CN107840368B - A kind of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder and preparation method thereof - Google Patents
A kind of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder and preparation method thereof Download PDFInfo
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Abstract
A kind of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder and preparation method thereof, the present invention has synthesized the nanometer sheet self assembly sub-micrometer flower-shape hypovanadic oxide powder of high-purity using a step hydrothermal reaction at low temperature, and this method reaction process is simple, temperature is low, reaction condition that is easily-controllable and not needing large scale equipment and harshness.When applying above-mentioned product for lithium ion battery negative material with oxygen elctro-catalyst is produced, it can show excellent chemical property and electrocatalysis characteristic.It is made of by nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder made of preparation method of the invention the sub-micro popped rice that uniform diameter is about 1 μm, part sub-micro popped rice is assembled, sub-micro popped rice is that the nanometer sheet for being about 10nm by thickness is assembled in a manner of intercalation, and nanometer sheet shows the characteristic along the growth of (011) high preferred orientation.
Description
Technical field
The present invention relates to a kind of M-phase vanadium dioxide powders and preparation method thereof, and in particular to a kind of nanometer sheet self assembly is sub-
Flower-shaped M-phase vanadium dioxide powder of micron and preparation method thereof.
Background technique
Vanadium dioxide is a kind of complicated polycrystalline material with a variety of adjustable functions.Up to now, it has been reported that
It is equal more than the vanadium dioxide of 10 kinds of crystal phases, including B phase, M phase, R phase, A phase and C.In these vanadium dioxide, due to crystallizing
It can be realized the reversible transition of level-one metallic state and semiconductor form under room temperature, M phase hypovanadic oxide is widely used
[Liang S,Shi Q,Zhu H,et al.One-Step Hydrothermal Synthesis of W-Doped VO2(M)
Nanorods with a Tunable Phase-Transition Temperature for Infrared Smart
Windows[J].2016,1(6):1139-1148.].Although having there is a large amount of researcher to report the synthesis of vanadium dioxide,
But it is but very rare as the report of reaction raw materials using sodium metavanadate and thioacetamide.Currently, answering about M phase hypovanadic oxide
With infrared detector is concentrated mainly on, [Li Dengbing, Li Ming, Pan Jing wait the preparation of the monodispersed M phase hypovanadic oxide nano particle of
Method:, CN104071843A [P] .2014.], intelligent temperature control film, gas sensor, catalyst, thermochromism [Liu Xiangli,
A kind of method using a large amount of m phase vanadium dioxide nanowires of pulsed laser deposition technique fast-growth of Wang Chengqian:, CN
104762605A [P] .2015.] and fields such as switch, about its as lithium ion battery negative material using being rarely reported.
Synthesis M phase hypovanadic oxide pattern be mostly it is spherical, rodlike, rare nanometer sheet independently fills the report of micron floriform appearance.
Summary of the invention
That the purpose of the present invention is to provide a kind of reaction process is simple, temperature is low, easily-controllable and do not need large scale equipment and severe
Carve the nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder and preparation method thereof of reaction condition.
In order to achieve the above objectives, of the invention the preparation method comprises the following steps:
Step 1: taking 0.8~1.2g sodium metavanadate and 1.6~2.0g thioacetamide at the same be added to 55~65ml go from
In sub- water, magnetic agitation or ultrasonic disperse obtain half clear solution A；
Step 2: and then the ammonia spirit of 0.4~0.6mol/L is added dropwise dropwise into solution A, until solution ph reaches
10~10.2, obtain solution B；
Step 3: it is sealed after solution B is poured into reaction liner by 55~65% packing ratio, by liner loaded on solid in outer kettle
Surely it is placed in homogeneous reaction instrument, it is anti-by room temperature to be heated to 155~165 DEG C of progress hydro-thermals under the speed conditions of 5~15r/min
It answers；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, by product after water and alcohol alternately clean
Collect product；
Step 5: the product of collection being placed in the cold well of freeze drier and freezed, then by the product after freezing
It is placed in pallet, covers seal closure, be evacuated down to 10~20Pa, collect product after dry 12~18h and obtain nanometer sheet from group
Fill sub-micrometer flower-shape M-phase vanadium dioxide powder.
