CN114373895A - Preparation method and application of antimony-sodium alloy electrode - Google Patents
Preparation method and application of antimony-sodium alloy electrode Download PDFInfo
- Publication number
- CN114373895A CN114373895A CN202111574330.8A CN202111574330A CN114373895A CN 114373895 A CN114373895 A CN 114373895A CN 202111574330 A CN202111574330 A CN 202111574330A CN 114373895 A CN114373895 A CN 114373895A
- Authority
- CN
- China
- Prior art keywords
- antimony
- sodium
- alloy electrode
- sodium alloy
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000528 Na alloy Inorganic materials 0.000 title claims abstract description 56
- BMUJWLXKZUCOEI-UHFFFAOYSA-N antimony sodium Chemical compound [Na].[Sb] BMUJWLXKZUCOEI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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 claims abstract description 46
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 46
- 239000011734 sodium Substances 0.000 claims abstract description 46
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 34
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 34
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005096 rolling process Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 3
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 description 8
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A preparation method and application of an antimony sodium alloy electrode are disclosed, wherein the preparation method comprises the following steps: putting antimony acetate into an ethylene glycol solution, magnetically stirring and heating to dissolve the antimony acetate to obtain an antimony acetate solution with the concentration of 20 g/L; reducing the obtained antimony acetate solution to prepare antimony nanoparticles; and rolling the antimony nano particles and metal sodium to prepare the antimony sodium alloy electrode. The antimony sodium alloy electrode is applied to a metal sodium battery. According to the invention, antimony acetate is used as a raw material, reduced into antimony nanoparticles, and compounded with sodium metal in a rolling manner to prepare an antimony sodium alloy electrode which is used as a negative electrode material of a sodium metal battery; the preparation method of the material is simple, the operation is safe and green, the period is short, the material is suitable for large-scale industrial production, and the prepared antimony sodium alloy electrode is high in specific capacity, good in cycle performance and good in rate capability.
Description
Technical Field
The present invention relates to an alloy electrode. In particular to a preparation method and application of an antimony sodium alloy electrode.
Background
With the rapid development of new energy sources, safe and pollution-free renewable clean energy sources such as solar energy, tidal energy and wind energy are converted into electric energy, which becomes a hot point of research at the present stage, but the clean energy sources such as wind energy and solar energy are unstable, so that the development of large-scale and reliable energy storage technology is very important. At present, a more effective energy storage means is a secondary battery, wherein the lithium ion battery technology is mature, and a sodium ion battery has the advantage of low cost as an effective substitute of the lithium ion battery. And the metallic sodium cathode has the highest theoretical specific capacity (1166 mA.h/g) and the lowest electrode potential (-2.71V) in a sodium-ion battery system. Therefore, the method has considerable application prospect in the field of energy storage. However, researches show that the metal sodium battery has serious dendritic growth in the charging and discharging processes, and the practical application of the metal sodium battery in the aspect of energy storage is severely limited.
The metallic antimony with sodium affinity is found to be capable of reacting with Na+Is induced efficiently to Na+The metal sodium battery can be uniformly deposited on the surface of the negative electrode, the growth of dendrites is inhibited in the subsequent circulation process, and the circulation stability of the metal sodium battery is improved. And the metal antimony has low price and abundant reserves, and has important research value in the field of energy storage. At present, in the research of antimony in the metal sodium battery, researchers have coated the synthetic antimony powder on the copper foil to assemble the metal sodium battery, but the preparation method is troublesome and brings difficulty to the practical application of the metal sodium battery.
Therefore, it is necessary to use a simple method to perform alloying reaction between metal antimony and metal sodium to form antimony-sodium alloy, and it is also highly desirable for large-scale energy storage systems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method and application of an antimony sodium alloy electrode, wherein the preparation method is simple and high in yield.
The technical scheme adopted by the invention is as follows: a preparation method of an antimony sodium alloy electrode comprises the following steps:
step 1: putting antimony acetate into an ethylene glycol solution, magnetically stirring and heating to dissolve the antimony acetate to obtain an antimony acetate solution with the concentration of 20 g/L;
step 2: reducing the obtained antimony acetate solution to prepare antimony nanoparticles;
and step 3: and rolling the antimony nano particles and metal sodium to prepare the antimony sodium alloy electrode.
The magnetic stirring speed in the step 1 is 600 r/min.
The stirring time in step 1 is 30 min.
