CN102412400A - Silver vanadium oxide / polymer three coaxial nanowire and preparation method and application thereof - Google Patents
Silver vanadium oxide / polymer three coaxial nanowire and preparation method and application thereof Download PDFInfo
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- CN102412400A CN102412400A CN2011102960026A CN201110296002A CN102412400A CN 102412400 A CN102412400 A CN 102412400A CN 2011102960026 A CN2011102960026 A CN 2011102960026A CN 201110296002 A CN201110296002 A CN 201110296002A CN 102412400 A CN102412400 A CN 102412400A
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Abstract
The invention relates to a silver vanadium oxide / polymer three coaxial nanowire and preparation method and application thereof, as well as the application of the materials as lithium ion battery anode active materials has a obvious three coaxial structure, the length is 10 to 30microns, the diameter is 60-100nm, in which the nuclear is the beta-AgVO3 nanowire, a middle layer is a silver vanadium oxide layer produced by the surface of the beta-AgVO3the nanowire losing parts of silver ions, an outer layer is a polymer layer, the thickness of the outer layer is 6 to10 nm, the thickness of the middle layer is 6 to10 nm, the beneficial effects of the invention are that: when the nanowire as the lithium ion battery anode active materials, the specific capacity and the cycle stability are significantly improved; and the prepared materials is high purity and good dispersion; also, the method related to the other three coaxial nanowire preparation, in-situ chemical polymerization is with water as the medium, the synthesis of the three coaxial nanowire can be achieved under normal temperature and normal pressure after a short time stirring, which is benefit for the market promotion.
Description
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of silver-vanadium oxide/polymer three co-axial nano lines and preparation method thereof, and this material is as the application of anode active material of lithium ion battery.
Background technology
Lithium ion battery is as a kind of green energy resource; Be applied to portable electric appts and electric automobile, research is one of forward position and focus of current low-carbon economy epoch Study on Li-ion batteries using based on high power capacity, microminiaturization, high power, the low-cost lithium ion battery of novel nano heterostructure.Ag
2V
4O
11Have advantages such as energy density height, performance be safe and reliable and be used as lithium ion primary cell material application to cardiac pacemaker.And Ag
2V
4O
11Compare β-AgVO
3Because of having higher Ag:V than being considered to have better chemical property.But, present β-AgVO
3Research as lithium ion secondary battery anode material also rarely has report, and silver-vanadium oxide still exists that conductance is low, capacity attenuation very fast, the shortcoming of cyclic reversibility difference etc.
In recent years, labyrinth nano wire (like coaxial nano wire, three co-axial nano lines etc.) has obtained increasing concern because of having a series of excellent specific properties in electrochemistry and energy field.Conducting polymer has air stability preferably, higher conductivity, environment avirulence, reversible characteristics such as redox characteristic, is widely used in constructing and electrochemical modification of co-axial nano line.But, be that three co-axial nano lines of shell also do not appear in the newspapers with the conducting polymer.
Summary of the invention
Technical problem to be solved by this invention is to provide to above-mentioned prior art that a kind of preparation technology is simple, the requirement that meets Green Chemistry, have silver-vanadium oxide/polymer three co-axial nano lines of good electric chemical property and preparation method thereof.
A further object of the invention provides the application of said silver-vanadium oxide/polymer three co-axial nano lines.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: silver-vanadium oxide/polymer three co-axial nano lines, it is characterized in that it has tangible three coaxial configurations, and length is 10 ~ 30 microns, and diameter is the 60-100 nanometer, and its center is β-AgVO
3Nano wire, intermediate layer are β-AgVO
3Nanowire surface loses the part silver ion and the silver-vanadium oxide layer that produces, and outermost layer is a polymeric layer, and outermost layer thickness is 6 ~ 10 nanometers, and intermediate layer thickness is 6 ~ 10 nanometers.
Press such scheme, described polymer is polyaniline, polypyrrole or polythiophene.
