CN113488641A - Rapid preparation method of lithium ion battery anode material vanadium pentoxide nanosheet - Google Patents
Rapid preparation method of lithium ion battery anode material vanadium pentoxide nanosheet Download PDFInfo
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002135 nanosheet Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010405 anode material Substances 0.000 title claims abstract description 9
- WFHSPNCGYSVLCW-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;oxovanadium(2+) Chemical compound [V+2]=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WFHSPNCGYSVLCW-UHFFFAOYSA-K 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000013110 organic ligand Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims 3
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002060 nanoflake Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 5
- 239000002064 nanoplatelet Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
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- 239000012535 impurity Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002120 nanofilm Substances 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention discloses a rapid preparation method of a two-dimensional large-area vanadium pentoxide nanosheet of a lithium ion battery anode material. The two-step synthesis method is characterized by adopting solvothermal and oxidation treatment, firstly taking ammonium fluoride as a structure directing agent and vanadyl citrate as a solute, preparing a two-dimensional flaky VO organic ligand precursor by a solvothermal method, and then carrying out low-temperature oxidation heat treatment on the precursor to synthesize large-area V2O5And (4) nano flakes. Two-dimensional V prepared by the invention2O5The thickness of the nano-sheet is about 20nm, the transverse size exceeds 5 μm, the surface is rough and porous, and the specific surface area is larger; in particular, the process flow takes no more than 24 hours. When used as the anode of a lithium ion batteryIn the form of porous sheet V2O5The contact area of the electrolyte is increased, the diffusion transmission path of ions is effectively shortened, and the high rate performance and the high cycle stability are shown. The preparation process is rapid, efficient, simple and easy to operate, and enriches and expands the two-dimensional V2O5The preparation method of (1).
Description
Technical Field
The invention belongs to the field of preparation and application of metal oxide micro-nano materials, and particularly relates to a rapid preparation method of vanadium pentoxide nanosheets, which is mainly used in the field of rechargeable secondary batteries, especially in the technical direction of lithium ion batteries.
Background
Vanadium pentoxide (V)2O5) The lithium ion battery cathode material has the remarkable advantages of rich resources, low price, excellent safety, easiness in preparation and the like, and is considered to have great application potential. In particular, V2O5The theoretical specific capacity for storing two lithium ions is up to 294 mAh g-1Obviously higher than the anode material widely used at present, such as LiFePO4（170 mAh g-1），LiMn2O4（148 mAh g-1) And LiCoO2（140 mAh g-1). However, V2O5The development of applications is limited by the low electron/ion conductivity, the slow kinetics of electrochemical reactions and the poor cycling stability. At present, solve V2O5One common measure of the problem is to reduce its size to the nanometer scale. In domestic and foreign research, the nano-structure V with different shapes is publicly reported2O5The nano-fiber nano-belt comprises a one-dimensional nano-belt, nano-rods, nano-fibers, two-dimensional nano-sheets, nano-films, three-dimensional nano-flowers, nano-microspheres and the like. Notably, compared with other nanostructures, the two-dimensional nanosheet has unique advantages in improving the electrochemical performance of the electrode material: 1) the material volume effect can be effectively accommodated to maintain the circulation stability; 2) high electrode/electrolyte contact area; 3) short electron/ion diffusion transport paths; 4) low ion diffusion barrier. Based on the above advantages, it is easy to find that various two-dimensional V preparations are mentioned in domestic and foreign published documents2O5Wet chemical methods of nanosheets; interestingly, V synthesized in the above preparation method2O5The thickness of the nano-sheet is often more than 50 nm; otherwise, it often takes more than 3-9 days to obtain thinner V2O5Nanoplatelets (below 50 nm) resulting from the fact that most synthetic methods involve long-term aging, freezing and stirringAnd (5) working procedures. The liquid phase stripping method is a method for quickly preparing ultrathin V2O5An effective method of nanosheet (2-5 nm); however, this method involves vigorous sonication, which tends to synthesize nanoplatelets having a lateral dimension of less than 1 μm, which reduces the structural advantage of the two-dimensional nanoplatelets to some extent. It is evident that a simple, efficient and fast method has been developed for synthesizing two-dimensional V's with large lateral dimensions2O5Nanoflakes remain a significant challenge.