The step 2 comprises the following steps:
(2.1) dissolving sodium borohydride in ultrapure water, adding sodium hydroxide, adjusting the pH to 12-14, and preparing a sodium borohydride solution with the concentration of 10 g/L;
(2.2) adding the following components in percentage by weight: dropwise adding the sodium borohydride solution into an antimony acetate solution in a volume ratio of 1, heating to 60 ℃, stirring for 2 hours, and fully reducing to obtain black flocs;
(2.3) centrifugally washing the obtained black floc, and drying at 30 ℃ for 12 hours to obtain the antimony nanoparticles.
And (3) the centrifugal washing in the step (2.3) is firstly washed by deionized water and then washed by absolute ethyl alcohol.
The step 3 comprises the following steps:
(3.1) cutting off oxide skin on the surface of the sodium block in a glove box filled with argon, pressing the sodium block into a sodium sheet with the thickness of 0.3-0.8 mm by using a tablet press, and weighing;
(3.2) pouring antimony nanoparticles with set weight on the surface of the sodium sheet, and wrapping the antimony nanoparticles in the sodium sheet;
and (3.3) transferring the sodium sheet wrapped with the antimony nanoparticles into a freshness protection package, repeatedly rolling by using a tablet press to obtain silver-white antimony-sodium alloy, and preparing the antimony-sodium alloy into an antimony-sodium alloy electrode by using a blundmill with the diameter of 14 mm.
The weight ratio of the antimony nano particles to the sodium sheet in the step (3.2) is 1: 4.
An application of the antimony sodium alloy electrode prepared by the preparation method of the antimony sodium alloy electrode is disclosed, wherein the antimony sodium alloy electrode is applied to a metal sodium battery.
According to the preparation method and the application of the antimony sodium alloy electrode, antimony acetate is used as a raw material and is reduced into antimony nano particles, the antimony sodium alloy electrode is prepared by compounding the antimony nano particles with metal sodium in a rolling mode and is used as a negative electrode material of a metal sodium battery; the preparation method of the material is simple, the operation is safe and green, the period is short, the material is suitable for large-scale industrial production, and the prepared antimony sodium alloy electrode is high in specific capacity, good in cycle performance and good in rate capability.
According to the invention, the prepared antimony sodium alloy electrode is used as a metal sodium battery cathode, the conductive agent is acetylene black, the binder is polyvinylidene fluoride, and the mass ratio is 8: 1: 1; the electrolyte is 1 mol of sodium trifluoromethanesulfonate (CF)3NaO3S) ethylene carbonate/diethyl carbonate (EC/DEC ═ 1:1) solution; the battery case is 2032, a current collector is not needed, and the diaphragm is made of glass fiber; the counter electrode adopts a sodium vanadium phosphate electrode plate, and the used sodium vanadium phosphateFor commercial sodium vanadium phosphate, the cell was assembled under protection of argon (0.01PPM) atmosphere. The antimony sodium alloy electrode is used as a negative electrode material of a sodium metal battery, the first discharge specific capacity can reach 106.7mAh/g when the charge-discharge current density is 20mA/g, the second charge-discharge reversible specific capacity can reach 105.4mAh/g, and the specific capacity can be maintained at 79.7mAh/g after 50 times of charge-discharge. The raw materials adopted by the invention are environment-friendly antimony acetate, the reserves are rich, the cost is low, the construction of a novel energy storage material can be realized, meanwhile, no organic solvent is used in the preparation process of the material, and in addition, the method provided by the invention is simple, high in yield, good in reproducibility, easy for large-scale production and wide in application prospect and market.
Drawings
FIG. 1 is a scanning electron microscope image of antimony nanoparticles obtained according to the present invention;
FIG. 2 is a voltage-time graph of a symmetric Sb-Na alloy cell of the present invention;
FIG. 3 is a graph of long cycle and coulombic efficiency at 20mA/g for a full cell of the antimony sodium alloy of the present invention.
Detailed Description
The following describes the preparation method and application of an antimony sodium alloy electrode according to the present invention in detail with reference to the following examples and accompanying drawings.
The invention relates to a preparation method of an antimony sodium alloy electrode, which comprises the following steps:
step 1: putting antimony acetate into an ethylene glycol solution, magnetically stirring and heating to dissolve the antimony acetate to obtain an antimony acetate solution with the concentration of 20 g/L; wherein the magnetic stirring speed is 600r/min, and the stirring time is 30 min.
