CN113461056A - Preparation method of lithium ion battery negative electrode material hollow porous vanadium pentoxide microspheres - Google Patents

Preparation method of lithium ion battery negative electrode material hollow porous vanadium pentoxide microspheres Download PDF

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CN113461056A
CN113461056A CN202110757383.7A CN202110757383A CN113461056A CN 113461056 A CN113461056 A CN 113461056A CN 202110757383 A CN202110757383 A CN 202110757383A CN 113461056 A CN113461056 A CN 113461056A
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vanadium pentoxide
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颜波
高林
陶华超
张露露
杨学林
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China Three Gorges University CTGU
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Abstract

The invention discloses a preparation method of a lithium ion battery cathode material hollow porous vanadium pentoxide microsphere. The method is synthesized by adopting a two-step method of solvothermal and oxidation treatment, takes a mixed solution of n-propanol and ethylene glycol as a solvent and vanadyl citrate as a solute, prepares a hollow porous VO organic ligand precursor by a solvothermal method, and then treats the precursor through low-temperature oxidation heat to synthesize the hollow porous V2O5And (3) microspheres. Three-dimensional Structure V of the invention2O5Is a secondary hollow porous microsphere formed by disordered stacking of 10-20nm primary nano sheets, the diameter of the secondary hollow porous microsphere is about 1 mu m, the thickness of a shell layer is about 0.3 mu m, the aperture of the secondary hollow porous microsphere is 10-20nm, and the secondary hollow porous microsphere has a higher specific surface area of about 45-50 m2(ii)/g; when used as a negative electrode for lithium ion batteries, porous V2O5The nanosheets increase the contact area of the electrolyte, effectively shorten the diffusion transmission path of ions, provide buffer space with volume change due to the hollow structure, further show better rate performance and circulation stability, and expand the three-dimensional hollow porous V2O5A method for preparing microspheres.

Description

Preparation method of lithium ion battery negative electrode material hollow porous vanadium pentoxide microspheres
Technical Field
The invention belongs to the field of preparation and application of metal oxide micro-nano materials with special structures, and particularly relates to a simple preparation method of hollow porous vanadium pentoxide microspheres, which is mainly used in the field of rechargeable secondary batteries, in particular to the technical direction of lithium ion batteries.
Background
Vanadium pentoxide (V)2O5) The lithium ion battery cathode material has the remarkable advantages of abundant resources, low price, excellent safety, easiness in preparation and the like, and is widely researched as a lithium ion battery cathode material. However, since the 2000 transformation mechanism was introduced, V2O5It is also considered to be a potential high-energy negative electrode material, mainly due to its discharge ability to combine with multiple lithium ions, and thus has a higher theoretical specific capacity. Although, V2O5The use as a negative electrode can incorporate more lithium, but this also means that there is more phase transition and greater volume effect, so its cycling stability is poor, which severely limits its application development. At present, solve V2O5The main measure of the stability of the cathode is to design or construct a special hollow porous nano structure, on one hand, the nano particles can effectively shorten the diffusion transmission path of ions to improve the reaction kinetics, and on the other hand, the hollow structure can provide an effective buffer space for volume change to maintain the structural stability. In domestic and foreign research, various prepared hollow porous V are published and reported2O5The synthesis of the microspheres is particularly represented by a hard template method, for example, a carbon sphere is used as a hard template, a vanadium-oxygen precursor is grown on the surface of the hard template, and then the vanadium-oxygen precursor is converted into V by oxidation treatment2O5And simultaneously, the carbon sphere template is oxidized into gas to be discharged. It is worth noting that the shell thickness of the hollow structure prepared by the hard template method is very limited, and the phenomena of shell collapse and the like are easy to occur in the template removing process; more importantly, the hard template method generally involves the preparation, utilization and removal of the template, and its poor economy and practicality limit its large-scale application. Another method for preparing hollow porous nano-structure isThe effective method is an Ostwald ripening mechanism, namely a template-free method. The published data show that the template-free method generally obtains relatively smooth hollow microspheres composed of nanoparticles, the specific surface area of the hollow microspheres is relatively low, the controllability of the hollow microspheres is relatively poor, the structural advantages of the three-dimensional hollow microspheres are reduced to a certain extent, and the effect of improving the cycling stability of the material is poor. Clearly, developing a simple, efficient and fast synthesis system or method for constructing hollow porous vanadium pentoxide microspheres remains a great challenge.