The step 1 magnetic agitation or ultrasonic time are 55~65min, and speed of agitator is 800~1000r/min.
Ammonia spirit will be added dropwise dropwise under the conditions of adjusting the continuous magnetic agitation of pH in the step 2 in solution A, control ammonia
The rate of addition of aqueous solution is 0.05~0.07ml/min, drips previous drop ammonia spirit, and stirring is until solution ph is stablized
Afterwards, then next drop ammonia spirit is instilled, until reacting liquid pH value is adjusted to 10.1~10.2.
The step 3 the hydro-thermal reaction time is 23~25h.
The cleaning of the step 4 is carried out using suction filtration or centrifugation.
The collection of the step 4 is carried out using suction filtration or centrifugation.
The freezing conditions of the step 5 are as follows: -60~-40 DEG C, freeze 2~5 hours.
The step 5 product is sealed it before being put into pallet and being dried, with preservative film, and to preservative film
It carries out pricking hole processing, to guarantee to its abundant drying under lower pressure.
It is by uniform by nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder made of preparation method of the invention
Diameter be about 1 μm sub-micro popped rice composition, part sub-micro popped rice assembled, and it is about 10nm that sub-micro popped rice, which is by thickness,
Nanometer sheet is assembled in a manner of intercalation, and nanometer sheet shows the characteristic along the growth of (011) high preferred orientation.
The present invention has synthesized the nanometer sheet self assembly sub-micrometer flower-shape vanadium dioxide of high-purity using a step hydrothermal reaction at low temperature
Powder, this method reaction process is simple, temperature is low, reaction condition that is easily-controllable and not needing large scale equipment and harshness.When will be upper
Product is stated to apply for lithium ion battery negative material and when producing oxygen elctro-catalyst, it can show excellent chemical property and
Electrocatalysis characteristic.
Specifically have the beneficial effect that:
(1) present invention is due to directly synthesizing final product using a step hydro-thermal reaction, thus has low synthesis temperature
Degree, simple synthesis path do not need large scale equipment and harsh reaction condition；
(2) vanadium source used in the present invention is sodium metavanadate, sulphur source is thioacetamide, both raw materials are Common materials,
Raw material is cheap and easy to get, at low cost, and yield is high, reacts easily-controllable, is not necessarily to post-processing, environmentally friendly, can be suitble to extensive life
It produces；
(3) the M phase hypovanadic oxide nanometer sheet prepared by the present invention has extra small thickness (~10nm), not only can produce
Biggish specific surface area, but also more surface-active sites can be provided, and then chemical property can be promoted and electricity is urged
Change performance.In addition, this extra small thickness can not only shorten charge transfer path, but also can be provided for the storage of lithium ion
More active sites, so as to promoting the specific capacity and high rate performance of material.Meanwhile the titanium dioxide of this extra small thickness
Vanadium surface can expose more polyoxy and provide sufficient guarantee to produce oxygen performance；
(4) the unique nanometer sheet of the M-phase vanadium dioxide powder self-assembled structures interconnected prepared by the present invention, a side
Face can play good restraining function, on the other hand also provide cushion space to the expansion of nanometer sheet and contraction, so as to
Greatly to alleviate the volume change of nanometer sheet, its cyclical stability is finally significantly improved；
(5) present invention prepared by the unique intercalation shape sub-micron floral structure of M-phase vanadium dioxide powder can guarantee electrolyte/
Electrolyte and vanadium dioxide come into full contact with, and then reduce electrochemical reaction/electro-catalysis resistance, further improve performance；
(6) M phase hypovanadic oxide nanometer sheet of the present invention has the characteristic along the growth of (011) high preferred orientation, biggish crystal face
Spacing can provide more fully boundary space for electrochemical reaction and electrocatalytic reaction；
(7) present invention needs the packing ratio in strict control reaction process, and higher packing ratio can promote S2-Ion exchange
Oxygen in vanadic acid root, to produce VS2.Lower packing ratio is conducive to S2 2-Formation, so as to cause VS4Generation.Therefore, instead
Packing ratio is answered to play conclusive effect for the synthesis of pure phase M phase hypovanadic oxide.
