CN111403730B - FePS for sodium ion battery3@ MXene nano composite anode material, preparation method thereof and sodium ion battery - Google Patents
FePS for sodium ion battery3@ MXene nano composite anode material, preparation method thereof and sodium ion battery Download PDFInfo
- Publication number
- CN111403730B CN111403730B CN202010068812.5A CN202010068812A CN111403730B CN 111403730 B CN111403730 B CN 111403730B CN 202010068812 A CN202010068812 A CN 202010068812A CN 111403730 B CN111403730 B CN 111403730B
- Authority
- CN
- China
- Prior art keywords
- feps
- mxene
- sodium ion
- ion battery
- nano composite
- 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.)
- Active
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 81
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 50
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002135 nanosheet Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 229910005318 FePS3 Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000006230 acetylene black Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 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
- 239000011230 binding agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to FePS for a sodium ion battery3A @ MXene nano composite negative electrode material, a preparation method thereof and a sodium ion battery, belonging to the technical field of sodium ion batteries. The FePS for the sodium ion battery of the invention3The preparation method of the @ MXene nano composite anode material comprises the following steps: adding Ti at 35-45 deg.C3AlC2With Ti3C2TxMixing MXene etching solution uniformly, and performing first solid-liquid separation; uniformly mixing the solid obtained by the first solid-liquid separation with water, carrying out ultrasonic treatment for 1-3h in an inert atmosphere, and then carrying out the second solid-liquid separation to obtain a liquid, namely MXene solution; FePS is prepared3And (3) uniformly mixing the aqueous dispersion of the nanosheet with the prepared MXene solution, and freeze-drying to obtain the nano/MXene composite material. The nano composite negative electrode material can provide more channels for the migration of sodium ions, and further improves the specific capacity and the cycle performance of the composite negative electrode material.
Description
Technical Field
The invention relates to FePS for a sodium ion battery3A @ MXene nano composite negative electrode material, a preparation method thereof and a sodium ion battery, belonging to the technical field of sodium ion batteries.
Background
With the increasing importance of new energy industry in various countries around the world, more and more renewable and clean energy sources such as solar energy, wind energy, geothermal energy and the like are developed. The development of the clean energy can reduce the dependence on fossil energy reserves, but the clean energy is often limited by natural conditions in practical application, the energy storage device can improve the utilization efficiency of various energy sources and make up for the defect that the clean energy is limited by the natural conditions, and the battery is a common energy storage device.
The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, environmental friendliness and the like, and is a battery with excellent performance and wide application range. However, the shortage of metallic lithium resources on earth has limited the large-scale application of lithium ion batteries. The sodium ion battery, as a successor of the lithium ion battery, is not limited by resource reserves, and can replace the lithium ion battery in many fields. In the electrode reaction process of the sodium ion battery, the insertion/removal process of the sodium ion battery is slower due to larger radius and molar mass of sodium ions, so that the specific capacity and the cycle life of the sodium ion battery are difficult to exert higher levels, and the development of the sodium ion battery is severely restricted. In the sodium ion battery, the negative electrode material plays an important role in the capacity and the cycle life of the battery, so that the development of the negative electrode material with high specific capacity and long cycle life has very important significance in improving the performance of the sodium ion battery.
The two-dimensional nanomaterial has a special structure, can provide a more convenient and faster channel for the embedding and the separation of sodium, has good stability, and has important significance on the development of the two-dimensional nanomaterial with high specific capacity and long cycle life for a sodium-ion battery.
Disclosure of Invention
The invention provides FePS for a sodium ion battery3The preparation method of the @ MXene nano composite anode material has the advantages of high specific capacity and long cycle life.
The invention also provides FePS for the sodium ion battery prepared by the preparation method3The @ MXene nano composite anode material has higher specific capacity and longer cycle life.