Disclosure of Invention
The invention aims to provide a simple preparation method of hollow porous vanadium pentoxide microspheres. The preparation method disclosed by the invention is simple and easy to operate, high in efficiency, strong in controllability and high in reproducibility, and greatly enriches and enriches the three-dimensional hollow porous V2O5A method for preparing microspheres; in particular, hollow porous V2O5The microsphere is used as a lithium ion battery cathode material and shows better electrochemical performance.
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 into a certain volume of mixed solvent of n-propanol and ethylene glycol, then transferring the mixed solvent into a reaction kettle, sealing the reaction kettle, reacting the mixture for a period of time at a specified temperature, naturally cooling the mixture, 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 hollow porous V2O5And (3) microspheres.
The lithium ion battery cathode material of the invention is hollow and porous V2O5The simple preparation method of the microsphere is characterized by utilizing a solvothermal method and an oxidation treatment two-step method for synthesis.
The preparation method comprises the following specific steps:
step 1, dissolving vanadium pentoxide and citric acid in deionized water, and stirring to obtain a vanadyl citrate solution with a certain concentration; adding a certain volume of vanadyl citrate solution into a certain volume of mixed solvent of n-propanol and ethylene glycol, stirring and mixing uniformly at room temperature, reacting for 18-24 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 a 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 cathode material hollow porous vanadium pentoxide microsphere.
The molar ratio of the vanadium pentoxide to the citric acid is 1: 2-4, and the molar concentration of the vanadyl citrate is 0.1-0.2 mol/L. (in a preferred scheme, the molar ratio of the vanadium pentoxide to the citric acid is 1:3, and the molar concentration of the vanadyl citrate is 0.11 mol/L).
The volume ratio of the n-propanol to the ethylene glycol is 1: 0.5-2, and the volume ratio of the vanadyl citrate solution to the mixed solvent (n-propanol and ethylene glycol) is 1: 8-12. (in a preferred scheme, the volume ratio of the n-propanol solvent to the ethylene glycol solvent is 1:1, and the volume ratio of the vanadyl citrate solution to the mixed solvent is 1: 10)
The heating rate of the heat treatment is 1-4 DEG/min.
The invention also provides a hollow porous V obtained by the preparation method2O5The application of the microspheres in the electrode material of the lithium ion battery.
The invention discloses a hollow porous V2O5Compared with the prior art, the microsphere preparation and application method has the positive effects that:
(1) the invention provides a three-dimensional hollow porous V2O5The preparation method of the microsphere is rapid, efficient, simple and easy to operate, strong in controllability, large in shell thickness and high in specific surface area of the product, and on one hand, the defect that the shell of the hollow structure prepared by a hard mask method is thin or easy to collapse is effectively overcome; on the other hand, compared with a template-free method, the method has better controllability, and the product has higher specific surface area. (2) Three-dimensional V prepared by the invention2O5The structure is a secondary hollow porous microsphere formed by disordered stacking of 10-20nm primary nano sheets, the diameter of the secondary hollow porous microsphere is about 1 mu m, the thickness of a shell layer is about 0.3 mu m, the pore diameter of the secondary hollow porous microsphere is 10-20nm, and the secondary hollow porous microsphere has a higher specific surface area of about 45-50 m2Per g, the field of application thereofAnd has wide prospect. (3) Three-dimensional hollow porous V2O5The microspheres are used as the negative electrode material of the lithium ion battery and are porous V2O5The nanosheets increase the contact area of the electrolyte, effectively shorten the diffusion transmission path of ions, provide a buffer space with variable volume due to the hollow structure, effectively maintain the structural stability, and finally show excellent rate capability and cycle stability.
Drawings
Fig. 1 is an X-ray diffraction pattern of the VO precursor and vanadium pentoxide microspheres prepared in example 1.
FIG. 2 is a scanning electron microscope (a-c) and a transmission electron microscope (d-f) image of the VO precursor prepared in example 1.