(8) present invention also needs strict control pH value in reaction simultaneously, and higher pH value can make thioacetamide hydrolysis big
The S of amount2-, to promote VS2It is formed, while higher pH value can make in solution that there are a large amount of OH-, to form VOOH.It is lower
PH value can make a large amount of H of thioacetamide hydrolysis2S, to promote VS4It is formed.Therefore, higher lower pH value is all unfavorable
In the synthesis of pure phase M phase hypovanadic oxide.
(9) concentration of ammonia spirit and regulative mode will have a direct impact on depositing for the source V and the source S in precursors in the present invention
In state, to influence the generation chemically reacted in water-heat process, eventually leading to can be with the presence of this many miscellaneous phase in product.
In addition, if the OH- that sodium hydroxide is fully hydrolyzed generation can induce the shape of VOOH after changing weak base ammonium hydroxide into highly basic sodium hydroxide
At.
(10) present invention does not introduce any template or surface-active during synthesizing three-dimensional self-assembled structures
Agent, entire self assembling process be by reaction raw materials self-template effect control, thus entirely react it is simple, easily-controllable, efficient and
Low cost；
(11) product chemistry composition prepared by the present invention is uniform, with high purity, pattern is uniform, is used as negative electrode of lithium ion battery
Excellent performance can be shown when material and electro-catalysis regenerative agent.When being applied to lithium ion battery negative material, performance
Excellent chemical property out, in 0.01~3.0 voltage range, 30,50,100,200,500,1000mAg-1Electric current
Under density, up to 324,254,207,163,102,65mAhg are shown-1Specific capacity；When return to 30mAg-1Electric current
Under density, still there is 309mAhg-1Capacity be kept.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) figure that the embodiment of the present invention 1 prepares product.
Fig. 2 is (other conditions are identical with embodiment 1) institute after packing ratio in the embodiment of the present invention 1 is adjusted to 70%
Obtain the XRD diagram of product.
Fig. 3 is (other conditions is identical with embodiment 1) after packing ratio in the embodiment of the present invention 1 is adjusted to 50%,
The XRD diagram of products therefrom.
Fig. 4 is low power scanning electron microscope (SEM) figure that the embodiment of the present invention 1 prepares product.
Fig. 5 is the high power SEM figure that the embodiment of the present invention 1 prepares product.
Fig. 6 is the super-high power SEM figure that the embodiment of the present invention 1 prepares product.
Fig. 7 is low power transmission electron microscope (TEM) figure that the embodiment of the present invention 1 prepares product.
Fig. 8 is the high power TEM figure that the embodiment of the present invention 1 prepares product.
Fig. 9 is the super-high power TEM figure that the embodiment of the present invention 1 prepares product.
Figure 10 is the HRTEM figure that the embodiment of the present invention 1 prepares product.
Figure 11 is that the embodiment of the present invention 1 prepares high rate performance of the product as lithium ion battery negative material when.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1:
Step 1: 1.0g sodium metavanadate and 1.8g thioacetamide are taken while being added in 60ml deionized water, in 900r/
Magnetic agitation 60min obtains half clear solution A under the speed conditions of min；
Step 2: will be added drop-wise to dropwise 0.5mol/L ammonia spirit in solution A under the conditions of magnetic agitation, control ammonia spirit
Rate of addition be 0.06ml/min, drip previous drop ammonia spirit, after stirring is until solution ph stablizes, then instill next
Ammonia spirit is dripped, until reacting liquid pH value is adjusted to 10.1, obtains solution B；
Step 3: it is sealed after solution B is poured into reaction liner by 60% packing ratio, liner is loaded in outer kettle and fixes postposition
In homogeneous reaction instrument, 160 DEG C of hydro-thermal reactions are heated to for 24 hours by room temperature under the speed conditions of 5r/min；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, by product through water and alcohol alternately cleaning 3 times
After collect product；
The cleaning and collection is carried out using suction filtration；
Step 5: the product of collection is placed in the cold well of freeze drier and freezes 2 hours under the conditions of -40 DEG C, then
Product after freezing is placed in pallet, it is sealed with preservative film, and preservative film is carried out to prick hole processing, covered later
Seal closure is evacuated down to 12Pa, collects product after dry 12h and obtain nanometer sheet self assembly sub-micrometer flower-shape M phase hypovanadic oxide
Powder.
