 0.8g of antimony trichloride into 15mL of ethanol, and stirring to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and stirring for 60 minutes until no gas is generated to obtain a precursor solution;
transferring the precursor solution into 2 polytetrafluoroethylene hydrothermal kettles with the capacity of 100mL, wherein the filling degree of the hydrothermal kettles is 50-70%, reacting for 20 hours in a hydrothermal reaction kettle closed system at 100 ℃, and centrifuging and washing the product solution after the reaction is finished to obtain the reaction product, namely selenium-doped nano antimony particles.
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing selenium-doped nano antimony includes the following steps:
a. preparing a reducing solution containing sodium hydroselenide:
weighing 30mg of selenium powder and 0.8g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 30mL of ethanol, stirring for 20min, and fully reacting reactants to obtain a reducing solution containing sodium hydroselenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 1.3g of antimony trichloride into 25mL of ethanol, stirring for 20nim to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and stirring for 60 minutes until no gas is generated to obtain a precursor solution;
transferring the precursor solution into 2 polytetrafluoroethylene hydrothermal kettles with the capacity of 100mL, wherein the filling degree of the hydrothermal kettles is 50-70%, reacting for 20 hours in a hydrothermal reaction kettle closed system at 100 ℃, and centrifuging and washing the product solution after the reaction is finished to obtain the reaction product of selenium-doped nano antimony particles.
Example five:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for preparing selenium-doped nano antimony includes the following steps:
a. preparation of reducing solution containing sodium hydroselenide:
weighing 60mg of selenium powder and 1.6g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 100mL of ethanol, and stirring to fully react to obtain a reducing solution containing sodium hydroselenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 2.6g of antimony trichloride into 50mL of ethanol, and stirring to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and stirring for 20 minutes until no gas is generated to obtain a precursor solution;
transferring the precursor solution into 2 polytetrafluoroethylene hydrothermal kettles with the capacity of 75mL, wherein the filling degree of the hydrothermal kettles is 50-70%, reacting for 10 hours in a hydrothermal reaction kettle closed system at 130 ℃, and centrifuging and washing the product solution after the reaction is finished, wherein the rotation speed of the centrifugation is 8000rpm; after the solution after the reaction is centrifuged, an absolute ethyl alcohol solvent is used for cleaning, and one centrifugation and washing process is completed; then the centrifugation and washing process was repeated 2 times; then, washing with deionized water, and centrifuging to finish a subsequent centrifuging and washing process; then repeating the subsequent centrifugation and cleaning process for 2 times; and finally, washing by using an absolute ethyl alcohol solvent, centrifuging, collecting the obtained product, and drying the product in an oven at the temperature of 50-70 ℃ to obtain pure and dry selenium-doped nano antimony particles.
In summary, the doped product prepared by the embodiment is a pure phase and does not contain the second phase of antimony selenide, the particle size of the obtained doped product is small, the appearance is uniform, and the prepared selenium-doped nano antimony has good quality and excellent performance; example Sb described above 1-x Se x The composite material is used as a negative electrode material of a sodium ion battery and shows outstanding specific charge capacity, the solid solution of selenium in the crystal lattice of nano antimony is beneficial to the rapid diffusion of sodium ions, and the synthesized product has good electrochemical performance and can be used in the technical fields of energy material application and the like; the embodiment has the advantages of simple method, easy realization and low cost.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention should be replaced with equivalents as long as the object of the present invention is met, and the technical principle and the inventive concept of the present invention are not departed from the scope of the present invention.
Claims (6)
1. A preparation method of selenium-doped nano antimony is characterized by comprising the following steps: using a solvothermal method, using absolute ethyl alcohol as a solvent, selenium powder as a selenium source, antimony trichloride as an antimony source and sodium borohydride as a reducing agent to perform hydrothermal reaction to obtain Sb with the maximum particle diameter of 20-50nm and uniform size distribution 1-x Se x Nano material particles, wherein x is more than 0 and less than 1, and the phase characterization shows that the phase is a pure phase;
the preparation method of the selenium-doped nano antimony comprises the following steps:
a. preparing a reducing solution containing sodium hydroselenide:
weighing 10-60mg of selenium powder and 0.6-1.6g of sodium borohydride, putting the selenium powder and the sodium borohydride into a flask, adding 30-100mL of ethanol, and stirring to fully react to obtain a reducing solution containing sodium selenide for later use;
b. preparing an ethanol solution of antimony trichloride:
dissolving 0.8-2.6g of antimony trichloride into 15-50mL of ethanol, and stirring to completely dissolve the antimony trichloride to obtain a uniform and transparent ethanol solution of antimony trichloride for later use;
c. preparation of Sb 1-x Se x Precursor solution of material:
dropwise adding the ethanol solution of antimony trichloride prepared in the step b into the reduction solution containing sodium hydroselenide prepared in the step a, and stirring for 20-60 minutes until no gas is generated to obtain a precursor solution;
transferring the precursor solution into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 50-70%, reacting for 10-20 hours in a hydrothermal reaction kettle closed system at 100-130 ℃, and centrifuging and washing the product solution after the reaction is finished to obtain the reaction product selenium-doped nano antimony particles.
2. The method for preparing the selenium-doped nano antimony of claim 1, wherein the method comprises the following steps: and b, when preparing the reducing solution containing the sodium hydroselenide in the step a, weighing 10-30mg of selenium powder and 0.6-0.8g of sodium borohydride, putting the selenium powder and the sodium hydroselenide into a flask, adding 30-50mL of ethanol, stirring for at least 20min, and fully reacting reactants to obtain the reducing solution containing the sodium hydroselenide.
3. The method of claim 1, wherein the selenium-doped nano-antimony comprises: and b, when preparing the ethanol solution of the antimony trichloride in the step b, dissolving 0.8-1.3g of the antimony trichloride into 15-25mL of ethanol, and stirring for at least 20min to completely dissolve the antimony trichloride.
4. The method of claim 1, wherein the selenium-doped nano-antimony comprises: in the step c, centrifuging and washing the product solution after the reaction is finished, wherein the centrifugal rotating speed is not lower than 8000rpm; after the solution after the reaction is centrifuged, an absolute ethyl alcohol solvent is used for cleaning, and one centrifugation and washing process is completed; repeating the centrifugation and washing process at least 2 times; then, washing by using deionized water, centrifuging, and finishing a subsequent centrifuging and washing process; repeating the subsequent centrifugation and washing processes at least 2 times; and finally, washing by using an absolute ethyl alcohol solvent, centrifuging, collecting the obtained product, and drying in an oven at 50-70 ℃ to obtain pure and dry selenium-doped nano antimony particles.
5. A selenium-doped nano antimony is characterized in that: the selenium-doped nano antimony is prepared by the preparation method of claim 1.
6. The application of the selenium-doped nano antimony is characterized in that: an electrode assembly prepared by using the selenium-doped nano antimony of claim 5 as an active material component in an electrode material component in a sodium ion battery.
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