The preparation method of silver-vanadium oxide/polymer three co-axial nano lines is characterized in that including following steps:
1) the vanadium source aqueous solution is mixed under stirring condition with the silver-colored source aqueous solution, obtain precursor solution;
2) step 1) gained precursor solution is transferred to agitated reactor, reacts, naturally cool to room temperature, centrifugal filtration obtains sediment;
3) with deionized water cyclic washing step 2) sediment that obtains, and oven dry obtains β-AgVO
3Nano wire;
4) with β-AgVO
3Nano wire is scattered in the deionized water, adds polymer monomer, wherein, and β-AgVO
3The mass ratio of nano wire and polymer monomer is 2:1, and stirring at room 10-14 hour, the aqueous oxidizing agent solution of amount of substances such as adding and polymer monomer continued stirring at room 10 ~ 14 hours, the centrifugal precipitated product that obtains then;
5) with the precipitated product of deionized water and absolute ethyl alcohol cyclic washing step 4) gained, oven dry obtains silver-vanadium oxide/polymer three co-axial nano lines.
Press such scheme, described vanadium source includes but not limited to ammonium metavanadate or vanadic oxide colloidal sol.
Press such scheme, described silver-colored source includes but not limited to silver nitrate, silver acetate or silver carbonate.
Press such scheme, described polymer monomer includes but not limited to aniline monomer, pyrrole monomer or thiophene monomer.
Press such scheme, step 2) described reaction temperature is 160 ℃ ~ 200 ℃, the reaction time is 12 ~ 36 hours.
Press such scheme, described oxidant comprises but is not limited to ammonium persulfate, potassium bichromate or ferric trichloride.
Described silver-vanadium oxide/polymer three co-axial nano lines are in the application as anode active material of lithium ion battery.
The invention has the beneficial effects as follows: based on β-AgVO<sub >3</sub>Nano wire; Prepare silver-vanadium oxide/polymer nano rice noodles of providing obvious three coaxial configurations in conjunction with chemical situ aggregation method and solid-liquid interface redox reaction method; Its center is β-AgVO3 nano wire, and the intermediate layer is that β-AgVO3 nanowire surface loses the Ag that the part silver ion produces<sub >x</sub>VO<sub >(2.5+0.5x)</sub>(0<x<1) layer, outermost layer is a polymeric layer, this structure can effectively improve conductivity of electrolyte materials, helps electronics and ion transfer; Polymeric layer can also play the effect of resilient coating; Effectively prevent the structural deterioration that electrode material embeds at lithium ioncauses because of change in volume when deviating from; Effectively improve the cyclical stability of electrode material; Cooperative effect between inorganic silver barium oxide and the polymer also helps to improve the chemical property of β-AgVO3.Therefore, silver-vanadium oxide/polymer three co-axial nano lines can keep improving the removal lithium embedded ability of material under the long stable effect state, and therefore, this nano wire shows the specific capacity and the cyclical stability that significantly improve during as anode active material of lithium ion battery; In addition, preparation β-AgVO<sub >3</sub>The simple hydro thermal method that nano wire adopted, in not containing any surfactant and aqueous organic, through changing pattern and the size that reactant concentration, reaction temperature and time can control material, and the material purity that makes is high, good dispersion; Also have, prepare the method for three co-axial nano lines with respect to other, chemical in-situ polymerization is medium with water, stirs through the short time at normal temperatures and pressures and can realize the synthetic of three co-axial nano lines, meets the requirement of Green Chemistry, is beneficial to the marketization and promotes.
Description of drawings
Fig. 1 is silver-vanadium oxide/polyaniline three co-axial nano line and β-AgVO of embodiment 1
3The XRD figure of nano wire; Wherein Fig. 1 (a) is the XRD figure of silver-vanadium oxide/polyaniline three co-axial nano lines, and Fig. 1 (b) is β-AgVO
3The XRD figure of nano wire;
Fig. 2 is silver-vanadium oxide/polyaniline three co-axial nano line and β-AgVO of embodiment 1
3The FTIR figure of nano wire; Wherein Fig. 2 (a) is the FTIR figure of silver-vanadium oxide/polyaniline three co-axial nano lines, and Fig. 2 (b) is β-AgVO
3The FTIR figure of nano wire;
Fig. 3 is the FESEM figure of silver-vanadium oxide/polyaniline three co-axial nano lines of embodiment 1;
Fig. 4 is the TEM figure of silver-vanadium oxide/polyaniline three co-axial nano lines of embodiment 1;
Fig. 5 is the EDS figure in nuclear and intermediate layer of silver-vanadium oxide/polyaniline three co-axial nano lines of embodiment 1; Fig. 5 (a) is the EDS figure in the stratum nucleare zone of silver-vanadium oxide/polyaniline three co-axial nano lines, and Fig. 5 (b) is the EDS figure in the interlayer region of silver-vanadium oxide/polyaniline three co-axial nano lines;
