CN102064323B - Mesoporous vanadium dioxide nano strip material as well as preparation method and application thereof - Google Patents
Mesoporous vanadium dioxide nano strip material as well as preparation method and application thereof Download PDFInfo
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- CN102064323B CN102064323B CN201010581078A CN201010581078A CN102064323B CN 102064323 B CN102064323 B CN 102064323B CN 201010581078 A CN201010581078 A CN 201010581078A CN 201010581078 A CN201010581078 A CN 201010581078A CN 102064323 B CN102064323 B CN 102064323B
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Abstract
The invention discloses a mesoporous vanadium dioxide nano strip material as well as a preparation method and application thereof. The mesoporous vanadium dioxide nano strip material is prepared by using the following steps of: mixing vanadium pentoxide with hydrogen peroxide to obtain vanadium pentoxide sol; uniformly mixing and ultrasonically dispersing the vanadium pentoxide sol, glucose and polyethylene glycol and transferring to a reactor; reacting at the constant temperature of 100-240 DEG C, cooling and centrifugally separating a solid; and washing the solid sequentially with deionized water and cyclohexane; then drying in vacuum to obtain a black mesoporous vanadium dioxide nano strip with the hole diameter mainly distributed in 3-5 nano. The mesoporous vanadium dioxide nano strip disclosed in the invention is a good magnesium secondary battery anode material. The constant current charge and discharge performance research of a magnesium secondary battery formed by the anode material indicates that the circulating volume and magnification discharge performance of the material are obviously improved. The method disclosed in the invention has the advantages of mild reaction condition, simple reaction process, high yield of products, high purity and high reproducibility.
Description
Technical field
The present invention relates to a kind of meso-porous titanium dioxide vanadium nano belt material and preparation method and the application in secondary cell thereof.
Background technology
A key factor that influences the Mg secondary cell charge-discharge magnification is the diffusion of magnesium ion in material, and the microcellular structure of diffusion coefficient and diffusion admittance and material has confidential relation.Mesoporous material was successfully prepared by Mobil company in 1992 first, had caused extensive concern.Mesoporous material contains fairly regular and very orderly aperture, and between 2-20nm, the size in aperture can utilize different assembling molecules and reaction condition to regulate greatly.Mesoporous material is introduced in the Mg secondary cell positive electrode, and it has stable structure, and the aperture can be regulated and control as required, and this will have a great breakthrough for the cycle life and the high-rate discharge ability that improve material.
In transition metal oxide, barium oxide becomes one of Mg secondary cell positive electrode that has development prospect most with advantages such as its high power capacity, low costs.The special construction of meso-porous titanium dioxide vanadium nano belt helps the embedding of object atom or ion.The synthetic method of vanadium dioxide nano band is more to have liquid phase reduction, chemical vapour deposition (CVD), hydro thermal method etc., but does not all have meso-hole structure.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of meso-porous titanium dioxide vanadium nano belt material is provided.
Second purpose of the present invention provides a kind of meso-porous titanium dioxide vanadium nano belt preparation methods.
The 3rd purpose of the present invention provides a kind of application of meso-porous titanium dioxide vanadium nano belt material.
Technical scheme of the present invention is summarized as follows:
A kind of meso-porous titanium dioxide vanadium nano belt material is characterized in that processing with following method:
(1) be 1 in mass ratio: the ratio of 20-100 is the hydrogen peroxide solution hybrid reaction of 5%-15% with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be the ratio of 20-85: 5-30: 10-50; Vanadic oxide colloidal sol, glucose and polyethylene glycol are mixed also ultrasonic dispersion 5-30 minute; Transfer to and have in the teflon-lined agitated reactor, at 100-240 ℃ of following isothermal reaction 4-48 hour, cooling; Centrifugalize out solid; Solid is successively with the washing of deionized water and cyclohexane, and then at 50-90 ℃ of following vacuumize 5-12 hour, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
Said polyethylene glycol is PEG-1000, PEG-2000, PEG-4000 or PEG-10000.
A kind of meso-porous titanium dioxide vanadium nano belt preparation methods is characterized in that comprising the steps:
(1) be 1 in mass ratio: the ratio of 20-100 is the aqueous hydrogen peroxide solution hybrid reaction of 5%-15% with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be the ratio of 20-85: 5-30: 10-50; Vanadic oxide colloidal sol, glucose and polyethylene glycol are mixed and ultrasonic dispersion 5-30 minute, transfer to and have in the teflon-lined agitated reactor, filling rate is 75%; At 100-240 ℃ of following isothermal reaction 4-48 hour; Cooling centrifugalizes out solid, and solid is successively with deionized water and cyclohexane washing; Then at 50-90 ℃ of following vacuumize 5-12 hour, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
Said polyethylene glycol is PEG-1000, PEG-2000, PEG-4000 or PEG-10000.
Meso-porous titanium dioxide vanadium nano belt material is in the application of Mg secondary cell positive electrode.
Meso-porous titanium dioxide vanadium nano belt of the present invention is extraordinary Mg secondary cell positive electrode.The constant current charge-discharge performance study of the Mg secondary cell that this positive electrode is formed shows, the circulation volume of this material and multiplying power discharging property have and significantly improve.