The technical scheme adopted by the invention for solving the technical problems is as follows:
FePS for sodium ion battery3The preparation method of the @ MXene nano composite anode material comprises the following steps:
1) adding Ti at 35-45 deg.C3AlC2With Ti3C2TxMixing MXene etching solution uniformly, and performing first solid-liquid separation; mixing the solid obtained by the first solid-liquid separation with water uniformlyCarrying out ultrasonic treatment for 1-3h in inert atmosphere, and then carrying out second solid-liquid separation to obtain a liquid which is MXene solution;
2) FePS is prepared3Uniformly mixing the aqueous dispersion of the nanosheets and the MXene solution prepared in the step 1), and freeze-drying to obtain the nano/MXene composite material.
The FePS for the sodium ion battery of the invention3The preparation method of the @ MXene nano composite anode material comprises the steps of preparing an MXene solution dispersed with MXene nanosheets by a liquid phase peeling method, and then mixing the MXene solution with FePS3Uniformly mixing the aqueous dispersion of the nano-sheets, and uniformly dispersing the MXene nano-sheets in the FePS3Forming FePS on the nano-sheet3@ MXene hybrid. The unique 2D/2D structure can promote the rapid transfer of electrons/ions and reduce the volume expansion of the electrode. Particularly, when the lithium ion battery is used as an anode of a sodium ion battery, the lithium ion battery can show good cycling stability and rate capability, and the sodium storage performance is more outstanding. In addition, FePS3The required electrochemical performance of the battery can be further improved. Due to the difference of the discharge potential, the generated mixed phases can be used as buffer substances of each other, and electrode powdering or agglomeration caused by volume expansion is inhibited. In the whole charging and discharging process, the superfine active substances are uniformly distributed in the conductive MXene, so that the rapid transfer of charges is ensured, and the specific capacity of the composite material is further improved.
Ti in step 1)3C2TxThe MXene etching solution is prepared by uniformly mixing hydrochloric acid and lithium fluoride, and the proportion of the lithium fluoride to HCl in the hydrochloric acid is 0.1-0.15mol of HCl per gram of lithium fluoride. Preference is given to 0.12 to 0.14 mol of HCl. The hydrochloric acid and the lithium fluoride are uniformly mixed and stirred for 3-8 min. The concentration of the hydrochloric acid is 8-10 mol/L.
Ti in step 1)3AlC2With Ti3C2TxThe MXene etching solution is evenly mixed and stirred for 30-40 h. Ti in step 1)3AlC2With Ti3C2TxThe mass ratio of the lithium fluoride in the MXene etching solution is 1: 1-2. Ti in step 1)3AlC2With Ti3C2TxMixing MXene etching solution uniformly, washing the product with water to obtain washing solutionAnd carrying out solid-liquid separation after the pH value is not lower than 6. The inert atmosphere in step 1) is an argon atmosphere or a nitrogen atmosphere.
The amount of water when the solid obtained by the first solid-liquid separation in the step 1) is uniformly mixed with water is 2g of Ti3AlC2Correspondingly adding 220-280mL of water. The second solid-liquid separation in the step 1) is centrifugal separation, the rotating speed of the centrifugal separation is 3200-3600rpm, and the time of the centrifugal separation is 1-2 h.
FePS in step 2)3The dispersion liquid of the nano-sheets in water is 100-120mg of FePS3The nano-sheets are dispersed in 100-150mL of ultrapure water and then are subjected to ultrasonic treatment for 20-30min to obtain the nano-particles.
FePS per 100mL in step 2)3The aqueous dispersion of the nanosheet corresponds to 3-6mL of MXene solution. The step 2) is to mix evenly and stir for 20 to 30 hours.
FePS in step 2)3The nanosheet is prepared by a method comprising the steps of:
FePS is prepared3The crystal is insulated for 5-7 days at 800 ℃ under the vacuum condition, then insulated for 1.5-2.5 hours at 550 ℃ under the inert atmosphere, and then dispersed in water, treated by ultrasonic treatment and freeze-dried. The ultrasonic treatment is carried out under ice bath conditions.
FePS for sodium ion battery prepared by preparation method3And @ MXene nano composite negative electrode material.
The sodium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is FePS for the sodium ion battery3And @ MXene nano composite negative electrode material.