Fig. 6 is the synthesis mechanism figure of silver-vanadium oxide/polyaniline three co-axial nano lines of embodiment 1;
Fig. 7 is silver-vanadium oxide/polyaniline three co-axial nano line and β-AgVO of embodiment 1
3The cycle performance of battery curve chart of nano wire, Fig. 7 (a) are the cycle performance of battery curves of silver-vanadium oxide/polyaniline three co-axial nano lines, and Fig. 7 (b) is β-AgVO
3The cycle performance of battery curve of nano wire.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
The preparation method of silver-vanadium oxide/polyaniline three co-axial nano lines, it comprises the steps:
1) take by weighing the ammonium metavanadate that contains 2 mmol vanadium ions and be dissolved in 40 mL deionized waters, the silver nitrate that amount of substance such as takes by weighing again is dissolved in 40 mL deionized waters, and two parts of solution are mixed under stirring condition, continues to stir 1 hour, obtains precursor solution, and is subsequent use;
2) precursor solution that step 1) is obtained is transferred to 150 mL agitated reactors, reacts 24 hours down at 180 ℃, takes out agitated reactor, naturally cools to room temperature, and centrifugal filtration obtains sediment;
3) with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, finally obtain β-AgVO
3Nano wire, subsequent use;
4) take by weighing β-AgVO that step 3) obtains
3Nano wire 0.1g; Be distributed in the 20 mL deionized waters through stirring, sonicated; Under stirring condition, slowly inject the 0.05g aniline monomer; Stirring at room 12 hours, the ammonium persulfate aqueous solution of amount of substances such as adding 20 mL and aniline monomer under stirring condition continued stirring at room 12 hours then;
5) with reaction gained precipitated product centrifugal filtration in the step 4), use deionized water and absolute ethyl alcohol to be washed till filtrating repeatedly, placed 80 ℃ of baking ovens then dry 12 hours, finally obtain silver-vanadium oxide/polyaniline three co-axial nano lines for colourless.
Product silver-vanadium oxide/polyaniline three its structures of co-axial nano line of embodiment 1 are confirmed by x-ray diffractometer and Fourier transformation infrared spectrometer.X-ray diffracting spectrum (XRD) shows that silver-vanadium oxide/polyaniline three co-axial nano lines are consistent with original silver-vanadium oxide nano wire peak position, are β-AgVO
3Pure phase, the diffraction maximum of product all match with JCPDS card 29-1154, and be as shown in Figure 1; FFIR (FTIR) has shown the formation of polyaniline, and is as shown in Figure 2; Field emission scanning electron microscope (FESEM) test shows, about 10 ~ 30 microns of the length of silver-vanadium oxide/polyaniline three co-axial nano lines, diameter is the 60-100 nanometer, and is as shown in Figure 3; Transmission electron microscope (TEM) test can clear view to three coaxial configurations, about 8 nanometers of outermost layer thickness, about 8 nanometers of intermediate layer thickness, as shown in Figure 4; The nuclear of energy dispersion X ray spectrum (EDS) test shows silver-vanadium oxide/polyaniline three co-axial nano lines and intermediate layer be by Ag, V, and the O element is formed, and intermediate layer Ag content is less, as shown in Figure 5.This is because the Ag in intermediate layer
xVO
(2.5+0.5x)(0<x<1) be by β-AgVO
3Nanowire surface is separated out Ag
+And form, Ag
+With aniline monomer in solid-liquid interface generation redox reaction and produce silver-colored simple substance, also found the existence of silver-colored particle in the transmission electron microscope picture, confirmed the generation of this reaction; After adding oxidant, the polyaniline layer forms, and is coated on the silver-colored particle surface of silver-vanadium oxide nano wire and generation, forms three co-axial nano lines.
Silver-vanadium oxide/polymer three co-axial nano lines of the present invention's preparation are as anode active material of lithium ion battery, and all the other steps of the preparation method of lithium ion battery are identical with common preparation method.The preparation method of positive plate is following, adopts silver-vanadium oxide/polymer three co-axial nano lines as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, polytetrafluoroethylene is 70:25:5; After their abundant in proportion mixing, add a small amount of isopropyl alcohol, grind evenly, on twin rollers, press the thick electrode slice of about 0.5mm; The positive plate that presses places behind 80 ℃ the oven drying 24h subsequent use.Be dissolved in vinyl carbonate (EC) and the dimethyl carbonate (DMC) as electrolyte with the LiPF6 of 1M, the lithium sheet is a negative pole, and celgard2325 is a barrier film, and CR2025 type stainless steel is that battery case is assembled into the buckle type lithium-ion battery.