FIG. 3 is a scanning electron microscope (a-c) and a transmission electron microscope (d-f) showing the preparation of vanadium pentoxide microspheres in example 1.
FIG. 4 is a graph showing the adsorption/desorption curves and pore size distribution curves of the vanadium pentoxide microspheres prepared in example 1.
Fig. 5 is a charge-discharge curve and a rate cycle performance curve of the vanadium pentoxide microsphere prepared in example 1 as a negative electrode of a lithium ion battery, where a is the charge-discharge curve and b is the rate cycle performance curve.
Fig. 6 is a scanning electron microscope for preparing the VO precursor material in example 2.
Fig. 7 is a scanning electron microscope (a) and transmission electron microscope (b) image of the VO precursor material prepared in example 3.
Fig. 8 is a scanning electron microscope (a) and a transmission electron microscope (b) image of the VO precursor material prepared in example 4.
Fig. 9 is a scanning electron microscope image of the VO precursor material prepared in example 5.
Fig. 10 is a scanning electron microscope image of the VO precursor material prepared in example 6.
Fig. 11 is a scanning electron microscope image of the VO precursor material prepared in example 7.
Fig. 12 is a scanning electron microscope image of the VO precursor material prepared in example 8.
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 0.4g of vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of mixed solvent of n-propanol and ethylene glycol with the volume ratio of 1:1, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the three-dimensional hollow porous vanadium pentoxide microsphere.
(3) Preparing the lithium ion battery electrode piece for testing: mixing a three-dimensional hollow porous vanadium pentoxide microsphere active substance, a conductive agent acetylene black and a binder polyvinylidene fluoride according to a certain ratio (8: 1: 1) to prepare slurry, coating the slurry on a copper foil, drying and cutting into pieces to obtain the lithium ion battery negative electrode testing 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 0.01V-3.0V; constant charge and dischargeCurrent mode is performed, and the current density is set to 0.1-3.0A g-1。
FIG. 1 is an XRD (X-ray diffraction) pattern of the prepared VO precursor and vanadium pentoxide microspheres, and the VO precursor exists in the form of an organic ligand, so that no obvious characteristic diffraction peak exists; after heat treatment, the characteristic diffraction peak presented by the target product is sharp and is consistent with the matching of a standard card, and no obvious impurity diffraction peak exists, which shows that the prepared vanadium pentoxide material has high purity and crystallinity.
FIG. 2 is a scanning electron microscope (a-c) and a transmission electron microscope (d-f) of the prepared VO precursor under different magnifications, wherein the VO precursor microsphere is formed by stacking disordered nano sheets, has a uniform size of about 1 μm, and has a shell thickness of about 0.3 μm.
FIG. 3 is the scanning electron microscope (a-c) and the transmission electron microscope (d-f) of the prepared vanadium pentoxide microspheres under different multiplying powers. It is easy to find that: after heat treatment, the shape and the structural characteristics of the vanadium pentoxide of the target product are almost consistent with those of the precursor, which shows that the shape of the precursor basically determines the shape and the structural characteristics of the target product.
FIG. 4 is a graph showing the adsorption/desorption curves and pore size distribution curves of the prepared vanadium pentoxide microspheres, wherein the pore size distribution of the material is mainly concentrated at 10-20nm, and the specific surface area is about 47 m2/g。
FIG. 5 shows the charge-discharge curve (a) and the rate cycle performance (b) of the prepared vanadium pentoxide microsphere, the material is at 0.1A g-1The stable reversible capacity is up to 510 mAh g under the current density-1And after the material is cycled for 90 weeks under different current densities, the capacity retention rate exceeds 100 percent.
Example 2
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of mixed solvent of n-propanol and ethylene glycol with the volume ratio of 1:1, stirring and mixing uniformly at room temperature, reacting for 6h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the three-dimensional vanadium pentoxide microspheres.
(3) Preparing the lithium ion battery electrode piece for testing: mixing the three-dimensional vanadium pentoxide microsphere active substance, the conductive agent acetylene black and the binding agent polyvinylidene fluoride according to a certain ratio (8: 1: 1) to prepare slurry, coating the slurry on a copper foil, drying and cutting pieces to obtain the lithium ion battery negative electrode testing pole piece.