The invention has the beneficial effects that:
the FePS for the sodium ion battery of the invention3The @ MXene nano composite anode material has a porous layered structure, can provide more channels for the migration of sodium ions, and further improves the specific capacity and the cycle performance of the composite anode material. The FePS for the sodium ion battery of the invention3The charging and discharging specific capacity of the sodium ion battery prepared from the @ MXene nano composite negative electrode material under the current density of 0.1A/g can reach about 800 mAh/g.
Drawings
FIG. 1 shows FePS used in example 13SEM scan image of material;
FIG. 2 shows FePS for sodium ion battery prepared in example 13Scanning SEM image of @ MXene nano composite negative electrode material;
FIG. 3 shows FePS for sodium ion battery prepared in example 23A TEM image of the @ MXene nanocomposite negative electrode material;
FIG. 4 shows FePS for sodium ion battery prepared in example 13The charge-discharge curve of the sodium ion battery is prepared from the @ MXene nano composite negative electrode material;
FIG. 5 shows FePS used in example 13Materials, FePS for sodium ion Battery produced in example 13@ MXene nanocomposite negative electrode material and FePS for sodium ion battery prepared in example 23The charge-discharge cycle curve of the sodium ion battery prepared from the @ MXene nano composite anode material;
FIG. 6 shows FePS used in example 13Materials, FePS for sodium ion Battery produced in example 13@ MXene nanocomposite negative electrode material and FePS for sodium ion battery prepared in example 23The charge and discharge performance curve of the sodium ion battery prepared from the @ MXene nano composite negative electrode material under different multiplying powers is shown.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
FePS in the following examples3The nanosheet is prepared by a method comprising the steps of:
mixing Fe powder, P powder and S powder according to the proportion of Fe, P and S being 1:1:3, packaging in an ampoule bottle, heating at 750 ℃ for 6d under the vacuum condition, and carrying out low-temperature solid-phase reaction to obtain three elementary substances which react to generate FePS3And (3) crystallizing, and then heating the obtained sample to 500 ℃ in an argon atmosphere, keeping the temperature for 2 hours, and removing residual sulfur and red phosphorus in the sample to obtain blocky crystals.
Dispersing 100mg of blocky crystals in 100mL of deionized water, and performing ultrasonic treatment under ice bath conditionConditioning for 8h, and freeze drying to obtain FePS3Nanosheets.
Example 1
FePS for sodium ion battery of this example3The preparation method of the @ MXene nano composite anode material comprises the following steps:
1) adding 2g of lithium fluoride into 30mL of 9.0mol/L hydrochloric acid, and stirring for 5min to obtain Ti3C2TxMXene etching solution.
2) At 40 ℃, 2g of Ti3AlC2Powder addition of Ti3C2TxAnd stirring the MXene etching solution for 36 hours, washing the solid obtained after the centrifugal separation of the mixed system after stirring for 36 hours by using water until the pH value of the washing solution is not lower than 6, and then carrying out centrifugal separation. And dispersing the centrifuged solid in 250mL of deionized water, carrying out ultrasonic treatment for 2h under the argon atmosphere, centrifuging at 3500rpm for 1h, collecting the separated liquid, and freezing and storing to obtain the MXene solution.
3) 100mg of FePS3Dispersing the nanosheets in 100mL of ultrapure water, performing ultrasonic treatment for 30min to obtain a dispersion liquid, adding 3mL of Xene solution into the dispersion liquid, stirring for 24h, and performing freeze drying to obtain FePS3@ MXene sample, noted FePS3@MXene-1。
Example 2
FePS for sodium ion battery of this example3The preparation method of the @ MXene nano composite anode material comprises the following steps:
1) adding 2g of lithium fluoride into 30mL of 9.0mol/L hydrochloric acid, and stirring for 5min to obtain Ti3C2TxMXene etching solution.
2) At 40 ℃, 2g of Ti3AlC2Powder addition of Ti3C2TxAnd stirring MXene etching solution for 36h, washing the solid obtained after centrifugal separation of the mixed system stirred for 36h by using water until the pH value of the washing solution is not lower than 6, and then carrying out centrifugal separation. And dispersing the centrifuged solid in 250mL of deionized water, carrying out ultrasonic treatment for 2h under the argon atmosphere, centrifuging at 3500rpm for 1h, collecting the separated liquid, and freezing and storing to obtain the MXene solution.