With silver-vanadium oxide/polyaniline three co-axial nano lines is example, and the constant current charge-discharge test result of under the 30mA/g current density, carrying out shows that its first discharge specific capacity can reach and be 211mAh/g, is 131 mAh/g after 20 circulations, and 20 times capability retention reaches 62%; β-AgVO
3Nano wire first with 20 times the circulation after specific discharge capacity be respectively 199 and 76 mAh/g, conservation rate is merely 41.7%, and is as shown in Figure 7.Above-mentioned performance shows that silver-vanadium oxide/polyaniline three co-axial nano lines have specific capacity and the cyclical stability that significantly improves, and is a kind of potential anode material for lithium-ion batteries.
Embodiment 2:
The preparation method of silver-vanadium oxide/polyaniline three co-axial nano lines, it comprises the steps:
1) take by weighing the ammonium metavanadate that contains 2 mmol vanadium ions and be dissolved in 40 mL deionized waters, the silver acetate that amount of substance such as takes by weighing again is dissolved in 40 mL deionized waters, and two parts of solution are mixed under stirring condition, continues to stir 1 hour, obtains precursor solution, and is subsequent use;
2) precursor solution that step 1) is obtained is transferred to 150 mL agitated reactors, reacts 36 hours down at 160 ℃, takes out agitated reactor, naturally cools to room temperature, and centrifugal filtration obtains sediment;
3) with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, finally obtain β-AgVO
3Nano wire, subsequent use;
4) take by weighing β-AgVO that step 3) obtains
3Nano wire 0.1g; Be distributed in the 20 mL deionized waters through stirring, sonicated; Under stirring condition, slowly inject the 0.05g aniline monomer; Stirring at room 10 hours, the potassium dichromate aqueous solution of amount of substances such as adding 20 mL and aniline monomer under stirring condition continued stirring at room 10 hours then;
5) with reaction gained precipitated product centrifugal filtration in the step 4), use deionized water and absolute ethyl alcohol to be washed till filtrating repeatedly, placed 80 ℃ of baking ovens then dry 12 hours, finally obtain silver-vanadium oxide/polyaniline three co-axial nano lines for colourless.
Embodiment 3:
The preparation method of silver-vanadium oxide/polyaniline three co-axial nano lines, it comprises the steps:
1) takes by weighing the vanadic oxide colloidal sol that contains 3 mmol vanadium ions and be dissolved in 40 mL deionized waters; The silver carbonate that amount of substance such as takes by weighing again is dissolved in 40 mL deionized waters, and two parts of solution are mixed under stirring condition, continues to stir 1 hour; Obtain precursor solution, subsequent use;
2) precursor solution that step 1) is obtained is transferred to 150 mL agitated reactors, reacts 12 hours down at 200 ℃, takes out agitated reactor, naturally cools to room temperature, and centrifugal filtration obtains sediment;
3) with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, finally obtain β-AgVO
3Nano wire, subsequent use;
4) take by weighing β-AgVO that step 3) obtains
3Nano wire 0.1g; Be distributed in the 20 mL deionized waters through stirring, sonicated; Under stirring condition, slowly inject the 0.05g aniline monomer; Stirring at room 14 hours, the ferric chloride aqueous solutions of amount of substances such as adding 20 mL and aniline monomer under stirring condition continued stirring at room 14 hours then;
5) with reaction gained precipitated product centrifugal filtration in the step 4), use deionized water and absolute ethyl alcohol to be washed till filtrating repeatedly, placed 80 ℃ of baking ovens then dry 12 hours, finally obtain silver-vanadium oxide/polyaniline three co-axial nano lines for colourless.