Disclosure of Invention
The invention aims to provide a rapid preparation method of a two-dimensional large-area vanadium pentoxide nanosheet. The preparation method disclosed by the invention is rapid, efficient, simple and easy to operate, strong in controllability and high in reproducibility, and greatly enriches and enriches the preparation method of the two-dimensional nanosheet; in particular, two-dimensional large area V2O5The nano-sheet has good electrochemical performance when used as a lithium ion battery anode material.
The technical scheme adopted by the invention for solving the technical problem is as follows: adding a certain volume of vanadyl citrate solution with specified concentration and a proper amount of ammonium fluoride solid into a certain volume of glycol solvent, then transferring the solution into a reaction kettle, sealing the reaction kettle, reacting the solution for a period of time at a specified temperature, naturally cooling the reaction kettle, carrying out solid-liquid separation, washing and drying to obtain a precursor product, and finally carrying out low-temperature oxidation heat treatment on the precursor to obtain the two-dimensional large-area V2O5Nanosheets.
The invention relates to a rapid preparation method of a two-dimensional large-area vanadium pentoxide nanosheet of a lithium ion battery anode material, which is characterized by being synthesized by a solvothermal method and an oxidation treatment two-step method.
The preparation method comprises the following specific steps:
The molar ratio of the vanadium pentoxide to the citric acid is 1: 2-4, and the molar concentration of the vanadyl citrate is 0.3-0.4 mol/L (in a preferable scheme, the molar ratio of the vanadium pentoxide to the citric acid is 1:3, and the molar concentration of the vanadyl citrate is 0.33 mol/L).
The molar ratio of the vanadyl citrate to the ammonium fluoride is 1: 0.8-1, and the volume ratio of the vanadyl citrate solution to the glycol solvent is 1: 8-12. (in a preferred scheme, the molar ratio of the vanadyl citrate to the ammonium fluoride is 1:1, and the volume ratio of the vanadyl citrate solution to the glycol solvent is 1: 10).
The heating rate of the heat treatment is 1-4 ℃/min.
The invention also provides a two-dimensional large-area V obtained by the preparation method2O5The application of the nano-thin sheet in the electrode material of the lithium ion battery.
Compared with the prior art, the preparation and application method of the two-dimensional large-area vanadium pentoxide nanosheet disclosed by the invention has the positive effects that:
(1) the preparation method of the two-dimensional large-area vanadium pentoxide nanosheet provided by the invention is rapid, efficient, simple and easy to operate, strong in controllability and high in reproducibility, and solves the problem that the vanadium pentoxide nanosheet is difficult to effectively give consideration to the thin thickness (< 50 nm), the large transverse size (> 1 μm) and the short synthesis period (< 1 day).
(2) The vanadium pentoxide nanosheet prepared by the method is about 20nm in thickness, over 5 microns in transverse dimension, rough and porous in surface, large in specific surface area, short in synthesis period of less than 24h, and wide in application field and prospect.
(3) The two-dimensional large-area vanadium pentoxide nanosheets are used as the anode material of the lithium ion battery, the contact area of the electrolyte is increased due to the porous lamellar structure, the diffusion transmission path of ions is effectively shortened, and the good rate performance and the good circulation stability are shown.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the vanadium pentoxide material prepared in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the vanadium pentoxide material prepared in example 1.
FIG. 3 is a Transmission Electron Microscope (TEM) image of the vanadium pentoxide material prepared in example 1.
Fig. 4 shows the charge-discharge curve and the rate cycle performance of the vanadium pentoxide material prepared in example 1 as the positive electrode of the lithium ion battery, where a is a charge-discharge curve and b is a rate cycle performance graph.