Step 2: reducing the obtained antimony acetate solution to prepare antimony nanoparticles shown in figure 1; the preparation process comprises the following steps:
(2.1) dissolving sodium borohydride in ultrapure water, adding sodium hydroxide, adjusting the pH to 12-14, and preparing a sodium borohydride solution with the concentration of 10 g/L;
(2.2) adding the following components in percentage by weight: dropwise adding the sodium borohydride solution into an antimony acetate solution in a volume ratio of 1, heating to 60 ℃, stirring for 2 hours, and fully reducing to obtain black flocs;
(2.3) centrifugally washing the obtained black floc, and drying at 30 ℃ for 12 hours to obtain antimony nanoparticles; the centrifugal washing is that the washing is carried out by using deionized water and then absolute ethyl alcohol.
And step 3: rolling the antimony nano particles and metal sodium to prepare an antimony sodium alloy electrode; the method comprises the following steps:
(3.1) cutting off oxide skin on the surface of the sodium block in a glove box filled with argon, pressing the sodium block into a sodium sheet with the thickness of 0.3-0.8 mm by using a tablet press, and weighing;
(3.2) pouring antimony nanoparticles with set weight on the surface of the sodium sheet, and wrapping the antimony nanoparticles in the sodium sheet; the weight ratio of the antimony nano particles to the sodium sheet is 1: 4;
and (3.3) transferring the sodium sheet wrapped with the antimony nanoparticles into a freshness protection package, repeatedly rolling by using a tablet press to obtain silver-white antimony-sodium alloy, and preparing the antimony-sodium alloy into an antimony-sodium alloy electrode by using a blundmill with the diameter of 14 mm.
The antimony sodium alloy electrode prepared by the preparation method of the antimony sodium alloy electrode is applied to a metal sodium battery.
In the preparation method of the antimony sodium alloy electrode, antimony acetate is not limited to be used as a raw material for preparing antimony nanoparticles, and the antimony acetate in the step 1 is replaced by antimony chloride to prepare the antimony nanoparticles.
By adopting the preparation method of the antimony sodium alloy electrode, the prepared antimony sodium alloy electrode plate is used as the cathode of the sodium metal battery, and the electrolyte is 1 mol of sodium trifluoromethanesulfonate (CF)3NaO3S) ethylene carbonate/diethyl carbonate (EC/DEC ═ 1:1) solution, cell case type 2032, no current collector needed, and separator glass fiber. The counter electrode adopts a sodium vanadium phosphate electrode plate, the used sodium vanadium phosphate is commercial sodium vanadium phosphate, the conductive agent is acetylene black, the binder is polyvinylidene fluoride, and the mass ratio is 8: 1: and (1) assembling the battery under the protection of argon (0.01PPM) atmosphere, and applying the assembled battery to an energy storage device. The antimony-sodium alloy electrode is used as the negative electrode material of the metal sodium battery, and the charge-discharge current of the symmetrical battery isThe density was 1mA · cm-2The deposition capacity is 1mAh cm-2The cycle time can be stabilized for more than 160h, and the voltage-time curve diagram of the antimony sodium alloy symmetrical battery shown in figure 2 is shown. When the charge-discharge current density of the full battery is 20mA/g, the first discharge specific capacity can reach 106.7mAh/g, and the second charge-discharge reversible specific capacity can reach 105.4mAh/g, as shown in a long circulation and coulombic efficiency diagram of the antimony-sodium alloy full battery under 20mA/g in figure 3. After 50 times of charging and discharging, the specific capacity is kept at 79.7 mAh/g.
Specific examples are given below
Example 1:
(1) 0.8035g of antimony acetate is put into 40mL of glycol and stirred for 30min at a speed of 600r/min to obtain a uniform solution;
(2) dissolving 0.4g of sodium borohydride in 40mL of ultrapure water, adding 3g of sodium hydroxide to adjust the pH value to 12, and preparing a sodium borohydride solution with the concentration of 10 g/L;
(3) dropwise adding the sodium borohydride solution into an antimony acetate solution, heating to 60 ℃, stirring for 2 hours, and fully reducing to obtain black flocs;
(4) washing the black floc with deionized water, then washing with absolute ethyl alcohol, drying at 30 ℃ for 12 hours, and rolling and compounding with a sodium sheet with the thickness of 0.3mm according to the weight ratio of 1:4 to prepare the antimony-sodium alloy electrode serving as a negative electrode material.