Embodiment 4:
The preparation method of silver-vanadium oxide/polypyrrole three co-axial nano lines, it comprises the steps:
1) takes by weighing the vanadic oxide colloidal sol that contains 3 mmol vanadium ions and be dissolved in 40 mL deionized waters; The silver nitrate that amount of substance such as takes by weighing again is dissolved in 40 mL deionized waters, and two parts of solution are mixed under stirring condition, continues to stir 1 hour; Obtain precursor solution, subsequent use;
2) precursor solution that step 1) is obtained is transferred to 150 mL agitated reactors, reacts 24 hours down at 180 ℃, takes out agitated reactor, naturally cools to room temperature, and centrifugal filtration obtains sediment;
3) with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, finally obtain β-AgVO
3Nano wire, subsequent use;
4) take by weighing β-AgVO that step 3) obtains
3Nano wire 0.1g; Be distributed in the 20 mL deionized waters through stirring, sonicated; Under stirring condition, slowly inject the 0.05g pyrrole monomer; Stirring at room 12 hours, the ammonium persulfate aqueous solution of amount of substances such as adding 20 mL and pyrrole monomer under stirring condition continued stirring at room 12 hours then;
5) with reaction gained precipitated product centrifugal filtration in the step 4), use deionized water and absolute ethyl alcohol to be washed till filtrating repeatedly, placed 80 ℃ of baking ovens then dry 12 hours, finally obtain silver-vanadium oxide/polypyrrole three co-axial nano lines for colourless.
Embodiment 5:
The preparation method of silver-vanadium oxide/polythiophene three co-axial nano lines, it comprises the steps:
1) take by weighing the ammonium metavanadate that contains 2.5 mmol vanadium ions and be dissolved in 40 mL deionized waters, the silver carbonate that amount of substance such as takes by weighing again is dissolved in 40 mL deionized waters, and two parts of solution are mixed under stirring condition, continues to stir 1 hour, obtains precursor solution, and is subsequent use;
2) precursor solution that step 1) is obtained is transferred to 150 mL agitated reactors, reacts 24 hours down at 180 ℃, takes out agitated reactor, naturally cools to room temperature, and centrifugal filtration obtains sediment;
3) with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, finally obtain β-AgVO
3Nano wire, subsequent use;
4) take by weighing β-AgVO that step 3) obtains
3Nano wire 0.1g; Be distributed in the 20 mL deionized waters through stirring, sonicated; Under stirring condition, slowly inject the 0.05g thiophene monomer; Stirring at room 10 hours, the ammonium persulfate aqueous solution of amount of substances such as adding 20 mL and thiophene monomer under stirring condition continued stirring at room 14 hours then;
5) with reaction gained precipitated product centrifugal filtration in the step 4), use deionized water and absolute ethyl alcohol to be washed till filtrating repeatedly, placed 80 ℃ of baking ovens then dry 12 hours, finally obtain silver-vanadium oxide/polythiophene three co-axial nano lines for colourless.
Claims (9)
1. silver-vanadium oxide/polymer three co-axial nano lines is characterized in that it has tangible three coaxial configurations, and length is 10 ~ 30 microns, and diameter is the 60-100 nanometer, and its center is β-AgVO
3Nano wire, intermediate layer are β-AgVO
3Nanowire surface loses the part silver ion and the silver-vanadium oxide layer that produces, and outermost layer is a polymeric layer, and outermost layer thickness is 6 ~ 10 nanometers, and intermediate layer thickness is 6 ~ 10 nanometers.
2. silver-vanadium oxide/polymer three co-axial nano lines as claimed in claim 1 is characterized in that described polymer is polyaniline, polypyrrole or polythiophene.
3. the preparation method of the described silver-vanadium oxide/polymer three co-axial nano lines of claim 1 is characterized in that including following steps:
1) the vanadium source aqueous solution is mixed under stirring condition with the silver-colored source aqueous solution, obtain precursor solution;
2) step 1) gained precursor solution is transferred to agitated reactor, reacts, naturally cool to room temperature, centrifugal filtration obtains sediment;
3) with deionized water cyclic washing step 2) sediment that obtains, and oven dry obtains β-AgVO
3Nano wire;
4) with β-AgVO
3Nano wire is scattered in the deionized water, adds polymer monomer, wherein, and β-AgVO
3The mass ratio of nano wire and polymer monomer is 2:1, and stirring at room 10-14 hour, the aqueous oxidizing agent solution of amount of substances such as adding and polymer monomer continued stirring at room 10 ~ 14 hours, the centrifugal precipitated product that obtains then;
5) with the precipitated product of deionized water and absolute ethyl alcohol cyclic washing step 4) gained, oven dry obtains silver-vanadium oxide/polymer three co-axial nano lines.
4. the preparation method of silver-vanadium oxide/polymer three co-axial nano lines as claimed in claim 3 is characterized in that described vanadium source is ammonium metavanadate or vanadic oxide colloidal sol.