Fig. 5 is a graph of the long life cycle performance of the vanadium pentoxide material prepared in example 1 as a positive electrode for a lithium ion battery.
FIG. 6 is a Scanning Electron Microscope (SEM) image of the vanadium pentoxide material prepared in example 2.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a vanadium pentoxide material prepared in example 3.
FIG. 8 is a Scanning Electron Microscope (SEM) image of a vanadium pentoxide material prepared in example 4.
FIG. 9 is a Scanning Electron Microscope (SEM) image of a vanadium pentoxide material prepared in example 5.
FIG. 10 is a Scanning Electron Microscope (SEM) image of a vanadium pentoxide material prepared in example 6.
FIG. 11 is a Scanning Electron Microscope (SEM) image of a vanadium pentoxide material prepared in example 7.
Detailed Description
The present invention is described in detail with reference to the following embodiments, which are not intended to limit the invention, but rather, may be modified based on the teachings of the present invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are all commercial products, and unless otherwise specified, reagents were purchased from stores by default.
Example 1
(1) Adding 0.6g of commercial vanadium pentoxide and 1.9g of citric acid into 20 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution and 0.032g of ammonium fluoride solid (the molar ratio of vanadyl citrate to ammonium fluoride is 1: 0.88) into 30 mL of glycol solvent, stirring at room temperature for 0.5h, transferring into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 400 ℃ at a heating rate of 4 DEG/min in air for heat treatment for 4h, naturally cooling, and collecting the product to obtain two-dimensional large-area V2O5Nanosheets.
(3) Preparing the lithium ion battery electrode piece for testing: to two-dimensional large area V2O5Mixing the nano-sheet active substance, the conductive agent acetylene black and the binder PVDF (polyvinylidene fluoride) according to a certain ratio (7: 2: 1) to prepare slurry, coating the slurry on an aluminum foil, drying and cutting pieces to obtain the lithium ion battery positive electrode test pole piece.
(4) And (3) electrochemical performance testing: in a dry glove box ([ O ]) filled with argon gas2],[H2O]Less than or equal to 0.01ppm) to assemble the CR2025 coin cell. Transferring the dry electrode plate prepared in the step (3) into a glove box, matching with a metal lithium plate, separating the middle part by a polyolefin porous membrane, and dropwise adding a plurality of 1M LiPF6Electrolyte solution dissolved in EC-DEC-5% FEC; finally, the cell seal was sealed and allowed to stand for 6 hours. The batteries after standing were tested with a blue test system, wherein: setting a charge-discharge cut-off voltage window to be 2.0V-4.0V; the charging and discharging are carried out in a constant current mode, and the current density is set to be 0.1-3.0A g-1。
FIG. 1 is an XRD (X-ray diffraction) spectrum of a prepared two-dimensional large-area vanadium pentoxide nanosheet, wherein a phase diffraction peak is relatively sharp and is consistent with a standard card in matching manner, and no obvious impurity diffraction peak exists, so that the prepared material is high in purity and crystallinity.
FIG. 2 is an SEM image of a two-dimensional large-area vanadium pentoxide nanosheet prepared as a nanosheet having a lateral dimension of greater than 5 μm and a thickness of about 20nm, and a and b are attached drawings at different magnifications.
FIG. 3 is a TEM image of a prepared two-dimensional large-area vanadium pentoxide nanosheet, the nanosheet having a transverse dimension of more than 5 μm and a surface with obvious pores or cavities, wherein a and b are attached drawings under different magnifications.
FIG. 4 shows the charge-discharge curve and rate cycle performance of the two-dimensional large-area vanadium pentoxide nanoplatelets prepared from the material at 0.1A g-1Under the current density, the first discharge specific capacity is as high as 291.7 mAh g-1And the multiplying power cycling performance is better.
