CN108493425B - Preparation method of Sn4P3 nanoparticle sodium ion battery cathode material coated by mesoporous carbon nanotube - Google Patents
Preparation method of Sn4P3 nanoparticle sodium ion battery cathode material coated by mesoporous carbon nanotube Download PDFInfo
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- 238000003756 stirring Methods 0.000 claims description 31
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- 239000002070 nanowire Substances 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
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- 238000005406 washing Methods 0.000 claims description 12
- 239000007833 carbon precursor Substances 0.000 claims description 11
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
Abstract
The invention discloses Sn coated by mesoporous carbon nano-tubes4P3The preparation method of the negative electrode material of the nano-particle sodium ion battery is SnO coated by mesoporous carbon2And sodium hypophosphite as a raw material, and heating and carrying out a phosphorization reaction to obtain the sodium hypophosphite. The material has high specific surface area, good conductivity and Sn4P3Presence of nanoparticles as Sn4P3When @ mC is used as the cathode material of the sodium-ion battery, the obtained battery material has good stable stability and high cyclic specific capacity, and the battery performance is excellent; and the preparation method of the product is simple, the yield is high, and the used raw materials are cheap and easy to obtain, thereby being beneficial to commercial application.
Description
Technical Field
The invention relates to a sodium ion battery cathode material, in particular to Sn coated with mesoporous carbon nano tubes4P3A preparation method of a negative electrode material of a nano-particle sodium-ion battery.
Background
The development of efficient and stable secondary battery energy storage technology is an important means for dealing with the current increasingly urgent energy and environmental problems, and under the condition that the reserve of the lithium ion battery is not abundant, the sodium ion battery becomes a substitute of the lithium ion battery due to the abundant reserve. High-end consumer electronics products (such as smart phones, wearable devices, etc.) that are rapidly developing are in need of secondary batteries with high specific energy.
Mesoporous carbon coated Sn4P3The sodium ion negative electrode material can still keep higher specific capacity and cycle performance under the density cycle of large current, thereby being capable of meeting the requirements of people in the contemporaryThere is a need for high energy density batteries. Tin phosphide has the defects of poor conductivity, large volume expansion during charge and discharge and the like, and in order to solve the defects, the tin phosphide mixed carbon material and the like are mainly used at present, so that the performance of the product is limited. The low yield, which is not suitable for mass production, seriously hinders the practical application thereof.
Disclosure of Invention
In order to avoid the problems in the prior art, the invention provides Sn coated by mesoporous carbon nanotubes4P3The preparation method of the negative electrode material of the nano-particle sodium-ion battery aims at further improving the conductivity of the material and relieving the volume expansion to improve the Sn4P3Performance of sodium ion batteries as negative electrode materials.
Sn coated with mesoporous carbon nanotubes4P3The preparation method of the negative electrode material of the nano-particle sodium-ion battery comprises the following steps:
step 1: mixing 1.8-2.5g of
The powder was uniformly dispersed in a beaker containing 30ml of deionized water solvent; step 2: sequentially adding 1.0-1.8g of phenol, 3.8-4.8ml of formaldehyde and 20-40ml of sodium hydroxide solution with the concentration of 0.01mol/L into a conical flask, and stirring for 20-50min at the temperature of 60-80 ℃;
and step 3: adding the solution prepared in the step 1 into the reaction solution in the step 2, reducing the temperature by 4 ℃ on the basis of the original temperature, and stirring at the speed of 280 plus 400rpm for 1.5-3 h;
and 4, step 4: adding 80-120ml of deionized water into a conical flask, stirring for 15-24h while keeping the original temperature and the original stirring speed, observing whether the bottom is precipitated or not after stirring is finished, if the bottom is precipitated, failing the experiment, and if the bottom is not precipitated, cooling with cold water to room temperature to obtain a mesoporous carbon precursor F127Solution for later use;
