CN103420418A - Hydrothermal preparation method of V10O24.12H2O - Google Patents
Hydrothermal preparation method of V10O24.12H2O Download PDFInfo
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- CN103420418A CN103420418A CN2012101496503A CN201210149650A CN103420418A CN 103420418 A CN103420418 A CN 103420418A CN 2012101496503 A CN2012101496503 A CN 2012101496503A CN 201210149650 A CN201210149650 A CN 201210149650A CN 103420418 A CN103420418 A CN 103420418A
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- hydrothermal
- acidic solution
- deionized water
- preparing process
- vanadium compound
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Abstract
The invention provides a hydrothermal preparation method of V10O24.12H2O. According to the method of the invention, an acidic solution is prepared from an organic acid and deionized water; then after a vanadium compound is added to the acidic solution, the vanadium compound is reacted with ingredients in the acidic solution under a hydrothermal condition; next after the reacted solution is cooled down, the product obtained by the reaction is soaked in deionized water then is filtered and dried, thus the obtained V10O24.12H2O has dark green color, has silvery luster after sheeting, has a micron-sized ribbon-shaped morphology under a scanning electron microscope, and has relatively high crystallinity as shown in X-ray diffraction. The method has low cost and simple synthesis process path, allows the reaction conditions to be easy to control, allows the final product to have high purity and high crystallinity, enables the particle size and the particle size distribution to be adjusted and controlled, and is convenient for industrialized mass production.
Description
Technical field
The present invention relates to a kind of V
10O
2412H
2The hydrothermal preparing process of O.
Background technology
Lithium ion battery because thering is height ratio capacity, high-voltage, discharge and recharge that the life-span is long, environmental pollution is little etc., and advantage receives much concern, the development of the battery material of lithium ion is study hotspot always.Embed deepening continuously of de-embedding mechanism from chemistry redox mechanism to lithium ion along with Study on Li-ion batteries using, attracted the research of large quantities of investigators to 3d group 4 transition metal element oxide/salt, the materials such as cobalt acid lithium, lithium manganate, Co-Ni-Mn ternary material, iron lithium phosphate are developed and are applied to industrial production in succession.But the investigator finds the step of new type lithium ion battery material not to stop.Vanadium, can be with oxygen in conjunction with forming with V as a typical multivalence state transition metal
xO
yThe many oxide that state exists, wherein vanadium can be with+5 ,+4 ,+3 ,+the divalent state exists.In the barium oxide system, the existence of multiple oxidation state and coordination polyhedron makes it have the open architecture that can embed metal ion, so its applied research aspect lithium ion battery material more and more comes into one's own.
As far back as 20th century 70, the eighties, oxyvanadium compound just is found to have good embedding lithium performance, and research mainly concentrates on V
2O
5, V
6O
13And Li
1+xV
3O
8On three compounds.V wherein
6O
13Each molecule can embed 8 Li
+, its theoretical capacity can reach 420mAh/g(referring to document: Insertion electrode materials for rechargeable lithium batteries.Adv Mater, and 1998,10:725-763); Li
l+xV
3O
8Also there is the advantages such as electrical capacity is high, making method is simple, the life-span is long, the speed that discharges and recharges is fast and stable in the air (referring to document: Microwave solid-state synthesis of LiV
3O
8Aseathode material for lithium batteries[J] .J Phys Chem B, 2005,109:11186-1119).Therefore, oxyvanadium compound electrode materials specific storage is high, can heavy-current discharge etc. advantage it is had a wide range of applications on the high tension battery material.
V
10O
2412H
2O, as a kind of oxyvanadium compound, has the laminate structure that can hold a large amount of lithium ions, is a kind of potential lithium ion battery material.Manlio Occhiuzzi in 2005 etc. (referring to document: Reactivity of some vanadium oxides:An EPR and XRD study[J] .Solid State Chem, 2005,178 (5): 1551) by different valence state vanadium oxide pyroreaction first synthetic the V of quasi-crystalline state
10O
2412H
2The O material, and it has been carried out to the research of EPR and XRD aspect; W.G-Menezas in 2007 etc. (referring to document: Vanadium oxide nanostructures derived from a novel vanadium (IV) alkoxide precursor[J] .Chem Phys Lett, 2007,445 (4-6): 293) by the organic salt hydrolysis method, synthesized class V
10O
2412H
2The fibrous V of O structure
10O
249H
2The O material, shown good electrochemical behavior; Sun Juan duckweeds in 2009 etc. at low temperatures, with V
2O
5Powder is raw material, adopts sol-gel technique, peroxidation method and solvent replacing technique to prepare nanoporous V
10O
2412H
2O, be studied in detail (referring to document: novel oxyvanadium compound V its chemical property
100
2412H
2The preparation of O and ac impedance characteristic [J] material Leader, 2009,23(8): 22), and applied for patent, referring to Chinese patent CN101565205B: " nano-material V
10O
2412H
2O preparation ".