(4) And (3) electrochemical performance testing: the same test conditions as in example 1 were used.
Fig. 6 is a scanning electron microscope of different photographed parts of the prepared VO precursor, the microspheres do not completely exhibit a hollow structure, and the ostwald ripening process does not proceed completely due to the short solvothermal reaction time (6 h), which is in turn illustrated: the synthesis method has high controllability, namely the porous microspheres with the yolk-like core-shell structures can be obtained by simply controlling the solvothermal reaction time. The product after heat treatment has almost no difference in morphological characteristics from the precursor, but has a specific surface area of only about 32 m2(ii)/g; in addition, when the vanadium pentoxide microsphere material is used as a negative electrode of a lithium ion battery, the material is 0.1A g-1The stable reversible capacity is about 420 mAh g under the current density-1And the capacity retention of the material after 90-week cycling at different current densities was about 81%.
Example 3
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of glycol solvent, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the three-dimensional vanadium pentoxide microspheres.
(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. 7 is a scanning electron microscope (a) and a transmission electron microscope (b) image of the prepared VO precursor. The observation shows that: when ethylene glycol is used singly as a reaction solvent, the synthesized product is solid monodisperse smooth microspheres. In addition, after the microsphere precursor is subjected to heat treatment, the specific surface area is only 21 m2(ii)/g; when used as the negative electrode of a lithium ion battery, the material is 0.1A g-1The stable reversible capacity is about 348 mAh g under the current density-1And after the material is cycled for 90 weeks under different current densities, the capacity retention rate is lower than 50%.
Example 4
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of n-propanol solvent, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the three-dimensional vanadium pentoxide microspheres.
(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 a scanning electron microscope (a) and a transmission electron microscope (b) image of the prepared VO precursor. The observation shows that: when the n-propanol is singly used as a reaction solvent, the synthesized product is hollow porous microspheres, but the microspheres have obvious agglomeration and form a communicated worm-like structure. In addition, after the microsphere precursor is subjected to heat treatment, the specific surface area of the microsphere precursor is about 36 m2(ii)/g; when used as lithiumWhen the material is used as the negative electrode of the ion battery, the material is 0.1A g-1The stable reversible capacity is about 461 mAh g under the current density-1And the capacity retention of the material after 90-week cycling at different current densities was about 72%.
Example 5
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of mixed solvent of n-propanol and ethylene glycol with the volume ratio of 2:1, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the three-dimensional hollow porous vanadium pentoxide microsphere.
(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 a scanning electron microscope image of the prepared VO precursor at different magnifications. The observation shows that: the microsphere has a porous hollow structure, is consistent with the morphological structure characteristics of example 1, but the monodispersity of the microsphere is not very outstanding, namely the microsphere is slightly agglomerated. In addition, after the microsphere precursor is subjected to heat treatment, the specific surface area of the microsphere precursor is about 45 m2(ii)/g; when used as the negative electrode of a lithium ion battery, the material is 0.1A g-1The stable reversible capacity is about 502 mAh g at current density-1And after the material is cycled for 90 weeks under different current densities, the capacity retention rate is close to 100 percent.
Example 6
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of mixed solvent of n-propanol and ethylene glycol with the volume ratio of 1:2, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the three-dimensional hollow porous vanadium pentoxide microsphere.
(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 a scanning electron microscope image of the prepared VO precursor at different magnifications. The observation shows that: the microsphere has a porous hollow structure, is consistent with the morphological structure characteristics of the microsphere in the embodiment 1, and has obvious monodispersion characteristics. In addition, after the microsphere precursor is subjected to heat treatment, the specific surface area of the microsphere precursor is up to 49 m2(ii)/g; when used as the negative electrode of a lithium ion battery, the material is 0.1A g-1The stable reversible capacity is about 510 mAh g under the current density-1And after the material is cycled for 90 weeks under different current densities, the capacity retention rate exceeds 100 percent.
Example 7
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of mixed solvent of ethanol and ethylene glycol with the volume ratio of 1:1, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the vanadium pentoxide with the three-dimensional structure.