and 5: adding potassium permanganate into deionized water, uniformly stirring, adding PVP, uniformly stirring, cooling to room temperature after hydrothermal reaction, centrifuging, washing and drying to obtain MnOxA wire precursor;
step 6: will step withMnO obtained in step 5xAdding the linear precursor into the mixed solution of water and ethanol, stirring uniformly, and then sequentially adding urea and KSnO3·H2O and evenly stirring, cooling to room temperature after the hydrothermal reaction is finished, centrifuging, washing and drying the obtained product to obtain MnOx@SnO2The nano wires and the tin oxide particles are uniformly distributed on the surface of the manganese oxide;
and 7: MnO ofx@SnO2Adding the nanowire and CTAB into deionized water, ultrasonically dispersing uniformly, and then adding the mesoporous carbon precursor F obtained in the step (4)127Uniformly stirring the solution, cooling to room temperature after the hydrothermal reaction is finished, and centrifugally washing by water and ethanol to obtain the mesoporous carbon precursor coated MnOx@SnO2Nanowire, abbreviated MnOx@SnO2@CF127A nanowire;
and 8: subjecting the undried MnO obtained in step 7 to a reactionx@SnO2@CF127Nanowire is immersed in oxalic acid solution to remove precursor MnOxWire, SnO converted into hollow2@CF127A tube;
and step 9: mixing hollow SnO2@CF127The tube is calcined in an inert atmosphere and converted to SnO2@mC；
Step 10: SnO2Mixing @ mC and sodium hypophosphite, carrying out a phosphating reaction in an inert atmosphere, washing with 0.05mol/L HCl solution and ethanol after the reaction is finished, and drying in vacuum to obtain Sn coated by the mesoporous carbon nanotube4P3Nano-particle sodium ion battery cathode material, abbreviated as Sn4P3The @ mC sodium ion battery negative electrode material.
In the step 5, the mass ratio of potassium permanganate to PVP is 85: 40-60, preferably 76: 45; the mass volume ratio of potassium permanganate to solvent is 85 mg: 35-45ml, preferably 85 mg: 40 mL; the hydrothermal reaction temperature is 160 ℃, and the reaction time is 8-10h, preferably 9 h.
In step 6, MnOxUrea, KSnO3·H2The mass volume ratio of the O, the water and the ethanol mixed solution is 90-110 mg: 700-1000 mg: 100-164 mg: 25-35ml, preferably the mass-to-volume ratio is 100mg: 900 mg:144 mg: 30 ml. The volume content of ethanol in the mixed solution of water and ethanol is 37.5 percent; the hydrothermal reaction temperature is 170 ℃, and the reaction time is 1-3h, preferably 1 h.
In step 7, MnOx@SnO2Nanowire, CTAB and mesoporous carbon precursor F127The mass-volume ratio of the solution is 100mg to 70-120 mg: 1.0-3.5ml, preferably 100mg: 100mg: 1.5 ml; to MnOx@SnO2After the nano wire and the CTAB are dispersed uniformly, a mesoporous carbon precursor F is added127Stirring the solution for 2-8h after the solution is added; the hydrothermal reaction temperature is 120-130 ℃, preferably 130 ℃, and the hydrothermal reaction time is 24 h.
In step 8, the concentration of the oxalic acid solution is 0.4-0.6M, preferably 0.5M.
In step 9, the inert atmosphere is nitrogen; the roasting temperature is 500-700 ℃, preferably 500 ℃, and the roasting time is 40-80min, preferably 50 min.
In step 10, SnO2The mol ratio of @ mC to sodium hypophosphite is 1: 4-6; the inert atmosphere is nitrogen; the temperature of the phosphating reaction is 260 ℃ to 300 ℃, preferably 280 ℃, and the reaction time is 15-60min, preferably 50 min.
The invention has the beneficial effects that:
1. the invention relates to Sn coated with nano-tubular mesoporous carbon4P3The nano particles are used as the negative electrode material of the sodium ion battery, the specific surface area is high, the obtained battery has good cycling stability and high cycling specific capacity, and the battery performance is excellent.
2. The invention relates to Sn coated by nano tubular mesoporous carbon4P3The preparation method of the nano-particles is simple, and the used raw materials are cheap and easy to obtain, thereby being beneficial to commercial application.
Drawings
FIG. 1 shows a nanowire-like MnO obtained in example 1xSEM photograph of (a).
FIG. 2 shows a nanowire-shaped MnO obtained in example 1xTEM photograph of (a).
FIG. 3 shows a nanowire-shaped MnO obtained in example 1x@SnO2SEM photograph of (a).