Example 2:
(1) putting 1.205g of antimony acetate in 60mL of ethylene glycol, and stirring at 600r/min for 30min to obtain a uniform solution;
(2) dissolving 0.6g of sodium borohydride in 60mL of ultrapure water, adding 4.2g of sodium hydroxide to adjust the pH value to 13, and preparing a sodium borohydride solution with the concentration of 10 g/L;
(3) dropwise adding the sodium borohydride solution into an antimony acetate solution, heating to 60 ℃, stirring for 2 hours, and fully reducing to obtain black flocs;
(4) washing the black floc with deionized water, then washing with absolute ethyl alcohol, drying at 30 ℃ for 12 hours, and rolling and compounding with a sodium sheet with the thickness of 0.5mm according to the weight ratio of 1:4 to prepare the antimony-sodium alloy electrode serving as a negative electrode material.
Example 3:
(1) putting 1.607g of antimony acetate in 80mL of glycol, and stirring at 600r/min for 30min to obtain a uniform solution;
(2) dissolving 0.8g of sodium borohydride in 80mL of ultrapure water, adding 8g of sodium hydroxide to adjust the pH value to 14, and preparing a sodium borohydride solution with the concentration of 10 g/L;
(3) dropwise adding the sodium borohydride solution into an antimony acetate solution, heating to 60 ℃, stirring for 2 hours, and fully reducing to obtain black flocs;
(4) washing the black floc with deionized water, then washing with absolute ethyl alcohol, drying at 30 ℃ for 12 hours, and rolling and compounding with a sodium sheet with the thickness of 0.8mm according to the weight ratio of 1:4 to prepare the antimony-sodium alloy electrode serving as a negative electrode material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The preparation method of the antimony sodium alloy electrode is characterized by comprising the following steps of:
step 1: putting antimony acetate into an ethylene glycol solution, magnetically stirring and heating to dissolve the antimony acetate to obtain an antimony acetate solution with the concentration of 20 g/L;
step 2: reducing the obtained antimony acetate solution to prepare antimony nanoparticles;
and step 3: and rolling the antimony nano particles and metal sodium to prepare the antimony sodium alloy electrode.
2. The method for preparing the antimony sodium alloy electrode as claimed in claim 1, wherein the magnetic stirring speed in step 1 is 600 r/min.
3. The method for preparing the antimony sodium alloy electrode as claimed in claim 1, wherein the stirring time in step 1 is 30 min.
4. The method for preparing the antimony sodium alloy electrode according to claim 1, wherein the step 2 comprises the following steps:
(2.1) dissolving sodium borohydride in ultrapure water, adding sodium hydroxide, adjusting the pH to 12-14, and preparing a sodium borohydride solution with the concentration of 10 g/L;
(2.2) adding the following components in percentage by weight: dropwise adding the sodium borohydride solution into an antimony acetate solution in a volume ratio of 1, heating to 60 ℃, stirring for 2 hours, and fully reducing to obtain black flocs;
(2.3) centrifugally washing the obtained black floc, and drying at 30 ℃ for 12 hours to obtain the antimony nanoparticles.
5. The method for preparing an Sb-Na alloy electrode as claimed in claim 4, wherein the centrifugal washing in step (2.3) is carried out by washing with deionized water and then with absolute ethanol.
6. The method for preparing the antimony sodium alloy electrode according to claim 1, wherein the step 3 comprises the following steps:
(3.1) cutting off oxide skin on the surface of the sodium block in a glove box filled with argon, pressing the sodium block into a sodium sheet with the thickness of 0.3-0.8 mm by using a tablet press, and weighing;
(3.2) pouring antimony nanoparticles with set weight on the surface of the sodium sheet, and wrapping the antimony nanoparticles in the sodium sheet;
and (3.3) transferring the sodium sheet wrapped with the antimony nanoparticles into a freshness protection package, repeatedly rolling by using a tablet press to obtain silver-white antimony-sodium alloy, and preparing the antimony-sodium alloy into an antimony-sodium alloy electrode by using a blundmill with the diameter of 14 mm.
7. The method for preparing the antimony sodium alloy electrode as claimed in claim 6, wherein the weight ratio of the antimony nanoparticles to the sodium sheet in the step (3.2) is 1: 4.