(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 a scanning electron microscope image of the prepared VO precursor at different magnifications. The observation shows that: the microspheresIs a solid monodisperse smooth microsphere with a morphology that is similar to the morphology obtained using ethylene glycol alone, but with more pronounced agglomeration. In addition, after the microsphere precursor is subjected to heat treatment, the specific surface area of the microsphere precursor is about 18 m2(ii)/g; when used as the negative electrode of a lithium ion battery, the material is 0.1A g-1The stable reversible capacity is only 320 mAh g under the current density-1And after the material is cycled for 90 weeks under different current densities, the capacity retention rate is lower than 50%.
Example 8
(1) Adding 0.4g of commercial vanadium pentoxide and 1.27g of citric acid into 40 mL of deionized water, and stirring at 80 ℃ for 0.5h to obtain 0.11 mol/L vanadyl citrate solution; adding 3 mL of vanadyl citrate solution into 30mL of mixed solvent of n-propanol and ethanol with the volume ratio of 1:1, stirring and mixing uniformly at room temperature, reacting for 18h at 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.
(2) And (3) heating the VO organic ligand precursor to 400 ℃ in the air at a heating rate of 4 DEG/min for heat treatment for 1h, and collecting a product after natural cooling to obtain the vanadium pentoxide with the three-dimensional structure.
(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. 12 is a scanning electron microscope image of the prepared VO precursor at different magnifications. The observation shows that: the material presents a connected worm-like structure, the morphology of which is similar to that obtained by singly using n-propanol, but the agglomeration phenomenon is more obvious. In addition, after the microsphere precursor is subjected to heat treatment, the specific surface area of the microsphere precursor is about 30m2(ii)/g; when used as the negative electrode of a lithium ion battery, the material is 0.1A g-1The stable reversible capacity is about 410 mAh g under the current density-1And the capacity retention of the material after 90-week cycling at different current densities was about 63%.
Through the above embodiments, it can be concluded that:
the invention provides three-dimensional hollow porous pentoxideThe preparation method of the vanadium pentoxide microspheres is rapid, efficient, simple and easy to operate, strong in controllability, large in shell thickness of the product and high in specific surface area. Particularly, the use of the mixed solvent is crucial, and the two solvents respectively play unique functions or roles, namely, although the n-propanol synthetic product is easy to agglomerate, the n-propanol synthetic product can promote a porous hollow structure; the ethylene glycol synthesized product is solid and smooth microspheres, but can promote monodispersity. When the two are combined, the generation of the quasi-monodisperse hollow porous microspheres can be effectively promoted, so that the synthesis process and the method of the three-dimensional vanadium pentoxide microspheres are greatly enriched and enriched. The shell of the vanadium pentoxide microsphere prepared by the invention has the thickness of about 0.3 mu m, the aperture of 10-20nm and higher specific surface area of about 45-50 m2(iv)/g, which is expected to find practical application in a wide variety of fields; for example, when the material is used as a lithium ion battery cathode, the material shows better rate performance and cycle stability, and has better application potential and prospect.

Claims (4)

1. The preparation method of the lithium ion battery cathode material hollow porous vanadium pentoxide microspheres 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; adding a certain volume of vanadyl citrate solution into a certain volume of mixed solvent of n-propanol and ethylene glycol, stirring and mixing uniformly at room temperature, reacting for 18-24 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 a 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 cathode material hollow porous vanadium pentoxide microsphere.
2. The preparation method of the hollow porous vanadium pentoxide microsphere as the negative electrode material of the lithium ion battery as claimed in claim 1, wherein the molar ratio of vanadium pentoxide to citric acid is 1: 2-4, and the molar concentration of vanadyl citrate is 0.1-0.2 mol/L.
3. The preparation method of the lithium ion battery negative electrode material hollow porous vanadium pentoxide microsphere according to claim 1, wherein the volume ratio of the n-propanol to the ethylene glycol is 1: 0.5-2, and the volume ratio of the vanadyl citrate solution to the mixed solvent is 1: 8-12.
4. The simple preparation method of the lithium ion battery anode material hollow porous vanadium pentoxide microsphere according to claim 1, characterized in that the heating rate of the heat treatment is 1-4 ℃/min.
CN202110757383.7A 2021-07-05 2021-07-05 Preparation method of lithium ion battery negative electrode material hollow porous vanadium pentoxide microspheres Pending CN113461056A (en)

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