FIG. 4 is a drawing showingNanowire-shaped MnO obtained in example 1x@SnO2TEM photograph of (a).
FIG. 5 shows a nanowire-shaped MnO obtained in example 1x@SnO2@CF127SEM photograph of (a).
FIG. 6 shows the nanotubular SnO obtained in example 12@CF127TEM photograph of (a).
FIG. 7 shows the nanotubular SnO obtained in example 12TEM photograph of @ mC.
FIG. 8 shows the nanotubular Sn obtained in example 14P3SEM photograph of @ mC.
FIG. 9 shows the nanotubular Sn obtained in example 14P3TEM photograph of @ mC.
FIG. 10 shows the nanotubular Sn obtained in example 14P3The XRD pattern of @ mC.
FIG. 11 shows the nanotubular Sn obtained in example 14P3EDS plot of @ mC.
FIG. 12 shows the nanotubular Sn obtained in example 14P3The BET plot of @ mC.
FIG. 13 shows the nanotubular Sn obtained in example 14P3@ mC.
Detailed Description
The invention is explained in detail below with reference to the figures and the specific embodiments.
The experimental methods used in the following examples are all conventional methods unless otherwise specified. Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1:
in this embodiment, Sn coated with mesoporous carbon nanotubes4P3A preparation method of a negative electrode material of a nano-particle sodium-ion battery.
The following were used:
1. mixing 1.92g of
The powder was uniformly dispersed in a beaker containing 30ml of deionized water solvent;
2. sequentially adding 1.2g of phenol, 4.2ml of formaldehyde and 30ml of sodium hydroxide solution with the concentration of 0.01mol/L into a conical flask, and stirring for 30min at 70 ℃;
3. adding the solution prepared in the step 1 into the reaction solution in the step 2, adjusting the temperature to 66 ℃, and stirring at 340rpm for 2 h;
4. adding 100ml of deionized water into a conical flask, stirring for 18 hours at the original temperature and the original stirring speed, observing whether the bottom is precipitated or not after stirring is finished, failing the experiment if the bottom is precipitated, cooling with cold water if the bottom is not precipitated, and cooling to room temperature to obtain a mesoporous carbon precursor F127Solution for later use;
5. adding 85mg of potassium permanganate into 40mL of deionized water, uniformly stirring, adding 50mg of PVP, uniformly stirring, carrying out hydrothermal reaction at 160 ℃ for 9h, cooling to room temperature after the hydrothermal reaction is finished, centrifuging, washing and drying to obtain MnOxA wire precursor;
6. adding 100mg of MnO prepared in step 5xAdding the linear precursor into 30mL of mixed solution of water and ethanol (the ethanol content is 37.5 percent), uniformly stirring, and then sequentially adding 0.9g of urea and 0.144g of KSnO3·H2O and evenly stirring, carrying out hydrothermal reaction at 170 ℃ for 60min, cooling to room temperature after the hydrothermal reaction is finished, centrifuging, washing and drying the obtained product to obtain MnOx@SnO2A nanowire;
7. to convert 40mg of MnOx@SnO2Adding the nanowire and 40mg CTAB into 30mL of deionized water, ultrasonically dispersing uniformly, and then adding 1.5mL of mesoporous carbon precursor F obtained in the step 4127Stirring the solution for 6h, carrying out hydrothermal reaction at 130 ℃ for 24h, cooling to room temperature after the hydrothermal reaction is finished, and carrying out centrifugal washing on water and ethanol to obtain MnOx@SnO2@CF127A nanowire.
8. Subjecting the undried MnO obtained in step 7 to a reactionx@SnO2@CF127The nano wire is immersed into 100mL of 0.5M oxalic acid solution and reacts for 2h to remove the precursor MnOxWire, SnO converted into hollow2@CF127A tube;
9. mixing hollow SnO2@CF127The tube is placed in a nitrogen/argon atmosphere and roasted at 500 ℃ for 50min, to SnO2@mC；
10. SnO2Mixing @ mC and sodium hypophosphite according to the molar ratio of 1:5, carrying out solid phase reaction at 280 ℃ for 50min in a nitrogen atmosphere, washing with 0.05mol/L HCl solution and ethanol for four times respectively after the reaction is finished, and carrying out vacuum drying to obtain the nano-tube-shaped Sn4P3The @ mC sodium ion battery negative electrode material.