It can be clearly seen that the diffraction maximum of synthesized product and the standard card (PDF# of M phase hypovanadic oxide from Fig. 1
It 82-0661) fits like a glove, illustrates that the product of synthesis is pure phase M phase hypovanadic oxide.In addition, smooth elongated diffraction maximum explanation should
Product has good crystallinity, and the corresponding diffraction peak intensity of (011) crystal face is most strong, shows that the product has significant edge
(011) characteristic of high preferred orientation growth.
From figure 2 it can be seen that products therefrom is vanadium disulfide, when showing to increase reaction-filling ratio to 70%, product by
Vanadium dioxide is converted into vanadium disulfide, and reaction high pressure caused by higher packing ratio will promote S2-It has replaced in vanadium dioxide
Oxygen.Therefore, higher packing ratio is unfavorable for the synthesis of M phase hypovanadic oxide.
From figure 3, it can be seen that the main object Xiang Weisi vanadic sulfide of products therefrom, and along with sulphur simple substance miscellaneous phase, show
When reducing reaction-filling ratio to 50%, product is converted into four vanadic sulfides by vanadium dioxide, and lower packing ratio promotes S2 2-'s
It is formed, then promotes VS4Formation.Therefore, lower packing ratio is also unfavorable for the synthesis of M phase hypovanadic oxide.
Figure 4, it is seen that products therefrom is made of uniform spherical structure, pattern uniformity with higher,
Part-spherical is assembled.
From figure 5 it can be seen that the spherical structure of products therefrom shows sub-micrometer flower-shape, the diameter of micro-flowers is about 1 μ
m。
From fig. 6 it can be seen that the sub-micrometer flower-shape structure of products therefrom be by nanometer sheet in a manner of intercalation self assembly and
At the thickness of nanometer sheet is about 10nm.
It can be seen from figure 7 that products therefrom has solid micron flower-like structure, and the diameter of micro-flowers is about 1 μm.
As can be seen from Figure 8, the micron floral structure of products therefrom is that self assembly forms in a manner of intercalation by nanometer sheet, and
The thickness of nanometer sheet is about 10nm.
It can be seen in figure 9 that the nanometer sheet of products therefrom has ultra-thin thickness.
It can be clearly seen that lattice fringe corresponding to M phase hypovanadic oxide from Figure 10, it is higher to show that the product has
Crystallinity.
It can be seen from fig. 11 that in 0.01~3.00 voltage range, 30,50,100,200,500,
1000mAg-1Current density under, M phase hypovanadic oxide shows up to 324,254,207,163,102,65mAhg-1Ratio
Capacity；When return to 30mAg-1Current density under, still have 309mAhg-1Capacity be kept.
Embodiment 2:
Step 1: taking 0.8g sodium metavanadate and 1.7g thioacetamide while being added in 58ml deionized water,
Magnetic agitation 55min obtains half clear solution A under the speed conditions of 1000r/min；
Step 2: will be added drop-wise to dropwise 0.4mol/L ammonia spirit in solution A under the conditions of magnetic agitation, control ammonia spirit
Rate of addition be 0.05ml/min, drip previous drop ammonia spirit, after stirring is until solution ph stablizes, then instill next
Ammonia spirit is dripped, until reacting liquid pH value is adjusted to 10.2, obtains solution B；
Step 3: it is sealed after solution B is poured into reaction liner by 55% packing ratio, liner is loaded in outer kettle and fixes postposition
In homogeneous reaction instrument, 158 DEG C of hydro-thermal reaction 25h are heated to by room temperature under the speed conditions of 8r/min；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, by product through water and alcohol alternately cleaning 5 times
After collect product；
The cleaning and collection is carried out using centrifugation；
Step 5: the product of collection is placed in the cold well of freeze drier and freezes 4 hours under the conditions of -55 DEG C, then
Product after freezing is placed in pallet, it is sealed with preservative film, and preservative film is carried out to prick hole processing, covered later
Seal closure is evacuated down to 15Pa, collects product after dry 15h and obtain nanometer sheet self assembly sub-micrometer flower-shape M phase hypovanadic oxide
Powder.