5. the preparation method of silver-vanadium oxide/polymer three co-axial nano lines as claimed in claim 3 is characterized in that described silver-colored source is silver nitrate, silver acetate or silver carbonate.
6. the preparation method of silver-vanadium oxide/polymer three co-axial nano lines as claimed in claim 3 is characterized in that described polymer monomer is aniline monomer, pyrrole monomer or thiophene monomer.
7. the preparation method of silver-vanadium oxide/polymer three co-axial nano lines as claimed in claim 3 is characterized in that step 2) described reaction temperature is 160 ℃ ~ 200 ℃, the reaction time is 12 ~ 36 hours.
8. silver-vanadium oxide/polymer three co-axial nano line preparation methods as claimed in claim 3 is characterized in that described oxidant is ammonium persulfate, potassium bichromate or ferric trichloride.
9. the described silver-vanadium oxide/polymer three co-axial nano lines of claim 1 are in the application as anode active material of lithium ion battery.
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| CN102765756A (en) * | 2012-07-24 | 2012-11-07 | 武汉理工大学 | Radial beta-AgVO3 nanowire cluster and preparation method of radial beta-AgVO3 nanowire cluster |
| CN103094541A (en) * | 2013-01-16 | 2013-05-08 | 武汉理工大学 | MnO2-loaded V2O5/polymer coaxial structure nanowires as well as preparation method and application thereof |
| CN103208619A (en) * | 2013-03-13 | 2013-07-17 | 武汉理工大学 | Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof |
| WO2013158823A3 (en) * | 2012-04-19 | 2014-06-19 | Avox Systems, Inc. | Chemical oxygen generator |
| CN104828773A (en) * | 2015-03-28 | 2015-08-12 | 安徽师范大学 | Nanowire in polypyrrole/silver@ silver sulfide core shell structure, use thereof and preparation method therefor |
| CN108193500A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Catalyst that composite nano fiber and composite nano fiber support and its preparation and application |
| CN110665491A (en) * | 2019-10-15 | 2020-01-10 | 黑龙江大学 | Preparation method of vanadium dioxide nanorod |
| TWI762526B (en) * | 2016-11-08 | 2022-05-01 | 德商愛思強歐洲公司 | Mask holder with controlled adjustment |
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|---|---|---|---|---|
| US9662517B2 (en) | 2012-04-19 | 2017-05-30 | Avox Systems, Inc. | Chemical oxygen generator |
| WO2013158823A3 (en) * | 2012-04-19 | 2014-06-19 | Avox Systems, Inc. | Chemical oxygen generator |
| CN104302364A (en) * | 2012-04-19 | 2015-01-21 | 阿沃克斯系统公司 | Chemical oxygen generator |
| CN104302364B (en) * | 2012-04-19 | 2017-05-24 | 阿沃克斯系统公司 | Chemical oxygen generator |
| CN102765756A (en) * | 2012-07-24 | 2012-11-07 | 武汉理工大学 | Radial beta-AgVO3 nanowire cluster and preparation method of radial beta-AgVO3 nanowire cluster |
| CN103094541A (en) * | 2013-01-16 | 2013-05-08 | 武汉理工大学 | MnO2-loaded V2O5/polymer coaxial structure nanowires as well as preparation method and application thereof |
| CN103208619A (en) * | 2013-03-13 | 2013-07-17 | 武汉理工大学 | Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof |
| CN103208619B (en) * | 2013-03-13 | 2015-02-04 | 武汉理工大学 | Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof |
| CN104828773A (en) * | 2015-03-28 | 2015-08-12 | 安徽师范大学 | Nanowire in polypyrrole/silver@ silver sulfide core shell structure, use thereof and preparation method therefor |
| TWI762526B (en) * | 2016-11-08 | 2022-05-01 | 德商愛思強歐洲公司 | Mask holder with controlled adjustment |
| CN108193500A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Catalyst that composite nano fiber and composite nano fiber support and its preparation and application |
| CN108193500B (en) * | 2016-12-08 | 2020-04-24 | 中国科学院大连化学物理研究所 | Composite nanofiber, composite nanofiber supported catalyst, preparation method and application thereof |
| CN110665491A (en) * | 2019-10-15 | 2020-01-10 | 黑龙江大学 | Preparation method of vanadium dioxide nanorod |
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Application publication date: 20120411 |