8. The application of the antimony sodium alloy electrode prepared by the preparation method of the antimony sodium alloy electrode in claim 1 is characterized in that the antimony sodium alloy electrode is applied to a metal sodium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111574330.8A CN114373895B (en) | 2021-12-21 | 2021-12-21 | Preparation method and application of antimony-sodium alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111574330.8A CN114373895B (en) | 2021-12-21 | 2021-12-21 | Preparation method and application of antimony-sodium alloy electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114373895A true CN114373895A (en) | 2022-04-19 |
| CN114373895B CN114373895B (en) | 2024-01-30 |
Family
ID=81139962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111574330.8A Active CN114373895B (en) | 2021-12-21 | 2021-12-21 | Preparation method and application of antimony-sodium alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114373895B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317351A2 (en) * | 1987-11-20 | 1989-05-24 | Showa Denko Kabushiki Kaisha | Secondary battery |
| US20130260222A1 (en) * | 2012-03-28 | 2013-10-03 | Yuhao Lu | Electrode Forming Process for Metal-Ion Battery with Hexacyanometallate Electrode |
| CN103469307A (en) * | 2013-09-29 | 2013-12-25 | 哈尔滨工业大学 | Tetragonal phase lithium-antimony-tantalum co-doped potassium niobate sodium-based piezoelectric crystal and preparation method thereof |
| CN104900858A (en) * | 2015-06-15 | 2015-09-09 | 中南大学 | Preparation method for sodium-ion battery antimony/carbon anode composite material with yolk-shell structure |
| US20150372287A1 (en) * | 2014-06-23 | 2015-12-24 | Belenos Clean Power Holding Ag | Sb Nanocrystals or Sb-Alloy Nanocrystals for Fast Charge/Discharge Li- and Na-ion Battery Anodes |
| CN105671363A (en) * | 2016-01-11 | 2016-06-15 | 浙江工业大学 | Antimony-based alloy material and application thereof |
| KR20160136247A (en) * | 2015-05-19 | 2016-11-29 | 주식회사 엘지화학 | Negative electrode for sodium secondary battery, and sodium secondary battery comprising the same |
| CN107482115A (en) * | 2017-08-11 | 2017-12-15 | 太仓碧奇新材料研发有限公司 | A kind of preparation method of rhenium tungsten antimony composite base flexible piezoelectric film |
| CN108987738A (en) * | 2018-07-23 | 2018-12-11 | 合肥科晶材料技术有限公司 | A kind of technique preparing sodium stannum alloy cathode material and battery |
| CN109637837A (en) * | 2018-12-14 | 2019-04-16 | 深圳先进技术研究院 | Metal material is used as zinc ion aqueous super capacitor cathode and zinc ion water system hybrid super capacitor |
| CN110380038A (en) * | 2019-07-24 | 2019-10-25 | 东北大学秦皇岛分校 | Embed the pyrolysis carbon composite and preparation method of more shell antimony oxide-antimony alloys |
| CN110556513A (en) * | 2019-08-20 | 2019-12-10 | 华中科技大学 | Alkali metal composite electrode material, preparation and application thereof |
| CN111952532A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Sodium ion secondary battery cathode material subjected to pre-sodium treatment and mechanical pre-sodium treatment method thereof |
| CN113263184A (en) * | 2021-04-13 | 2021-08-17 | 上海大学 | Selenium-doped nano antimony, preparation method and application thereof |
| CN113707850A (en) * | 2021-08-30 | 2021-11-26 | 清华大学深圳国际研究生院 | Anode and preparation method thereof, and sodium metal full cell |
-
2021
- 2021-12-21 CN CN202111574330.8A patent/CN114373895B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317351A2 (en) * | 1987-11-20 | 1989-05-24 | Showa Denko Kabushiki Kaisha | Secondary battery |
| US20130260222A1 (en) * | 2012-03-28 | 2013-10-03 | Yuhao Lu | Electrode Forming Process for Metal-Ion Battery with Hexacyanometallate Electrode |
| CN103469307A (en) * | 2013-09-29 | 2013-12-25 | 哈尔滨工业大学 | Tetragonal phase lithium-antimony-tantalum co-doped potassium niobate sodium-based piezoelectric crystal and preparation method thereof |
| US20150372287A1 (en) * | 2014-06-23 | 2015-12-24 | Belenos Clean Power Holding Ag | Sb Nanocrystals or Sb-Alloy Nanocrystals for Fast Charge/Discharge Li- and Na-ion Battery Anodes |
| KR20160136247A (en) * | 2015-05-19 | 2016-11-29 | 주식회사 엘지화학 | Negative electrode for sodium secondary battery, and sodium secondary battery comprising the same |
| CN104900858A (en) * | 2015-06-15 | 2015-09-09 | 中南大学 | Preparation method for sodium-ion battery antimony/carbon anode composite material with yolk-shell structure |
| CN105671363A (en) * | 2016-01-11 | 2016-06-15 | 浙江工业大学 | Antimony-based alloy material and application thereof |