3) 100mg of FePS3Dispersing the nanosheets in 100mL of ultrapure water, performing ultrasonic treatment for 30min to obtain a dispersion liquid, adding 6mL of Xene solution into the dispersion liquid, stirring for 24h, and performing freeze drying to obtain FePS3@ MXene sample, noted FePS3@MXene-2。
Example 3
FePS for sodium ion battery of this example3The preparation method of the @ MXene nano composite anode material comprises the following steps:
1) adding 2g of lithium fluoride into 35mL of 8.0mol/L hydrochloric acid, and stirring for 8min to obtain Ti3C2TxMXene etching solution.
2) At 35 ℃, 2g of Ti3AlC2Powder addition of Ti3C2TxAnd (3) stirring MXene etching solution for 32 hours, washing the centrifugally separated solid of the mixed system stirred for 36 hours by using water until the pH value of the washing solution is not lower than 6, and then carrying out centrifugal separation. And dispersing the centrifugally separated solid in 260mL of deionized water, carrying out ultrasonic treatment for 1.5h in an argon atmosphere, centrifuging for 2h at the rotating speed of 3200rpm, collecting the separated liquid, and freezing and storing to obtain the MXene solution.
3) 110mg of FePS3Dispersing the nanosheets in 120mL of ultrapure water, carrying out ultrasonic treatment for 25min to obtain a dispersion liquid, then adding 5mL of Xene solution into the dispersion liquid, stirring for 22h, and then carrying out freeze drying to obtain FePS3@ MXene sample, noted FePS3@MXene-3。
Example 4
FePS for sodium ion battery of this example3The preparation method of the @ MXene nano composite anode material comprises the following steps:
1) adding 2.5g of lithium fluoride into 30mL of 10.0mol/L hydrochloric acid, and stirring for 6min to obtain Ti3C2TxMXene etching solution.
2) At 45 ℃, 2g of Ti3AlC2Powder addition of Ti3C2TxStirring MXene etching solution for 32h, washing the mixed system centrifugally separated solid after stirring for 36h with water to obtain a washing solutionUntil the pH of the solution is not lower than 6, and then centrifugal separation is carried out. Dispersing the centrifuged solid in 220mL of deionized water, carrying out ultrasonic treatment for 1h under argon atmosphere, then centrifuging at the rotating speed of 3300rpm for 1.5h, collecting the separated liquid, and freezing and storing to obtain the MXene solution.
3) 100mg of FePS3Dispersing the nanosheets in 120mL of ultrapure water, performing ultrasonic treatment for 20min to obtain a dispersion liquid, adding 5mL of Xene solution into the dispersion liquid, stirring for 26h, and performing freeze drying to obtain FePS3@ MXene sample, noted FePS3@MXene-4。
Example 5
FePS for sodium ion battery of this example3The preparation method of the @ MXene nano composite anode material comprises the following steps:
1) adding 2g of lithium fluoride into 30mL of 9.0mol/L hydrochloric acid, and stirring for 3min to obtain Ti3C2TxMXene etching solution.
2) At 43 ℃, 2g of Ti3AlC2Powder addition of Ti3C2TxAnd (3) stirring MXene etching solution for 32 hours, washing the centrifugally separated solid of the mixed system stirred for 36 hours by using water until the pH value of the washing solution is not lower than 6, and then carrying out centrifugal separation. Dispersing the centrifuged solid in 280mL of deionized water, carrying out ultrasonic treatment for 3h under the atmosphere of argon, then centrifuging at the rotating speed of 3600rpm for 1.2h, collecting the separated liquid, and freezing and storing to obtain the MXene solution.