In sum, in current literature research and domestic and international patent, mainly adopt the thinking that scorification, organic vanadium salt solution solution and sol-gel technique are combined with peroxidation method, solvent replacing technique to prepare V
10O
2412H
2The O material.There are no with V
2O
5, organic acid, the deionized water such as acetic acid or formic acid, citric acid, oxalic acid be initial feed, under hydrothermal condition, synthesizes V
10O
2412H
2The document of O layer structure material and patent.
Summary of the invention
The shortcoming of prior art, the object of the present invention is to provide a kind of V simple and easy to control in view of the above
10O
2412H
2The hydrothermal preparing process of O.
Reach for achieving the above object other relevant purposes, the invention provides a kind of V
10O
2412H
2The hydrothermal preparing process of O, it comprises step:
1) organic acid and deionized water are mixed with to acidic solution;
2) after vanadium compound is added to described acidic solution, then the composition in vanadium compound and acidic solution is reacted at hydrothermal condition;
3) solution after question response cooling after, will react products therefrom and soak in deionized water, filter and dry again.
Preferably, the pH value of described acidic solution is between 1.0～5.0.
Preferably, described vanadium compound comprises analytically pure V
2O
5Powder.
Preferably, described organic acid is at least one in formic acid, acetic acid, citric acid, oxalic acid.
Preferably, described hydrothermal condition comprises: temperature is 50～300 ℃, and the hydro-thermal reaction time is 10～48 hours.
Preferably, described bake out temperature is between 90-150 ℃.
As mentioned above, V of the present invention
10O
2412H
2The V that the hydrothermal preparing process of O is prepared
10O
2412H
2The O color is blackish green, has silvering after compressing tablet, is the banded pattern of micron order under scanning electron microscope, and X ray diffracting spectrum shows that it has higher crystallinity.
The accompanying drawing explanation
Fig. 1 is shown as V prepared by the present invention
10O
2412H
2The X ray diffracting spectrum of O.
Fig. 2 is shown as the present invention and prepares V
10O
2412H
2The X ray diffracting spectrum of the mix products formed in the O process.
Embodiment
Below, by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Embodiment mono-:
Get the acetic acid solution that 3ml concentration is 36%, with the 9ml deionized water, be mixed with mixing solutions; The solution prepared is inserted in the hydrothermal reaction kettle of 30ml, add 0.114gV
2O
5Powder, fully stir 30min with magnetic stirring apparatus, mixes; Reactor is inserted in baking oven to reaction after 24h hour under 180 ℃, room temperature naturally cooling; By reaction product washing by soaking, sedimentation 3 times repeatedly in deionized water, vacuum filtration, dry under 105 ℃, gets final product to obtain target product V
10O
2412H
2The O powder.
Embodiment bis-:
Get the acetic acid solution that 3ml concentration is 36%, with the 9ml deionized water, be mixed with mixing solutions; The solution prepared is inserted in the hydrothermal reaction kettle of 30ml, add 0.085gV
2O
5Powder, fully stir 30min with magnetic stirring apparatus, mixes; Reactor is inserted in baking oven to reaction after 48h hour under 150 ℃, room temperature naturally cooling; By reaction product washing by soaking, sedimentation 3 times repeatedly in deionized water, vacuum filtration, dry under 105 ℃, gets final product to obtain target product V
10O
2412H
2The O powder.
Embodiment tri-:
Get the acetic acid solution that 3ml concentration is 36%, with the 9ml deionized water, be mixed with mixing solutions; The solution prepared is inserted in the hydrothermal reaction kettle of 30ml, add 0.187gV
2O
5Powder, fully stir 30min with magnetic stirring apparatus, mixes; Reactor is inserted in baking oven to reaction after 24h hour under 240 ℃, room temperature naturally cooling; By reaction product washing by soaking, sedimentation 3 times repeatedly in deionized water, vacuum filtration, dry under 105 ℃, gets final product to obtain target product V
10O
2412H
2The O powder.
Embodiment tetra-:
Get the analytically pure formic acid solution of 1ml, with the 9ml deionized water, be mixed with mixing solutions; The solution prepared is inserted in the hydrothermal reaction kettle of 30ml, add 0.187gV
2O
5Powder, fully stir 30min with magnetic stirring apparatus, mixes; Reactor is inserted in baking oven to reaction after 24h hour under 180 ℃, room temperature naturally cooling; By reaction product washing by soaking, sedimentation 3 times repeatedly in deionized water, vacuum filtration, dry under 105 ℃, gets final product to obtain target product V
10O
2412H
2The O powder.
Embodiment five:
Get the analytically pure oxalic acid powder of 4g, with the 9ml deionized water, be mixed with mixing solutions; The solution prepared is inserted in the hydrothermal reaction kettle of 30ml, add 0.114gV
2O
5Powder, fully stir 30min with magnetic stirring apparatus, mixes; Reactor is inserted in baking oven to reaction after 24h hour under 180 ℃, room temperature naturally cooling; By reaction product washing by soaking, sedimentation 3 times repeatedly in deionized water, vacuum filtration, dry under 105 ℃, gets final product to obtain target product V
10O
2412H
2The O powder.
Embodiment six:
Get the analytically pure citric acid powder of 5g, with the 9ml deionized water, be mixed with mixing solutions; The solution prepared is inserted in the hydrothermal reaction kettle of 30ml, add 0.114gV
2O
5Powder, fully stir 30min with magnetic stirring apparatus, mixes; Reactor is inserted in baking oven to reaction after 24h hour under 180 degrees centigrade, room temperature naturally cooling; By reaction product washing by soaking, sedimentation 3 times repeatedly in deionized water, vacuum filtration, dry under 105 ℃, gets final product to obtain target product V
10O
2412H
2The O powder.
The prepared V based on preparation method of the present invention
10O
2412H
2The O color is blackish green, has silvering after compressing tablet, is the banded pattern of micron order under scanning electron microscope, and X ray diffracting spectrum shows that it has higher crystallinity, and specifically referring to Fig. 1 and Fig. 2, wherein, Fig. 1 is V prepared by the present invention
10O
2412H
2The X ray diffracting spectrum of O; In Fig. 2, curve a is V
2O
5The X ray diffracting spectrum of powder; Curve b is under 180 ℃, and hydro-thermal reaction 5h gained intermediate state mixture (is V
10O
2412H
2O and V
2O
5Coexist) X ray diffracting spectrum; Curve c is under 180 ℃, hydro-thermal reaction 12h reaction product (V
10O
2412H
2The O pure phase) X ray diffracting spectrum.Wherein, the coordinate of Fig. 1 and Fig. 2 adopts the English mark mode of the X ray diffracting spectrum current international practice, and the Y-axis Intensity in Fig. 1 means sample powder X-ray diffraction relative intensity, and X-axis 2 θ/degree means angle of diffraction; In Fig. 2, Y-axis Intensity (a.u.) means sample powder X-ray diffraction relative intensity, and a.u. means arbitraryunit, and arbitrary unit, only have relative meaning, and X-axis 2 θ/degree means angle of diffraction.
To sum up, V of the present invention
10O
2412H
2The raw materials cost that the hydrothermal preparing process of O adopts is cheap, and synthesis route is simple, and reaction conditions is easy to control, and final product purity is high, and degree of crystallinity is high, and particle fineness and size distribution can regulate and control, and are convenient to large-scale industrialization production.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, be modified or be changed above-described embodiment.Therefore, such as in affiliated technical field, have and usually know that the knowledgeable, not breaking away from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (6)
1. a V
10O
2412H
2The hydrothermal preparing process of O, is characterized in that, described V
10O
2412H
2The hydrothermal preparing process of O at least comprises step:
1) organic acid and deionized water are mixed with to acidic solution;
2) after vanadium compound is added to described acidic solution, then the composition in vanadium compound and acidic solution is reacted at hydrothermal condition;
3) solution after question response cooling after, will react products therefrom and soak in deionized water, filter and dry again.
2. V according to claim 1
10O
2412H
2The hydrothermal preparing process of O is characterized in that: the pH value of described acidic solution is between 1.0～5.0.
3. V according to claim 1
10O
2412H
2The hydrothermal preparing process of O is characterized in that: described vanadium compound comprises analytically pure V
2O
5Powder.
4. V according to claim 1
10O
2412H
2The hydrothermal preparing process of O is characterized in that: described organic acid is at least one in formic acid, acetic acid, citric acid, oxalic acid.
5. V according to claim 1
10O
2412H
2The hydrothermal preparing process of O is characterized in that: described hydrothermal condition comprises: temperature is 50～300 ℃, and the hydro-thermal reaction time is 10～48 hours.
6. V according to claim 5
10O
2412H
2The hydrothermal preparing process of O is characterized in that: described bake out temperature is between 90-150 ℃.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713305A (en) * | 2018-12-30 | 2019-05-03 | 常州大学 | A kind of crystallization water battery and preparation method thereof |
| CN110707299A (en) * | 2019-04-17 | 2020-01-17 | 中南大学 | Vanadium oxide/carbon/clay composite positive electrode material, preparation method thereof and application thereof in water-based battery |
| CN111056571A (en) * | 2020-01-19 | 2020-04-24 | 兰州大学 | Simple method for preparing low-crystallinity vanadium oxide in batches and doping modification thereof |
| WO2020138137A1 (en) * | 2018-12-27 | 2020-07-02 | 昭和電工株式会社 | Method for purifying vanadium oxide |
| CN115124080A (en) * | 2022-07-22 | 2022-09-30 | 浙江工业大学 | Vanadium oxide nanosheet array and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863511A (en) * | 2010-07-05 | 2010-10-20 | 中国科学技术大学 | Method for preparing monoclinic phase vanadium dioxide and doped nano powder thereof |
-
2012
- 2012-05-14 CN CN2012101496503A patent/CN103420418A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863511A (en) * | 2010-07-05 | 2010-10-20 | 中国科学技术大学 | Method for preparing monoclinic phase vanadium dioxide and doped nano powder thereof |
Non-Patent Citations (3)
| Title |
|---|
| BAI LINGYAN ET AL.: "Synthesis and Atmospheric Instability of well Crystallized Rod-shaped V2O4*2H2O Powders Prepared in an Aqueous Solution", 《JOURNAL OF THE CERAMIC SOCIETY OF JAPAN》, vol. 116, no. 3, 31 December 2008 (2008-12-31), pages 395 - 399 * |
| WILLIAN G. MENEZES ET AL.: "Vanadium oxide nanostructures derived from a novel vanadium(IV) alkoxide precursor", 《CHEMICAL PHYSICS LETTERS》, vol. 445, no. 46, 13 September 2007 (2007-09-13), pages 293 - 296, XP022233616, DOI: doi:10.1016/j.cplett.2007.08.026 * |
| 孙娟萍等: "新型纳米结构V10O24*12H2O的制备及结构表征", 《高等学校化学学报 》, vol. 30, no. 11, 30 November 2009 (2009-11-30), pages 2107 - 2111 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020138137A1 (en) * | 2018-12-27 | 2020-07-02 | 昭和電工株式会社 | Method for purifying vanadium oxide |
| CN109713305A (en) * | 2018-12-30 | 2019-05-03 | 常州大学 | A kind of crystallization water battery and preparation method thereof |
| CN109713305B (en) * | 2018-12-30 | 2022-06-17 | 常州大学 | Crystal water battery and preparation method thereof |
| CN110707299A (en) * | 2019-04-17 | 2020-01-17 | 中南大学 | Vanadium oxide/carbon/clay composite positive electrode material, preparation method thereof and application thereof in water-based battery |
| CN110707299B (en) * | 2019-04-17 | 2021-01-01 | 中南大学 | Vanadium oxide/carbon/clay composite positive electrode material, preparation method thereof and application thereof in water-based battery |
| CN111056571A (en) * | 2020-01-19 | 2020-04-24 | 兰州大学 | Simple method for preparing low-crystallinity vanadium oxide in batches and doping modification thereof |
| CN111056571B (en) * | 2020-01-19 | 2022-07-15 | 兰州大学 | Simple method for preparing low-crystallinity vanadium oxide in batches and doping modification thereof |
| CN115124080A (en) * | 2022-07-22 | 2022-09-30 | 浙江工业大学 | Vanadium oxide nanosheet array and preparation method and application thereof |
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