FIG. 5 shows the long-term cycle performance of the two-dimensional large-area vanadium pentoxide nanoplatelets prepared at 0.1A g-1 Lower cycle 100 weeks and 1.5A g-1The capacity retention rate of the lower cycle for 200 weeks is 84.1% and 94.2%, respectively, and a certain application potential is shown.
Example 2
(1) Adding 1.2g of commercial vanadium pentoxide and 3.8g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 6 mL of vanadyl citrate solution and 0.073g of ammonium fluoride solid (the molar ratio of vanadyl citrate to ammonium fluoride is 1: 1) into 60 mL of glycol solvent, stirring at room temperature for 0.5h, transferring into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 350 deg.C in air at a heating rate of 1 deg.C/min for heat treatment for 1h, naturally cooling, and collecting the product to obtain two-dimensional large-area V2O5Nanosheets.
(3) Preparing the lithium ion battery electrode piece for testing: to two-dimensional large area V2O5Mixing the nano-sheet active substance, the conductive agent acetylene black and the binder PVDF (polyvinylidene fluoride) according to a certain ratio (7: 2: 1) to prepare slurry, coating the slurry on an aluminum foil, drying and cutting the aluminum foil to obtain the lithium ion battery anode testAnd (6) pole pieces.
(4) And (3) electrochemical performance testing: the same test conditions as in example 1 were used.
FIG. 6 is an SEM image of a two-dimensional large-area vanadium pentoxide nanosheet prepared in a transverse dimension of greater than 5 μm and having a thickness of about 20nm and a surface with significant pores or voids, with little difference in topographical features from example 1; in addition, the electrochemical performance of the nanosheet material used as the lithium ion battery anode is not obviously different from that of the nanosheet material in example 1, namely when the prepared two-dimensional large-area vanadium pentoxide nanosheet is used as the lithium ion battery anode, the material is 0.1A g-1The first discharge specific capacity is about 290.8 mAh g under the current density-1And the multiplying power cycling performance is better, which is 0.1A g-1 Lower cycle 100 weeks and 1.5A g-1The capacity retention rate of the lower cycle for 200 weeks was 83.5% and 93.8%, respectively.
Example 3
(1) Adding 2.4g of commercial vanadium pentoxide and 7.6g of citric acid into 80 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 12 mL of vanadyl citrate solution and 0.146g of ammonium fluoride solid (the molar ratio of vanadyl citrate to ammonium fluoride is 1: 1) into 120 mL of glycol solvent, stirring at room temperature for 0.5h, transferring into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 400 ℃ at a heating rate of 4 ℃/min in air for heat treatment for 4h, naturally cooling, collecting the product, and obtaining a two-dimensional large-area V2O5Nanosheets.
(3) Preparing the lithium ion battery electrode piece for testing: to two-dimensional large area V2O5Mixing the nano-sheet active substance, the conductive agent acetylene black and the binder PVDF (polyvinylidene fluoride) according to a certain ratio (7: 2: 1) to prepare slurry, coating the slurry on an aluminum foil, drying and cutting pieces to obtain the lithium ion battery positive electrode test pole piece.
(4) And (3) electrochemical performance testing: the same test conditions as in example 1 were used.
FIG. 7 is an SEM image of a two-dimensional large-area vanadium pentoxide nanosheet prepared as having a lateral dimension of greater than 5 μm, a thickness of about 20nm, and a surface with distinct pores or voids, with little difference in topographical features from example 1; in addition, the electrochemical performance of the nanosheet material used as the lithium ion battery anode is not obviously different from that of the nanosheet material in example 1, namely when the prepared two-dimensional large-area vanadium pentoxide nanosheet is used as the lithium ion battery anode, the material is 0.1A g-1Under the current density, the first discharge specific capacity is about 291.2 mAh g-1And the multiplying power cycling performance is better, which is 0.1A g-1Lower cycle 100 weeks and 1.5A g-1The capacity retention rate of the lower cycle for 200 weeks was 83.8% and 93.5%, respectively.