Method reaction condition of the present invention is gentle, and reaction process is simple, and yield of product is high, and purity is high, favorable reproducibility.
Description of drawings
Fig. 1 is the XRD figure of the prepared meso-porous titanium dioxide vanadium nano belt of embodiment 1;
Fig. 2 is the SEM figure of the prepared meso-porous titanium dioxide vanadium nano belt of embodiment 1;
Fig. 3 is the nitrogen adsorption-desorption isotherm of the prepared meso-porous titanium dioxide vanadium nano belt of embodiment 1;
Fig. 4 is the graph of pore diameter distribution of the prepared meso-porous titanium dioxide vanadium nano belt of embodiment 1;
Fig. 5 is the charge-discharge performance figure of the prepared meso-porous titanium dioxide vanadium nano belt of embodiment 1;
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
Accurately take by weighing 1 gram vanadic oxide and 50mL concentration expressed in percentage by volume and be 10% H
2O
2Reactant aqueous solution prepares vanadic oxide colloidal sol; Then vanadic oxide colloidal sol, 0.1 gram glucose and 0.1 gram polyethylene glycol (PEG-2000) were mixed also ultrasonic dispersion after 20 minutes; Mixture transferred to have in the teflon-lined agitated reactor; 180 ℃ of following isothermal reactions 12 hours, cooling separated; In 90 ℃ of following vacuumizes 10 hours, just obtain the meso-porous titanium dioxide vanadium nano belt of black after washing each 3 times with deionized water and cyclohexane successively.The XRD figure of product is seen Fig. 1; SEM figure sees Fig. 2, explains that the pattern of preparation product is a nano belt; Nitrogen adsorption-desorption isotherm is seen Fig. 3, explains that product has the suction dissolubility indicatrix of typical mesoporous material; Graph of pore diameter distribution is seen Fig. 4, and the pore-size distribution that product is described is mainly between the 3-5 nanometer.
Embodiment 2
The preparation of electrode and constant current charge-discharge test:
As active substances in cathode materials, battery anode slice according to active material, acetylene black and binding agent (PTFE) by mass ratio is: 80: 15: 5 mixed pressuring plates with the meso-porous titanium dioxide vanadium nano belt material of embodiment 1 preparation.The electrode slice of making is the disk of diameter 8mm, and in vacuum drying chamber 80 ℃ dry 12 hours down; Negative pole is the magnesium sheet of polishing light; Electrolyte is the Mg (AlBu of 0.25mol/L
2Cl
2)
2/ THF; Barrier film is: celgard 2300.In being full of the glove box of high-purity argon gas, the content of water assembles simulated battery less than 5ppm.Charge-discharge performance figure when charging and discharging currents density is 50mA/g sees Fig. 5, and the product of preparation is applied to Mg secondary cell and has cyclical stability and higher capacity preferably.
Embodiment 3
A kind of meso-porous titanium dioxide vanadium nano belt material, process with following method:
(1) in mass ratio being 1: 50 ratio, is 10% hydrogen peroxide solution hybrid reaction with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be 20: 30: 50 ratio, vanadic oxide colloidal sol, glucose and PEG-1000 are mixed and ultrasonic dispersion 20 minutes, transfer to and have in the teflon-lined agitated reactor; 100 ℃ of following isothermal reactions 48 hours; Cooling centrifugalizes out solid, and solid is successively with deionized water and cyclohexane washing; Then 90 ℃ of following vacuumizes 5 hours, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
Embodiment 4
A kind of meso-porous titanium dioxide vanadium nano belt material, process with following method:
(1) in mass ratio being 1: 60 ratio, is 8% hydrogen peroxide solution hybrid reaction with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be 85: 5: 10 ratio, vanadic oxide colloidal sol, glucose and PEG-2000 are mixed and ultrasonic dispersion 30 minutes, transfer to and have in the teflon-lined agitated reactor; 240 ℃ of following isothermal reactions 4 hours; Cooling centrifugalizes out solid, and solid is successively with deionized water and cyclohexane washing; Then 50 ℃ of following vacuumizes 12 hours, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
Embodiment 5
A kind of meso-porous titanium dioxide vanadium nano belt material, process with following method:
(1) in mass ratio being 1: 20 ratio, is 15% hydrogen peroxide solution hybrid reaction with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be 45: 15: 40 ratio, vanadic oxide colloidal sol, glucose and PEG-4000 are mixed and ultrasonic dispersion 5 minutes, transfer to and have in the teflon-lined agitated reactor; 180 ℃ of following isothermal reactions 12 hours; Cooling centrifugalizes out solid, and solid is successively with deionized water and cyclohexane washing; Then 70 ℃ of following vacuumizes 8 hours, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
Embodiment 6
A kind of meso-porous titanium dioxide vanadium nano belt material, process with following method:
(1) in mass ratio being 1: 100 ratio, is 5% hydrogen peroxide solution hybrid reaction with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be 60: 20: 20 ratio, vanadic oxide colloidal sol, glucose and PEG-10000 are mixed and ultrasonic dispersion 10 minutes, transfer to and have in the teflon-lined agitated reactor; 120 ℃ of following isothermal reactions 36 hours; Cooling centrifugalizes out solid, and solid is successively with deionized water and cyclohexane washing; Then 60 ℃ of following vacuumizes 10 hours, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
Experiment proof embodiment 3-embodiment 8 prepares battery anode slice and carries out the constant current charge-discharge test by the method for embodiment 2, when being applied to Mg secondary cell, also has cyclical stability and higher capacity preferably.