Embodiment 3:
Step 1: 1.2g sodium metavanadate and 1.9g thioacetamide are taken while being added in 55ml deionized water, in 800r/
Magnetic agitation 65min obtains half clear solution A under the speed conditions of min；
Step 2: will be added drop-wise to dropwise 0.45mol/L ammonia spirit in solution A under the conditions of magnetic agitation, control ammonium hydroxide is molten
The rate of addition of liquid is 0.07ml/min, drips previous drop ammonia spirit, after stirring is until solution ph is stable, then is instilled down
One drop ammonia spirit obtains solution B until reacting liquid pH value is adjusted to 10.1；
Step 3: it is sealed after solution B is poured into reaction liner by 65% packing ratio, liner is loaded in outer kettle and fixes postposition
In homogeneous reaction instrument, 162 DEG C of hydro-thermal reaction 23h are heated to by room temperature under the speed conditions of 12r/min；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, by product through water and alcohol alternately cleaning 4 times
After collect product；
The cleaning and collection is carried out using suction filtration；
Step 5: the product of collection is placed in the cold well of freeze drier and freezes 3 hours under the conditions of -50 DEG C, then
Product after freezing is placed in pallet, it is sealed with preservative film, and preservative film is carried out to prick hole processing, covered later
Seal closure is evacuated down to 18Pa, collects product after dry 17h and obtain nanometer sheet self assembly sub-micrometer flower-shape M phase hypovanadic oxide
Powder.
Embodiment 4:
Step 1: taking 0.9g sodium metavanadate and 1.6g thioacetamide while being added in 62ml deionized water, ultrasound point
Scattered 55min obtains half clear solution A；
Step 2: will be added drop-wise to dropwise 0.55mol/L ammonia spirit in solution A under the conditions of magnetic agitation, control ammonium hydroxide is molten
The rate of addition of liquid is 0.07ml/min, drips previous drop ammonia spirit, after stirring is until solution ph is stable, then is instilled down
One drop ammonia spirit obtains solution B until reacting liquid pH value is adjusted to 10.2；
Step 3: it is sealed after solution B is poured into reaction liner by 58% packing ratio, liner is loaded in outer kettle and fixes postposition
In homogeneous reaction instrument, 155 DEG C of hydro-thermal reaction 25h are heated to by room temperature under the speed conditions of 15r/min；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, by product through water and alcohol alternately cleaning 6 times
After collect product；
The cleaning and collection is carried out using suction filtration；
Step 5: the product of collection is placed in the cold well of freeze drier and freezes 5 hours under the conditions of -60 DEG C, then
Product after freezing is placed in pallet, it is sealed with preservative film, and preservative film is carried out to prick hole processing, covered later
Seal closure is evacuated down to 20Pa, collects product after dry 14h and obtain nanometer sheet self assembly sub-micrometer flower-shape M phase hypovanadic oxide
Powder.
Embodiment 5:
Step 1: taking 1.1g sodium metavanadate and 2.0g thioacetamide while being added in 65ml deionized water, ultrasound point
Scattered 65min obtains half clear solution A；
Step 2: will be added drop-wise to dropwise 0.6mol/L ammonia spirit in solution A under the conditions of magnetic agitation, control ammonia spirit
Rate of addition be 0.05ml/min, drip previous drop ammonia spirit, after stirring is until solution ph stablizes, then instill next
Ammonia spirit is dripped, until reacting liquid pH value is adjusted to 10.2, obtains solution B；
Step 3: it is sealed after solution A is poured into reaction liner by 62% packing ratio, liner is loaded in outer kettle and fixes postposition
In homogeneous reaction instrument, 165 DEG C of hydro-thermal reaction 23h are heated to by room temperature under the speed conditions of 10r/min；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, by product through water and alcohol alternately cleaning 5 times
After collect product；
The cleaning and collection is carried out using suction filtration；
Step 5: the product of collection is placed in the cold well of freeze drier and freezes 4 hours under the conditions of -45 DEG C, then
Product after freezing is placed in pallet, it is sealed with preservative film, and preservative film is carried out to prick hole processing, covered later
Seal closure is evacuated down to 10Pa, collects product after dry 18h and obtain nanometer sheet self assembly sub-micrometer flower-shape M phase hypovanadic oxide
Powder.