Example 4
(1) Adding 0.6g of commercial vanadium pentoxide and 1.9g of citric acid into 20 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30 mL of glycol solvent, stirring at room temperature for 0.5h, transferring the mixture into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 400 ℃ at a heating rate of 4 ℃/min in air for heat treatment for 4h, naturally cooling, collecting the product, and obtaining a two-dimensional large-area V2O5Nanosheets.
(3) The conditions for the preparation, assembly and electrochemical performance test of the lithium ion battery electrode piece described in example 1 were used.
FIG. 8 is an SEM image of samples prepared as smooth submicrospheres of about 500nm when ammonium fluoride was not added, and the charge and discharge performance of the prepared submicrospheres as positive electrodes of lithium ion batteries was tested, resulting in a material at 0.1A g-1The first discharge specific capacity is about 230.9 mAh g under the current density-1And 0.1A g-1Lower cycle 100 weeks and 1.5A g-1The capacity retention rate of the lower cycle for 200 weeks was 63.6% and 73.3%, respectively.
Example 5
(1) Adding 0.6g of commercial vanadium pentoxide and 1.9g of citric acid into 20 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution and 0.008g of ammonium fluoride solid (the molar ratio of vanadyl citrate to ammonium fluoride is 1: 0.22) into 30 mL of glycol solvent, stirring at room temperature for 0.5h, transferring into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 400 ℃ at a heating rate of 4 ℃/min in air for heat treatment for 4h, naturally cooling, collecting the product, and obtaining a two-dimensional large-area V2O5Nanosheets.
(3) The conditions for the preparation, assembly and electrochemical performance test of the lithium ion battery electrode piece described in example 1 were used.
FIG. 9 is an SEM image of a prepared sample, which is a submicron sphere with a size of about 500nm composed of nanosheets when the molar ratio of vanadyl citrate to ammonium fluoride is 1:0.22, and the prepared flaky submicron sphere is tested for the charge and discharge performance of a positive electrode of a lithium ion battery, so that the material is 0.1A g-1The first discharge specific capacity is about 245.9 mAh g under the current density-1And 0.1A g-1Lower cycle 100 weeks and 1.5A g-1The capacity retention at 200 weeks of the lower cycle was 69.5% and 78.8%, respectively.
Example 6
(1) Adding 0.6g of commercial vanadium pentoxide and 1.9g of citric acid into 20 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution and 0.016g of ammonium fluoride solid (the molar ratio of vanadyl citrate to ammonium fluoride is 1: 0.44) into 30 mL of glycol solvent, stirring at room temperature for 0.5h, transferring into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 400 deg.C in air at a heating rate of 4 deg.C/min for heat treatment for 4 hr, naturally cooling, collecting the product,to obtain a two-dimensional large-area V2O5Nanosheets.
(3) The conditions for the preparation, assembly and electrochemical performance test of the lithium ion battery electrode piece described in example 1 were used.
FIG. 10 is an SEM image of a prepared sample, which is a nanosheet-constituted microsphere having a size of about 2.5 μm when the molar ratio of vanadyl citrate to ammonium fluoride is 1:0.44, and the prepared flaky microsphere is tested for charge and discharge performance as a positive electrode of a lithium ion battery, with the result that the material is at 0.1A g-1The first discharge specific capacity is about 269.6 mAh g under the current density-1And 0.1A g-1Lower cycle 100 weeks and 1.5A g-1The capacity retention rate of the lower cycle for 200 weeks was 78.3% and 84.2%, respectively.