3) 120mg of FePS3Dispersing the nanosheets in 150mL of ultrapure water, performing ultrasonic treatment for 30min to obtain a dispersion liquid, adding 5mL of Xene solution into the dispersion liquid, stirring for 30h, and performing freeze drying to obtain FePS3@ MXene sample, noted FePS3@MXene-5。
Example 6
The sodium ion battery of this embodiment includes a positive electrode, a negative electrode, an electrolyte, and a separator, where the negative electrode includes a negative electrode current collector and a negative electrode material layer disposed on the surface of the negative electrode current collector, the negative electrode material layer includes a negative electrode active material, a conductive agent, and a binder, and the negative electrode active material is the sodium ion prepared in the above embodiments 1 to 5FePS for battery3The @ MXene nano composite negative electrode material is characterized in that a conductive agent is acetylene black, a positive electrode is a sodium sheet, a diaphragm is a Celgard2325 membrane, and an electrolyte is a sodium perchlorate electrolyte. The preparation method of the sodium-ion battery comprises the following steps: firstly adopting the FePS for the sodium ion battery3The material is characterized in that a @ MXene nano composite negative electrode material is used as an active material, acetylene black is used as a conductive agent, sodium carboxymethylcellulose is used as a binder, and the mass ratio of the active material to the acetylene black to the sodium carboxymethylcellulose is 80: 15: 5; mixing an active material, acetylene black, sodium carboxymethylcellulose and a solvent, carrying out ultrasonic treatment to obtain a negative electrode slurry, coating the negative electrode slurry on a copper foil, carrying out vacuum drying, and then carrying out tabletting on a tabletting machine; and then, preparing the button sodium-ion battery by using a sodium sheet as a counter electrode, using sodium perchlorate electrolyte as electrolyte and using Celgard2325 as a diaphragm.
Test examples
(1) Topography testing
Taking FePS used in example 13SEM scans of the material are shown in FIG. 1.
As can be seen from FIG. 1, FePS used in example 13The material has a more obvious layered structure, and the layered structure is more compact.
FePS for sodium ion Battery obtained in example 1 was used3Scanning the @ MXene nanocomposite negative electrode material by SEM, and the scanning result is shown in FIG. 2.
As can be seen from FIG. 2, FePS for sodium ion battery prepared in example 13In the @ MXene nano composite anode material, FePS3MXene nano-sheets are distributed on the lamellar structure, and the MXene nano-sheets and the lamellar structure form a relatively loose lamellar structure.
FePS for sodium ion Battery obtained in example 23The scanning result of the @ MXene nanocomposite negative electrode material by TEM scanning is shown in FIG. 3.
As can be seen from FIG. 3, FePS for sodium ion battery prepared in example 23FePS in @ MXene nano composite anode material3With MXene, a very thin nanocomposite sheet structure can be formed with more pores.
(2) Electrochemical performance test
FePS for sodium ion Battery obtained in example 1 was used3The @ MXene nanocomposite negative electrode material was used to prepare a sodium ion battery according to the method in example 5. Then, charge and discharge were performed at room temperature at a rate of 0.1C, and the charge and discharge curves are shown in fig. 4.
As can be seen from FIG. 4, FePS for sodium ion battery prepared in example 13The charging and discharging voltage platform of the sodium ion battery prepared from the @ MXene nano composite negative electrode material is not obvious, but the charging and discharging capacity can reach about 800mAh/g, and the specific capacity is higher.
Taking FePS used in example 13Materials and FePS for sodium ion Battery prepared in example 13@ MXene nanocomposite negative electrode material and FePS for sodium ion battery prepared in example 23And @ MXene nano composite negative electrode material, and the sodium ion battery is prepared according to the method in the embodiment 5. Then, a charge-discharge cycle was carried out at room temperature at a current density of 0.5A/g, and a charge-discharge cycle curve was shown in FIG. 5.
As can be seen from FIG. 5, FePS for sodium ion battery prepared by the invention3The circulating performance of the @ MXene nano composite anode material is obviously higher than that of FePS3Material, and there was only a small decay after 90 cycles.