Fig. 1 and 2 are SEM and TEM photographs, respectively, of the first step product obtained in this example, from which it can be seen that the material has a linear shape at the microscopic level, providing a relatively uniform template for the next step product.
FIGS. 3 and 4 are SEM photograph and TEM photograph of the second-step product obtained in this example, respectively, from which it can be seen that the material is microscopically coated with a layer of tin dioxide nanoparticles.
FIG. 5 is a SEM photograph of the product of the third step obtained in this example, and it can be seen that the material is coated with a layer F127 of the product of the previous step at the microscopic level, so as to provide a carbon layer on the surface of tin oxide to prevent the tin oxide from peeling off.
FIG. 6 is a TEM photograph of the fourth step product obtained in this example, which shows that the material is microscopically removed from the manganese oxide lines by oxalic acid, providing sufficient internal space to alleviate the volume expansion of the final product tin phosphide.
FIG. 7 is a TEM photograph of the fifth-step product obtained in this example, in which it can be seen that SnO2@ CF are microscopic in the material127The surface of the tin dioxide is converted into a layer of mesoporous carbon.
Fig. 8 and 9 are SEM photograph and TEM photograph of the sixth step product obtained in this example, respectively, which show that the material is microscopically coated with granular substance and the original morphology is substantially maintained.
FIG. 10 is an XRD picture of the target product obtained in this example, which shows that the characteristic peak of the material is Sn4P3Peak of (2), proving that the material is Sn4P3@mC。
Fig. 11 is an EDS spectrum of the target product obtained in this example, and peaks of phosphorus element, tin element and carbon element are clearly seen from the spectrum.
Fig. 12 is a BET picture of the target product obtained in this example, and it can be seen that the target product is mesoporous carbon-coated tin phosphide, and has a large specific surface area, so as to provide more ion channels for sodium ion transmission.
The battery performance of the target product obtained in this example was tested using a blue cell test system:
uniformly mixing the mesoporous carbon-coated tin phosphide nano-material obtained in the embodiment with acetylene black and PVDF according to the mass ratio of 7:2:1, and dissolving the mixture in an NMP solution to prepare slurry; uniformly coating the obtained slurry on a copper foil current collector to prepare a working electrode; the polypropylene membrane is taken as a diaphragm, and the electrolyte is 1M NaPF containing EC and DEC with the volume ratio of 1:1 and 5 percent of FEC6A 2032 button cell is assembled in a glove box filled with argon according to the sequence of 'negative electrode shell, sodium sheet, diaphragm, electrolyte, working electrode, gasket, reed and positive electrode shell', the test voltage range is 0.01V-3V vs Na+/Na。
FIG. 13 shows the cycle performance of the target product obtained in this example, with a test magnification of 200mA g-1It can be seen that the sample has good coulombic efficiency retention capacity, the eighteenth circle to the third hundred circles are still kept at 98.9% on average, and 299.9mAh g is still retained after 300 circles of circulation-1The reversible specific capacity shows that the cycle performance is excellent.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. Sn coated by mesoporous carbon nano tube4P3The preparation method of the negative electrode material of the nano-particle sodium-ion battery is characterized by comprising the following steps of: SnO coated by mesoporous carbon nano-tube2The nano-particles and sodium hypophosphite are used as raw materials and are prepared by heating and phosphorizing reaction.
2. The method of claim 1, comprising the steps of:
step 1: mixing 1.8-2.5g of
F-127 powder was uniformly dispersed in a beaker containing 30ml of deionized water solvent;
step 2: sequentially adding 1.0-1.8g of phenol, 3.8-4.8ml of formaldehyde and 20-40ml of sodium hydroxide solution with the concentration of 0.01mol/L into a conical flask, and stirring for 20-50min at the temperature of 60-80 ℃;
and step 3: adding the solution prepared in the step 1 into the reaction solution in the step 2, reducing the temperature by 4 ℃ on the basis of the original temperature, and stirring at the speed of 280 plus 400rpm for 1.5-3 h;
and 4, step 4: adding 80-120ml of deionized water into a conical flask, stirring for 15-24h while keeping the original temperature and stirring speed, observing whether the bottom is precipitated or not after stirring is finished, if the bottom is precipitated, the experiment fails, if the bottom is not precipitated, cooling with cold water, and cooling to room temperature to obtain a mesoporous carbon precursor F127Solution for later use;
and 5: adding potassium permanganate into deionized water, uniformly stirring, adding PVP, uniformly stirring, cooling to room temperature after hydrothermal reaction, centrifuging, washing and drying to obtain MnOxA wire precursor;
step 6: MnO prepared in the step 5xAdding the linear precursor into the mixed solution of water and ethanol, stirring uniformly, and then sequentially adding urea and KSnO3·H2O and evenly stirring, cooling to room temperature after the hydrothermal reaction is finished, centrifuging, washing and drying the obtained product to obtain the MnO coated with the tin oxide nano particlesxI.e. MnOx@SnO2A nanowire;
and 7: MnO ofx@SnO2Adding the nanowire and CTAB into deionized water, ultrasonically dispersing uniformly, and then adding the mesoporous carbon precursor F obtained in the step (4)127Uniformly stirring the solution, cooling to room temperature after the hydrothermal reaction is finished, and centrifugally washing by water and ethanol to obtain the mesoporous carbon precursor coated MnOx@SnO2Nanowires, i.e. MnOx@SnO2@CF127A nanowire;
and 8: will step withUndried MnO obtained in step 7x@SnO2@CF127Nanowire is immersed in oxalic acid solution to remove precursor MnOxWire, SnO converted into hollow2@CF127A tube;
and step 9: mixing hollow SnO2@CF127The tube is calcined in an inert atmosphere and converted to SnO2@mC；
Step 10: SnO2Mixing @ mC and sodium hypophosphite, carrying out a phosphating reaction in an inert atmosphere, washing with 0.05mol/L HCl solution and ethanol after the reaction is finished, and drying in vacuum to obtain Sn coated by the mesoporous carbon nanotube4P3A negative electrode material of a nano-particle sodium ion battery.
3. The method of claim 2, wherein:
in the step 5, the adding proportion of potassium permanganate, PVP and solvent is 85-90 mg: 40-60 mg: 35-45 ml; the hydrothermal reaction temperature is 160 ℃, and the reaction time is 8-10 h.
4. The method of claim 2, wherein:
in step 6, MnOxUrea, KSnO3·H2The adding proportion of the mixed solution of O, water and ethanol is 90-110 mg: 700-1000 mg: 100-164 mg: 25-35 ml; the volume content of ethanol in the mixed solution of water and ethanol is 37.5 percent; the hydrothermal reaction temperature is 170 ℃, and the reaction time is 1-3 h.
5. The method of claim 2, wherein:
in step 7, MnOx@SnO2Nanowire, CTAB and mesoporous carbon precursor F127The mass-volume ratio of the solution is 100mg to 70-120 mg: 1.0-3.5 ml; the hydrothermal reaction temperature is 120-130 ℃.
6. The method of claim 2, wherein:
in step 8, the concentration of the oxalic acid solution is 0.4-0.6M.
7. The method of claim 2, wherein:
in the step 9 and the step 10, the inert atmosphere is nitrogen or argon.
8. The method of claim 2, wherein:
in step 9, the calcination temperature is 500-700 ℃, and the calcination time is 40-80 min.
9. The method of claim 2, wherein:
in step 10, SnO2The mol ratio of @ mC to sodium hypophosphite is 1: 4-6; the temperature of the phosphorization reaction is 260 ℃ and 300 ℃, and the reaction time is 15-60 min.
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| CN110071268B (en) * | 2019-03-25 | 2021-11-23 | 天津大学 | Method for preparing tri-tin tetraphosphorylation rivet-on-carbon framework composite material for sodium ion negative electrode material |
| CN112436117B (en) * | 2019-06-04 | 2021-09-28 | 中国地质大学（北京） | Sn-P-CNT composite material |
| CN110993913B (en) * | 2019-12-06 | 2021-01-01 | 湘潭大学 | Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof |
| CN112201782B (en) * | 2020-10-16 | 2022-09-30 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
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