Example 7
(1) Adding 0.6g of commercial vanadium pentoxide and 1.9g of citric acid into 20 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.33 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution and 0.024g of ammonium fluoride solid (the molar ratio of vanadyl citrate to ammonium fluoride is 1: 0.66) into 30 mL of glycol solvent, stirring at room temperature for 0.5h, transferring into a high-pressure reaction kettle, reacting at 200 ℃ for 12h, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
(2) heating VO organic ligand precursor to 400 ℃ at a heating rate of 4 ℃/min in air for heat treatment for 4h, naturally cooling, collecting the product, and obtaining a two-dimensional large-area V2O5Nanosheets.
(3) The conditions for the preparation, assembly and electrochemical performance test of the lithium ion battery electrode piece described in example 1 were used.
FIG. 11 is an SEM image of a prepared sample, which is a nanosheet-constituted microsphere having a size of about 5 μm when the molar ratio of vanadyl citrate to ammonium fluoride is 1:0.66, and the prepared flaky microsphere is tested for charge and discharge performance as a positive electrode of a lithium ion battery, with the result that the material is at 0.1A g-1The first discharge specific capacity is about 280.7 mAh g under the current density-1And 0.1A g-1Lower cycle 100 weeks and 1.5A g-1Lower circulation 20The capacity retention at 0 weeks was 80.3% and 89.8%, respectively.
Through the above embodiments, it can be concluded that:
the preparation method of the two-dimensional large-area vanadium pentoxide nanosheet provided by the invention is rapid, efficient, simple and easy to operate, strong in controllability and high in reproducibility, and especially the introduction of ammonium fluoride as a structure directing agent is of great importance; when the specified additive amount is reached, the rapid generation of the nano-sheets can be effectively promoted, so that the synthesis process and the method of the two-dimensional nano-sheets are greatly enriched and enriched. The two-dimensional large-area vanadium pentoxide nanosheet prepared by the method has the transverse dimension of more than 5 mu m, the thickness of about 20nm, rough and porous surface and large specific surface area, and is expected to be practically applied in a plurality of fields; particularly, when the nano sheet is used as the anode of the lithium ion battery, the nano sheet shows better rate performance and cycle stability, and has better application potential and prospect.
Claims (4)
1. The rapid preparation method of the lithium ion battery anode material vanadium pentoxide nanosheet is characterized by comprising the following steps:
step 1, dissolving vanadium pentoxide and citric acid in deionized water, and stirring to obtain a vanadyl citrate solution with a certain concentration; taking a certain volume of vanadyl citrate solution and a proper amount of ammonium fluoride (NH)4F) Adding the solid into a certain volume of glycol solvent, stirring and mixing uniformly at room temperature, reacting for 6-12 h at 160-200 ℃ in a high-pressure reaction kettle, naturally cooling, performing solid-liquid separation, washing with ethanol, and drying to obtain dark green powder, namely VO organic ligand precursor;
and 2, heating the VO organic ligand precursor to 350-450 ℃ in air at a specified heating rate for heat treatment for 1-4 h, and collecting a product after natural cooling to obtain the lithium ion battery anode material vanadium pentoxide nanosheet.
2. The method for rapidly preparing the vanadium pentoxide nanosheet as the positive electrode material of the lithium ion battery as claimed in claim 1, wherein the molar ratio of the vanadium pentoxide to the citric acid is 1: 2-4, and the molar concentration of the vanadyl citrate is 0.3-0.4 mol/L.
3. The method for rapidly preparing the vanadium pentoxide nanosheet as the positive electrode material of the lithium ion battery as claimed in claim 1, wherein the molar ratio of vanadyl citrate to ammonium fluoride is 1: 0.8-1, and the volume ratio of vanadyl citrate solution to glycol solvent is 1: 8-12.
4. The method for rapidly preparing the vanadium pentoxide nanosheet as the positive electrode material of the lithium ion battery according to claim 1, wherein the rate of temperature rise during the heat treatment is 1-4 ℃/min.
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| CN106904653A (en) * | 2017-01-22 | 2017-06-30 | 重庆大学 | The preparation method of vanadium dioxide nano material and applied in magnesium chargeable battery |
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