Claims (9)
1. a kind of preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder, it is characterised in that:
Step 1: 0.8~1.2g sodium metavanadate and 1.6~2.0g thioacetamide are taken while being added to 55~65ml deionized water
In, magnetic agitation or ultrasonic disperse obtain half clear solution A；
Step 2: and then the ammonia spirit of 0.4~0.6mol/L being added dropwise into solution A dropwise, until solution ph reach 10~
10.2, obtain solution B；
Step 3: it seals, liner is loaded in outer kettle after fixing after solution B is poured into reaction liner by 55~65% packing ratio
It is placed in homogeneous reaction instrument, 155~165 DEG C of progress hydro-thermal reactions is heated to by room temperature under the speed conditions of 5~15r/min；
Step 4: naturally cooling to room temperature for reaction kettle after hydro-thermal reaction, and product is collected after water and alcohol alternately clean
Product；
Step 5: the product of collection is placed in the cold well of freeze drier and is freezed, be then placed in the product after freezing
In pallet, seal closure is covered, is evacuated down to 10~20Pa, product is collected after dry 12~18h and obtains nanometer sheet self assembly Asia
The flower-shaped M-phase vanadium dioxide powder of micron.
2. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: the step 1 magnetic agitation or ultrasonic time are 55~65min, and speed of agitator is 800~1000r/min.
3. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: ammonia spirit will be added dropwise dropwise under the conditions of adjusting the continuous magnetic agitation of pH in the step 2 in solution A, control ammonium hydroxide
The rate of addition of solution is 0.05~0.07ml/min, drips previous drop ammonia spirit, after stirring is until solution ph is stable,
Next drop ammonia spirit is instilled again, until reacting liquid pH value is adjusted to 10.1~10.2.
4. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: the step 3 the hydro-thermal reaction time is 23~25h.
5. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: the cleaning of the step 4 is carried out using suction filtration or centrifugation.
6. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: the collection of the step 4 is carried out using suction filtration or centrifugation.
7. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: the freezing conditions of the step 5 are as follows: -60~-40 DEG C, freezes 2~5 hours.
8. the preparation method of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder according to claim 1, special
Sign is: the step 5 product is sealed it before being put into pallet and being dried, with preservative film, and to preservative film into
Row pricks hole processing, to guarantee to its abundant drying under lower pressure.
9. nanometer sheet self assembly sub-micrometer flower-shape M phase hypovanadic oxide powder made of a kind of preparation method as described in claim 1
Body, it is characterised in that: hypovanadic oxide powder is made of the sub-micro popped rice that uniform diameter is about 1 μm, part sub-micro popped rice into
Aggregation is gone, sub-micro popped rice is that the nanometer sheet for being about 10nm by thickness is assembled in a manner of intercalation, and nanometer sheet is shown
Along the characteristic of (011) high preferred orientation growth.
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| CN112209442B (en) * | 2020-10-16 | 2022-07-29 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing M-phase vanadium dioxide nano powder by salt-assisted ultrasonic pyrolysis method |
| CN113184906A (en) * | 2021-05-13 | 2021-07-30 | 陕西科技大学 | One-step hydrothermal method for preparing V2O3Method of nanosphere |
| CN113213543A (en) * | 2021-05-13 | 2021-08-06 | 陕西科技大学 | MnO (MnO)2/V2O3Process for preparing nano composite material |
| CN113247951A (en) * | 2021-05-13 | 2021-08-13 | 陕西科技大学 | Self-assembly sheet VS2Preparation method of/S nanosheet |
| CN115058728B (en) * | 2022-07-13 | 2023-06-20 | 陕西科技大学 | Flaky V 4 O 9 Self-assembled nanometer flower ball self-supporting electrode material and preparation method thereof |
| CN115092961B (en) * | 2022-07-14 | 2023-12-22 | 贵州大学 | Preparation method and application of hollow spherical shell structured vanadium oxyhydroxide |
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