Taking FePS used in example 13Materials and FePS for sodium ion Battery prepared in example 13@ MXene nanocomposite negative electrode material and FePS for sodium ion battery prepared in example 23And @ MXene nano composite negative electrode material, and the sodium ion battery is prepared according to the method in the embodiment 5. Then, charge and discharge cycle tests were carried out at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, and 5A/g, and the discharge cycle curves thereof are shown in FIG. 6.
As can be seen from FIG. 6, it is shown that3Compared with the materials, the FePS for the sodium ion battery prepared by the invention3The sodium ion battery prepared from the @ MXene nano composite anode material has better rate capability.
Claims (10)
1. FePS for sodium ion battery3@ MXene nano compositeThe preparation method of the cathode material is characterized by comprising the following steps: the method comprises the following steps:
1) adding Ti at 35-45 deg.C3AlC2With Ti3C2TxMixing MXene etching solution uniformly, and performing first solid-liquid separation; uniformly mixing the solid obtained by the first solid-liquid separation with water, carrying out ultrasonic treatment for 1-3h in an inert atmosphere, and then carrying out the second solid-liquid separation to obtain a liquid, namely MXene solution;
2) FePS is prepared3Uniformly mixing the aqueous dispersion of the nanosheets and the MXene solution prepared in the step 1), and freeze-drying to obtain the nano/MXene composite material.
2. FePS for sodium ion battery according to claim 13The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: ti in step 1)3C2TxThe MXene etching solution is prepared by uniformly mixing hydrochloric acid and lithium fluoride, and the proportion of the lithium fluoride to HCl in the hydrochloric acid is 0.1-0.15mol of HCl per gram of lithium fluoride.
3. FePS for sodium ion battery according to claim 23The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: ti in step 1)3AlC2With Ti3C2TxThe mass ratio of the lithium fluoride in the MXene etching solution is 1: 1-2.
4. FePS for sodium ion battery according to claim 13The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: the amount of water when the solid obtained by the first solid-liquid separation in the step 1) is uniformly mixed with water is 2g of Ti3AlC2Correspondingly adding 220-280mL of water.
5. FePS for sodium ion battery according to claim 13The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: FePS in step 2)3The aqueous dispersion of the nano-sheets consists of 100-120mg of FePS3Dispersing the nano-sheets in 100-150mL of ultrapure water, and then carrying out ultrasonic treatment for 20-3Is prepared in 0 min.
6. FePS for sodium ion battery according to claim 13The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: FePS per 100mL in step 2)3The aqueous dispersion of the nanosheet corresponds to 3-6mL of MXene solution.
7. FePS for sodium ion battery according to claim 13The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: the step 2) is to mix evenly and stir for 20 to 30 hours.
8. FePS for sodium ion battery according to any of claims 1 to 73The preparation method of the @ MXene nano composite anode material is characterized by comprising the following steps of: FePS in step 2)3The nanosheet is prepared by a method comprising the steps of: FePS is prepared3The crystal is insulated for 5-7 days at 800 ℃ under the vacuum condition, then insulated for 1.5-2.5 hours at 550 ℃ under the inert atmosphere, and then dispersed in water, treated by ultrasonic treatment and freeze-dried.
9. FePS for sodium ion battery prepared by the preparation method of claim 13And @ MXene nano composite negative electrode material.
10. A sodium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that: the negative electrode is FePS for the sodium-ion battery as defined in claim 93And @ MXene nano composite negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010068812.5A CN111403730B (en) | 2020-01-21 | 2020-01-21 | FePS for sodium ion battery3@ MXene nano composite anode material, preparation method thereof and sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010068812.5A CN111403730B (en) | 2020-01-21 | 2020-01-21 | FePS for sodium ion battery3@ MXene nano composite anode material, preparation method thereof and sodium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111403730A CN111403730A (en) | 2020-07-10 |
| CN111403730B true CN111403730B (en) | 2020-12-25 |
Family
ID=71430285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010068812.5A Active CN111403730B (en) | 2020-01-21 | 2020-01-21 | FePS for sodium ion battery3@ MXene nano composite anode material, preparation method thereof and sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111403730B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112928342B (en) * | 2021-02-08 | 2022-06-03 | 安徽大学 | Multifunctional zinc ion micro battery and preparation method and application thereof |
| CN114373917A (en) * | 2022-01-18 | 2022-04-19 | 山东大学 | Sodium-ion battery positive electrode composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1248309A1 (en) * | 2001-03-27 | 2002-10-09 | National Institute for Materials Science | Lithium iron thiophosphate compound, process for producing the compound, and lithium battery using the compound |
| CN110299523A (en) * | 2019-06-27 | 2019-10-01 | 山东大学 | A kind of self-supporting two dimension MXene@ZnMn2O4The preparation and its application of combination electrode material |
| CN110540204A (en) * | 2019-09-19 | 2019-12-06 | 北京化工大学 | Self-supporting three-dimensional porous MXene foam material and preparation method and application thereof |
-
2020
- 2020-01-21 CN CN202010068812.5A patent/CN111403730B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1248309A1 (en) * | 2001-03-27 | 2002-10-09 | National Institute for Materials Science | Lithium iron thiophosphate compound, process for producing the compound, and lithium battery using the compound |
| CN110299523A (en) * | 2019-06-27 | 2019-10-01 | 山东大学 | A kind of self-supporting two dimension MXene@ZnMn2O4The preparation and its application of combination electrode material |
| CN110540204A (en) * | 2019-09-19 | 2019-12-06 | 北京化工大学 | Self-supporting three-dimensional porous MXene foam material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Self‐Assemble and In Situ Formation of Ni1−xFexPS3 Nanomosaic‐Decorated MXene Hybrids for Overall Water Splitting;Cheng-Feng Du等;《Advanced Energy Materials》;20180806;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111403730A (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110600695B (en) | Yolk-eggshell structure tin@hollow mesoporous carbon sphere material and preparation method thereof | |
| CN105810914A (en) | Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material | |
| CN104659367A (en) | Preparation method of lithium ion battery cathode material | |
| CN109473663A (en) | A kind of anode material of lithium-ion battery and preparation method thereof of redox graphene load antimony | |
| Gao et al. | Preparation and modification of MIL-101 (Cr) metal organic framework and its application in lithium-sulfur batteries | |
| CN111403730B (en) | FePS for sodium ion battery3@ MXene nano composite anode material, preparation method thereof and sodium ion battery | |
| CN109742439A (en) | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application | |
| CN109830672A (en) | A kind of Preparation method and use of the porous carbon nano-complex of MnO N doping | |
| CN113299894A (en) | MnF2@ NC lithium ion battery cathode material and preparation method and application thereof | |
| CN113937261B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery positive electrode plate | |
| CN114613969A (en) | Molybdenum-based core-shell structure material and preparation method and application thereof | |
| CN111115618A (en) | Graphene/carbon/tin oxide nano composite material and preparation method and application thereof | |
| CN114142161A (en) | Preparation method of modified lithium ion battery diaphragm | |
| CN109346682B (en) | Preparation method of lithium ion battery cathode composite material | |
| CN114094063B (en) | Method for preparing battery anode material by combining cavity precursor and ZIF derivative | |
| CN114551891B (en) | Tin disulfide/titanium dioxide/carbon composite material and preparation method and application thereof | |
| CN102070199A (en) | Method for preparing micron frame-shaped manganese series lithium ion battery cathode material | |
| CN109873157A (en) | Co for lithium ion battery2(BDC)2Ted negative electrode material | |
| CN115207344B (en) | Preparation of FexSey@CN composite material and electrochemical energy storage application thereof | |
| CN115275151A (en) | Vanadium disulfide/titanium carbide composite material and preparation method and application thereof | |
| CN111261866B (en) | Preparation method of ZnO/C nano composite microsphere material with capsule structure | |
| CN110060880B (en) | Prussian blue analogue and preparation method and application thereof | |
| CN109103498B (en) | Sodium ion battery electrolyte and preparation method and application thereof | |
| CN111646514A (en) | MnO of sandwich structure2@rGO@MnO2Composite nanosheet material and preparation method thereof | |
| CN111293297A (en) | Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof |
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 |