Claims (2)
1. a meso-porous titanium dioxide vanadium nano belt preparation methods is characterized in that comprising the steps:
(1) in mass ratio being the ratio of 1:20-100, is the hydrogen peroxide solution hybrid reaction of 5%-15% with vanadic oxide and concentration expressed in percentage by volume, processes vanadic oxide colloidal sol;
(2) in mass ratio be the ratio of 20-85:5-30:10-50; Vanadic oxide colloidal sol, glucose and polyethylene glycol are mixed also ultrasonic dispersion 5-30 minute; Transfer to and have in the teflon-lined agitated reactor, then with agitated reactor 100-240 ℃ of following isothermal reactions 4-48 hours, cooling; Centrifugalize out solid; Solid is successively with the washing of deionized water and cyclohexane, and then at 50-90 ℃ of following vacuumize 5-12 hour, the pore-size distribution that promptly obtains black is mainly in the meso-porous titanium dioxide vanadium nano belt of 3-5 nanometer.
2. a kind of meso-porous titanium dioxide vanadium nano belt preparation methods according to claim 1 is characterized in that said polyethylene glycol is PEG-1000, PEG-2000, PEG-4000 or PEG-10000.
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| CN103400974B (en) * | 2013-08-09 | 2016-01-06 | 重庆大学 | Vanadium system oxide makes application and the sol-gel process for preparing thereof of magnesium secondary battery cathode material |
| CN103872322B (en) * | 2014-03-19 | 2016-04-06 | 上海交通大学 | Nano porous metal sulfide rechargeable magnesium cell anode material and application process |
| CN105836800A (en) * | 2016-03-24 | 2016-08-10 | 南京航空航天大学 | Synthetic method for dimension-controllable vanadium dioxide nano material, and lithium ion battery |
| CN107910541A (en) * | 2017-12-01 | 2018-04-13 | 中南大学 | A kind of preparation method of the spherical composite material of negative electrode of lithium ion battery |
| CN112271278B (en) * | 2020-09-30 | 2021-09-24 | 中科南京绿色制造产业创新研究院 | Self-healing branched polyethylene diamine hydrogel microcapsule composite material, and preparation method and application thereof |
| CN113066973A (en) * | 2021-03-15 | 2021-07-02 | 武汉理工大学 | Self-supporting vanadium graphene interface zinc storage material and preparation method and application thereof |
| CN115084489B (en) * | 2022-08-19 | 2022-11-04 | 河南师范大学 | Preparation method and application of ultrasonic-assisted intercalation vanadium-based oxide composite material |
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| US6420067B1 (en) * | 1998-07-06 | 2002-07-16 | Canon Kabushiki Kaisha | MG-based negative electrode active material, method of manufacturing the same, hydrogen-storage alloy electrode, and alkali secondary battery |
| CN1522965A (en) * | 2003-09-12 | 2004-08-25 | 武汉理工大学 | Vanadium dioxide nanometer rod and preparation method thereof |
| CN1905251A (en) * | 2006-03-01 | 2007-01-31 | 南开大学 | Mg secondary cell |
| CN101559981A (en) * | 2009-05-27 | 2009-10-21 | 中国科学技术大学 | Method for preparing vanadium dioxide and doping powder thereof by combustion method |
| CN101807685A (en) * | 2010-04-27 | 2010-08-18 | 青岛科技大学 | Preparation method and application of silver vanadate/vanadium oxide one-dimensional composite nano-electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004259650A (en) * | 2003-02-27 | 2004-09-16 | Kanegafuchi Chem Ind Co Ltd | Magnesium secondary battery |
| JP2004265675A (en) * | 2003-02-28 | 2004-09-24 | Sanyo Electric Co Ltd | Non-aqueous electrolyte battery |
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| US6420067B1 (en) * | 1998-07-06 | 2002-07-16 | Canon Kabushiki Kaisha | MG-based negative electrode active material, method of manufacturing the same, hydrogen-storage alloy electrode, and alkali secondary battery |
| CN1522965A (en) * | 2003-09-12 | 2004-08-25 | 武汉理工大学 | Vanadium dioxide nanometer rod and preparation method thereof |
| CN1905251A (en) * | 2006-03-01 | 2007-01-31 | 南开大学 | Mg secondary cell |
| CN101559981A (en) * | 2009-05-27 | 2009-10-21 | 中国科学技术大学 | Method for preparing vanadium dioxide and doping powder thereof by combustion method |
| CN101807685A (en) * | 2010-04-27 | 2010-08-18 | 青岛科技大学 | Preparation method and application of silver vanadate/vanadium oxide one-dimensional composite nano-electrode material |
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