| CN107482115A (en) * | 2017-08-11 | 2017-12-15 | 太仓碧奇新材料研发有限公司 | A kind of preparation method of rhenium tungsten antimony composite base flexible piezoelectric film |
| CN108987738A (en) * | 2018-07-23 | 2018-12-11 | 合肥科晶材料技术有限公司 | A kind of technique preparing sodium stannum alloy cathode material and battery |
| CN109637837A (en) * | 2018-12-14 | 2019-04-16 | 深圳先进技术研究院 | Metal material is used as zinc ion aqueous super capacitor cathode and zinc ion water system hybrid super capacitor |
| CN111952532A (en) * | 2019-05-16 | 2020-11-17 | 同济大学 | Sodium ion secondary battery cathode material subjected to pre-sodium treatment and mechanical pre-sodium treatment method thereof |
| CN110380038A (en) * | 2019-07-24 | 2019-10-25 | 东北大学秦皇岛分校 | Embed the pyrolysis carbon composite and preparation method of more shell antimony oxide-antimony alloys |
| CN110556513A (en) * | 2019-08-20 | 2019-12-10 | 华中科技大学 | Alkali metal composite electrode material, preparation and application thereof |
| CN113263184A (en) * | 2021-04-13 | 2021-08-17 | 上海大学 | Selenium-doped nano antimony, preparation method and application thereof |
| CN113707850A (en) * | 2021-08-30 | 2021-11-26 | 清华大学深圳国际研究生院 | Anode and preparation method thereof, and sodium metal full cell |
Non-Patent Citations (1)
| Title |
|---|
| 周小四;杜忆忱;包建春;: "锑基钠离子电池负极材料的研究进展", 化学教育(中英文), no. 14, pages 3 - 11 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114373895B (en) | 2024-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
| CN108767263B (en) | Preparation method and application of modified metal lithium negative electrode copper foil current collector | |
| CN108400292B (en) | Preparation method and application of bismuth elementary substance nanosheet composite electrode | |
| CN111017958A (en) | Preparation method of nano spherical Prussian blue compound | |
| CN113571698B (en) | Carbon point regulated metal selenide/carbon composite material and preparation method and application thereof | |
| CN110299510B (en) | Preparation of bimetallic sulfide with conductive carbon cloth as substrate and application of bimetallic sulfide in aspect of lithium ion battery cathode | |
| CN113104863A (en) | Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material | |
| CN108807912B (en) | C @ SnOx(x=0,1,2)Preparation and application of @ C mesoporous nano hollow sphere structure | |
| CN105206821A (en) | Method for synthesizing lithium ion battery positive electrode material | |
| CN108878858B (en) | Tin dioxide thin film material, lithium battery and preparation method | |
| CN110233251A (en) | A kind of preparation method and applications of porous silicon/carbon composite material | |
| CN113265766B (en) | Preparation method and application of nitrogen-doped carbon nanofiber composite hollow carbon shell film | |
| CN106938852A (en) | A kind of preparation method of lithium ion battery negative material nanometer CuO | |
| CN111900372B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN112980436A (en) | Carbon quantum dot derived carbon nanosheet composite silicon dioxide cathode material and preparation method thereof | |
| CN106542567A (en) | A kind of preparation method of lithium ion battery negative material nano-ZnO | |
| CN109809402A (en) | A kind of preparation method being used for sodium-ion battery material with three-dimensional hollow porous carbon made of pomace | |
| CN114373895B (en) | Preparation method and application of antimony-sodium alloy electrode | |
| CN112331812B (en) | MoO (MoO) 2 Preparation method of nanorod anode material | |
| CN112430089B (en) | ReO (ReO) 3 Shear structure MoNb 6 O 18 Method for producing materials and use thereof | |
| CN114824243A (en) | Preparation method of Co-doped niobium oxide negative electrode material capable of being rapidly charged | |
| CN108584889A (en) | A kind of lithium ion battery negative material of low-temperature heat polyalcohol synthesis and its application | |
| CN110289398A (en) | Mesoporous carbon coating zine stannate nano bar material derived from a kind of metal organic framework and its preparation method and application | |
| CN109950521A (en) | The super Unsteady Casting of laser prepares lithium ion battery tin-graphite combination electrode method | |
| CN110518194A (en) | A kind of original position carbon coating prepares the method and its application of hud typed silicon/carbon composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |