CN102398919B - Preparation method of rutile phase vanadium dioxide - Google Patents
Preparation method of rutile phase vanadium dioxide Download PDFInfo
- Publication number
- CN102398919B CN102398919B CN 201010275610 CN201010275610A CN102398919B CN 102398919 B CN102398919 B CN 102398919B CN 201010275610 CN201010275610 CN 201010275610 CN 201010275610 A CN201010275610 A CN 201010275610A CN 102398919 B CN102398919 B CN 102398919B
- Authority
- CN
- China
- Prior art keywords
- preparation
- rutile phase
- intercalation
- lipf
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a preparation method of rutile phase vanadium dioxide. The preparation method comprises the following steps of 1, inserting alkali metal Li between C axial layers of V2O5 having a sheet-shaped structure, wherein by control, an inserting amount ratio of the alkali metal Li to V2O5 is 2mol: 1mol, 2, immersing the intercalation products obtained by the step1 in a non-oxidative acid solution so that hydrogen ions in the non-oxidative acid solution replace lithium ions of the intercalation products, washing and drying, and 3, heating the dried products obtained by the step 2 at a temperature of 600 to 1000 DEG C in vacuum or in a non-oxidative atmosphere to obtain the rutile phase vanadium dioxide (VO2). The preparation method provided by the invention can realize high-yield and high-efficiency preparation of VO2, has safe, simple and convenient processes and a controllable process flow, and is easy for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of rutile phase hypovanadic oxide, relating to a kind of specifically is raw material with the Vanadium Pentoxide in FLAKES, reduces to prepare the method for rutile phase hypovanadic oxide by the alkali metal lithium electrochemical intercalation.Belong to oxide functional material preparation and Application Areas.
Background technology
From the 1950's, some inversion of phases compounds are found in succession.Its character shows as: with the reduction of temperature, in certain temperature range, material can take place from metallographic phase (M) to semi-conductor phase (S) or the unexpected transformation of isolator phase (I) characteristic, is called for short MST (or MIT) and changes, and be attended by crystal to the lower thaumatropy of symmetry degree.In many inversion of phases compounds, with the VO of transformation temperature near room temperature (Tc=68 ℃)
2The most noticeable.
VO
2Changing at the MST of T=340K is that its internal crystal structure changes the result of (being that inside undergoes phase transition).When temperature T＞340K, VO
2Have cubic rutile structure, be expressed as VO
2(R), the space point group is P4
2/ mnm; When temperature T＜340K, VO
2Be monocline, be expressed as VO
2(M), the space point group is P2
1/ c.Work as VO
2VO takes place
2(R) to VO
2When (M) changing, V
4+Move to appearance from octahedral body-centered, depart from the structure cell vertex position, crystallographic axis length and bond angle change simultaneously.Follow this variation, structure and the performance of material are undergone mutation simultaneously.Sudden change on the order of magnitude takes place in many physical propertiess such as susceptibility, resistivity, light refractive index, transmissivity and reflectivity etc. in the nanosecond time range.These character of phase transformation front and back can leap the sun power temperature control unit, photoelectric switch material, thermistor material, the fields such as optical storage material, energy-saving coating, photochromic material of can wiping that just make at for example buildings and have very big application potential.
VO
2Huge Commercial Prospect make the various countries scientific research personnel carry out broad research to it.Although developed multiple synthetic vanadium dioxide (VO
2) preparation method's (comprising: solid reaction process, thermal decomposition method, oxidation reduction process, the precipitator method, sol-gel method, hydrothermal method etc.) [(1) Kimizuka N. of powder, Isahii M., Kwaada M., et al, J.Solid State Chem., 1974,9 (1): 69-77. (2) Tsang S., Manthiram A., J.Electrochem.Soc., 1997,144 (2): 520-523. (3) Stanley A.L., Edward A.T., J.Am.Ceram.Soc., 1995,78 (1): 104-108; Zheng C.M., Zhang J.L., Journal of material science, 2000,35:3425-3429. (4) Tsang C., Manthiram A., J.Electrochem.Soc., 144 (2), 1997:520-524; Xu C.L., Ma L., Liu X., Su Z.X., Mater.Res.Bull, 2004,39:881-886. (5) Mnaivannan V., Goodenuogh J.B., Materials Research Bulletin, 1998,9 (33): 1353-1357. (6) Toshiyuki 0., Yasuhiro I., Kenkyu R.K., J.Photopolym Sci.Teehno1.10 (2), 1997:211-217], explore and design new synthetic method and still have value theoretical and that use.
Summary of the invention
The object of the present invention is to provide a kind of rutile phase (R phase) vanadium dioxide (VO
2) new preparation method, this method can realize rutile phase VO
2The preparation of big output high-level efficiency, simple and safe operation, process is controlled, is easy to large-scale production.
At VO
2In powder synthetic, V
2O
5Be a kind of raw material commonly used, by reductive agent with V
2O
5Can prepare VO after the reduction
2The present invention is from V
2O
5Crystalline structure start with because V
2O
5Be lamellar compound, interlayer can hold small-molecule substance, and the small molecules that therefore has reductibility can exist at interlayer, and then to V
2O
5Reduce.In addition, the present invention also combines the principle of work (in compound with laminate structure or tunnel embed and take off embedding discharge and recharge by lithium) that metallic lithium has reductibility and lithium cell, utilize the device of lithium cell first, as reductive agent, lithium is embedded V with metallic lithium
2O
5Interlayer and the pentavalent vanadium is reduced generates the precursor that contains the tetravalence vanadium, can prepare VO through after the subsequent disposal
2
For achieving the above object, the present invention is by the following technical solutions:
A kind of preparation method of rutile phase hypovanadic oxide may further comprise the steps:
1) alkali metal Li is inserted the V with synusia shape structure
2O
5C axle interlayer, control Li the intercalation amount to 2molLi/1mol V
2O
5
2) step 1) gained intercalation after product is soaked in non-oxidizable acid solution, make hydrogen ion in the acid solution replace the lithium ion in the described intercalation after product, washing and dry then;
3) with step 2) in dried product under vacuum or non-oxidizable shielding gas atmosphere, heat-treat in 600～1000 ℃, obtain rutile phase VO
2
In the aforesaid method, follow alkali the insertion of metal Li, the pentavalent vanadium (V in the Vanadium Pentoxide in FLAKES
5+) be reduced to tetravalence vanadium (V gradually
4+), the product of generation is LiV
2O
5, LiVO
2With B VO mutually
2This product changes HV into after the non-oxidizing acid solution soaking is handled
2O
5, HVO
2And VO
2, can obtain rutile phase VO through Overheating Treatment again
2
Described Vanadium Pentoxide in FLAKES can be block, powder or film.
Preferable, the pH value of described non-oxidizable acid solution is 2～6, described non-oxidizing acid is sulfuric acid, hydrochloric acid or acetic acid.
Preferable, described non-oxidizable shielding gas is nitrogen or argon gas.
Preferable, the present invention adopts electrochemical method alkali metal Li to be inserted the V with synusia shape structure
2O
5C axle interlayer, comprise following concrete steps:
A) with V
2O
5With the lithium sheet respectively as positive and negative two electrodes, separate with the polypropylene porous diaphragm between two electrodes, and soak into two electrodes and barrier film with the alkalimetal ion organic electrolyte; Under the anhydrous and oxygen-free condition above-mentioned all components is sealed in the electrochemical reactor;
B) positive and negative polarities in the electrochemical reactor that obtains in the step a) and pilot circuit are connected into the loop line, make the entire reaction system with certain current discharge, it is anodal that Li ion in electronics in the external circuit and the reactor is flowed to by negative pole by external circuit and electrolyte inside respectively, is 2mol Li/1molV until the intercalation amount of metal Li
2O
5
In the described step a), the solvent of alkalimetal ion organic electrolyte is selected from PC (propylene carbonate), EC (NSC 11801), DME (glycol dimethyl ether), DMC (methylcarbonate), EMC (Methyl ethyl carbonate), 2Me-THF (2-methyltetrahydrofuran) or DEC (diethyl carbonate) etc.; Its solute is selected from LiClO4, LiPF
6, LiAsF
6Or LiBPO
4Deng; The optimum concn of solute is 1mol/L in the described electrolytic solution.The preferred electrolyte system of the present invention has: LiPF
6/ EC/DEC, LiPF
6/ EC/DMC or LiPF
6/ EC/DEC/DMC etc.
In the described step b), by control discharging current size and the intercalation time with the intercalation amount of accurate control lithium to 2molLi/1mol V
2O
5(Li
2V
2O
5Loading capacity 295.64mAh/g).
Preferable, in the described step b), discharging current I is 0.1～10 milliampere, loading capacity is the every grams of 150～400 MAHs.The intercalation time is obtained divided by discharging current by loading capacity.
The present invention has made rutile phase hypovanadic oxide by four steps such as the preparation of electrochemical intercalation device, electrochemical intercalation, non-oxidizing acid solution soaking, thermal treatments; The described VO that makes
2Have purer thing phase, and strong phase transformation exothermic phenomenon is arranged about 68 ℃.Method provided by the invention can realize rutile phase VO
2The preparation of big output high-level efficiency, simple and safe operation, process is controlled, is easy to large-scale production.
Description of drawings
Fig. 1 is embodiment 1 discharge process graphic representation, and graphic representation as can be known thus: system exports positive voltage to external circuit in the constant-current discharge process, and this shows that the Li atom can spontaneously be inserted into anodal V
2O
5Interlayer, and have very big lithium storage content.
Fig. 2 is the synthetic hypovanadic oxide powder of embodiment 1 and the X ray diffracting spectrum of raw material Vanadium Pentoxide in FLAKES powder;
Fig. 3 is embodiment 1 gained rutile phase VO
2The thermogravimetric analysis collection of illustrative plates.As can be seen, the obtained rutile phase of present method VO
2Have purer thing phase, and strong phase transformation exothermic phenomenon is arranged about 68 ℃.
Embodiment
Embodiment 1:
With 0.4g Vanadium Pentoxide in FLAKES powder compressing tablet, place 2032 type button cell reaction unit positive poles; Negative pole is put into metal Li sheet; Separate with the polypropylene porous diaphragm between the positive and negative electrode; With electrolytic solution LiPF
6/ EC/DEC soaks into two electrodes and barrier film; Under the protection of Ar gas, above-mentioned all components is sealed in the electrochemical reactor.Reactor positive and negative polarities and extraneous constant current source are connected into the loop line, are that charging is after 29.56 hours under the 4mA at constant current, and it is supersound process centrifugal oven dry after 2 hours in 2 the sulphuric acid soln that anodal product is soaked in pH.Powder after will drying at last carries out thermal treatment in 30 minutes in 600 ℃ of nitrogen atmospheres, obtain rutile phase VO
2
Embodiment 2:
Place homemade multilayered electrochemical intercalation device as anodal 2g Vanadium Pentoxide in FLAKES powder; Negative pole is put into metal Li sheet; Separate with the polypropylene porous diaphragm between the positive and negative electrode; With electrolytic solution LiPF
6/ EC/DEC soaks into two electrodes and barrier film; Reactor positive and negative polarities and extraneous constant current source are connected into the loop line, are that charging is after 98.55 hours under the 6mA at constant current, and it is supersound process centrifugal oven dry after 2 hours in 4 the hydrochloric acid soln that anodal product is soaked in pH.Powder after will drying at last carries out thermal treatment in 30 minutes in 800 ℃ of nitrogen atmospheres, obtain rutile phase VO
2
Embodiment 3:
Place homemade roll type electrochemical intercalation reaction unit as anodal 2g Vanadium Pentoxide in FLAKES powder; Negative pole is put into metal Li volume; Separate with the polypropylene porous diaphragm between the positive and negative electrode; With electrolytic solution LiPF
6/ EC/DEC soaks into two electrodes and barrier film; Reactor positive and negative polarities and extraneous constant current source are connected into the loop line, are that charging is after 73.91 hours under the 8mA at constant current, and it is centrifugal oven dry after ultrasonic 2 hours in 6 the sulphuric acid soln that anode thin film is soaked in pH.Powder after will drying at last carries out thermal treatment in 30 minutes in 1000 ℃ of nitrogen atmospheres, obtain rutile phase VO
2
Embodiment 4:
With 0.4g Vanadium Pentoxide in FLAKES powder compressing tablet, place 2032 type button cell reaction unit positive poles; Negative pole is put into metal Li sheet; Separate with the polypropylene porous diaphragm between the positive and negative electrode; With electrolytic solution LiPF
6/ EC/DMC soaks into two electrodes and barrier film; Under the protection of Ar gas, above-mentioned all components is sealed in the electrochemical reactor.Reactor positive and negative polarities and extraneous constant current source are connected into the loop line, are that charging was soaked in supersound process centrifugal oven dry after 2 hours in the sulphuric acid soln that pH is 3-4 with anodal product after 300 hours under the 0.3mA at constant current.Powder after will drying at last carries out thermal treatment in 30 minutes in 800 ℃ of nitrogen atmospheres, obtain rutile phase VO
2
Embodiment 5:
With 0.4g Vanadium Pentoxide in FLAKES powder compressing tablet, place 2032 type button cell reaction unit positive poles; Negative pole is put into metal Li sheet; Separate with the polypropylene porous diaphragm between the positive and negative electrode; With electrolytic solution LiPF
6/ EC/DEC/DMC soaks into two electrodes and barrier film; Under the protection of Ar gas, above-mentioned all components is sealed in the electrochemical reactor.Reactor positive and negative polarities and extraneous constant current source are connected into the loop line, are that charging was soaked in supersound process centrifugal oven dry after 2 hours in the sulphuric acid soln that pH is 3-4 with anodal product after 120 hours under the 1mA at constant current.Powder after will drying at last carries out thermal treatment in 30 minutes in 600 ℃ of nitrogen atmospheres, obtain rutile phase VO
2
Claims (5)
1. the preparation method of a rutile phase hypovanadic oxide may further comprise the steps:
1) alkali metal Li is inserted the V with synusia shape structure
2O
5C axle interlayer, control Li the intercalation amount to 2molLi/1molV
2O
5
2) step 1) gained intercalation after product is soaked in non-oxidizable acid solution, make hydrogen ion in the acid solution replace the lithium ion in the described intercalation after product, washing and dry then;
3) with step 2) in dried product under vacuum or non-oxidizable shielding gas atmosphere, heat-treat in 600～1000 ℃, obtain rutile phase VO
2
In the step 1), adopt electrochemical method alkali metal Li to be inserted the V with synusia shape structure
2O
5C axle interlayer;
Described electrochemical method may further comprise the steps:
A) with V
2O
5With the lithium sheet respectively as positive and negative two electrodes, separate with the polypropylene porous diaphragm between two electrodes, and soak into two electrodes and barrier film with the alkalimetal ion organic electrolyte; Under the anhydrous and oxygen-free condition above-mentioned all components is sealed in the electrochemical reactor;
B) positive and negative polarities in the electrochemical reactor that obtains in the step a) and pilot circuit are connected into the loop line, make the entire reaction system with certain current discharge, it is anodal that Li ion in electronics in the external circuit and the reactor is flowed to by negative pole by external circuit and electrolyte inside respectively, is 2mol Li/1molV until the intercalation amount of metal Li
2O
5
2. the preparation method of rutile phase hypovanadic oxide as claimed in claim 1 is characterized in that, the pH value of described non-oxidizable acid solution is 2～6, and described non-oxidizing acid is selected from sulfuric acid, hydrochloric acid or acetic acid.
3. the preparation method of rutile phase hypovanadic oxide as claimed in claim 1 is characterized in that, in the described step a), the solvent of alkalimetal ion organic electrolyte is selected from PC, EC, DME, DMC, EMC, 2Me-THF or DEC; Its solute is selected from LiClO
4, LiPF
6And LiAsF
6
4. the preparation method of rutile phase hypovanadic oxide as claimed in claim 3 is characterized in that, in the described step a), the alkalimetal ion organic electrolyte is selected from LiPF
6/ EC/DEC, LiPF
6/ EC/DMC or LiPF
6/ EC/DEC/DMC.
5. the preparation method of rutile phase hypovanadic oxide as claimed in claim 1 is characterized in that, in the described step b), discharging current is 0.1～10 milliampere, and loading capacity is the every grams of 150～400 MAHs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010275610 CN102398919B (en) | 2010-09-08 | 2010-09-08 | Preparation method of rutile phase vanadium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010275610 CN102398919B (en) | 2010-09-08 | 2010-09-08 | Preparation method of rutile phase vanadium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102398919A CN102398919A (en) | 2012-04-04 |
| CN102398919B true CN102398919B (en) | 2013-07-17 |
Family
ID=45881634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010275610 Active CN102398919B (en) | 2010-09-08 | 2010-09-08 | Preparation method of rutile phase vanadium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102398919B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158883A (en) * | 2020-10-16 | 2021-01-01 | 成都先进金属材料产业技术研究院有限公司 | Process for preparing vanadium dioxide nano powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4957725A (en) * | 1988-07-05 | 1990-09-18 | The Johns Hopkins University | Vanadium dioxide formed by the sol-gel process |
| CN1693212A (en) * | 2005-04-25 | 2005-11-09 | 四川大学 | Process for preparing vanadium dioxide nano powder |
| CN101391814A (en) * | 2008-10-31 | 2009-03-25 | 中国科学院上海硅酸盐研究所 | Method for preparing rutile phase hypovanadic oxide powder |
-
2010
- 2010-09-08 CN CN 201010275610 patent/CN102398919B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4957725A (en) * | 1988-07-05 | 1990-09-18 | The Johns Hopkins University | Vanadium dioxide formed by the sol-gel process |
| CN1693212A (en) * | 2005-04-25 | 2005-11-09 | 四川大学 | Process for preparing vanadium dioxide nano powder |
| CN101391814A (en) * | 2008-10-31 | 2009-03-25 | 中国科学院上海硅酸盐研究所 | Method for preparing rutile phase hypovanadic oxide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102398919A (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102244257B (en) | High-temperature manganic acid lithium cathode material and preparation method thereof | |
| CN101591012B (en) | Preparation method of lithium iron phosphate as cathode material of lithium ion battery | |
| CN102013489B (en) | Metallic titanium doped carbon-coating lithium iron phosphate and preparation method thereof | |
| CN102034971B (en) | Lithium-ion battery lithium iron phosphate/polypyrrole pyridine composite anode material and preparation method thereof | |
| CN105914400B (en) | Electrolyte and sodium-ion battery | |
| CN101777644A (en) | Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| CN101800307A (en) | Method for preparing carbon-coated manganese-doped lithium titanate negative electrode material of lithium ion battery | |
| CN103682292B (en) | The lithium titanate material preparation method of high-tap density | |
| CN105789606A (en) | Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material | |
| CN103390748B (en) | A kind of preparation method of alumina-coated lithium cobaltate cathode material | |
| CN105742601A (en) | Method for in-situ synthesis of carbon coated-hydrated V3O7 nanobelt and lithium ion battery | |
| CN102249297A (en) | Method for preparing lithium titanate powder | |
| CN110556518A (en) | Fluorinated vanadium-titanium-sodium phosphate/carbon composite cathode material for sodium ion battery and preparation method thereof | |
| CN102583583A (en) | Cathode material of manganese, cobalt and lithium oxidate for lithium ion battery and preparation method of cathode material | |
| CN108306010B (en) | Lithium manganate positive electrode material and preparation method thereof | |
| CN103326014B (en) | Manganese-series layered lithium-rich cathode material, preparation method thereof and applications thereof | |
| CN102903918B (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN103050698A (en) | Vanadium lithium iron phosphate anode material and preparation method thereof | |
| CN102916186A (en) | Method for manufacturing sodion battery negative pole material and negative pole and sodion battery | |
| CN102479944B (en) | Preparation method and application of lithium iron phosphate composite material | |
| CN103050678A (en) | Preparation method of electrode material lanthanum doped lithium titanate for lithium ion battery | |
| CN106784657A (en) | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material | |
| CN105428619A (en) | Preparation method of high-performance Ti2Nb10O29/C composite electrode material | |
| CN102881904A (en) | Method for preparing double-carbon-source coated LiFePO4/C composite anode material through two-step sintering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201225 Address after: 215400 No.6 Liangfu Road, Chengxiang Town, Taicang City, Suzhou City, Jiangsu Province Patentee after: Zhongke sikas (Suzhou) Technology Development Co.,Ltd. Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |