CN103342389A - Bi2WO6 with ordered macrostructure and preparation method thereof - Google Patents

Bi2WO6 with ordered macrostructure and preparation method thereof Download PDF

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Publication number
CN103342389A
CN103342389A CN2013102614412A CN201310261441A CN103342389A CN 103342389 A CN103342389 A CN 103342389A CN 2013102614412 A CN2013102614412 A CN 2013102614412A CN 201310261441 A CN201310261441 A CN 201310261441A CN 103342389 A CN103342389 A CN 103342389A
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China
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orderly
body material
macrostructure
macroscopical
macroscopical body
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吴强
赵立
韩若冰
姚伟峰
齐雪梅
武文燕
张静
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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Shanghai University of Electric Power
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Abstract

The invention discloses Bi2WO6 with an ordered macrostructure and a preparation method thereof. The Bi2WO6 with an ordered macrostructure is a functional material which is compounded of an ordered macro substrate material with microparticles; in other words, a layer of microparticles Bi2WO6 which is 2.0 microns thick is cured on the surface of the ordered macro substrate material; and the ordered macro substrate material is SiO2 fibers or a honeycomb ceramic body. The preparation method of the Bi2WO6 comprises the following steps of: firstly, preparing carbon nanofibers on the ordered macro substrate material by a chemical vapor deposition method, and then preparing the Bi2WO6 with the ordered macrostructure by an alcohol-thermal method with the carbon naofibers as a template, wherein the prepared Bi2WO6 has the characteristics of large surface, compact structure and porosity. The Bi2WO6 with the ordered macrostructure provided by the invention is good in orientation and controllable in morphology, and thereby can be specially applied. The preparation method of the Bi2WO6 has the characteristics of low production cost, high repeatability and the like.

Description

A kind of Bi with orderly macrostructure 2WO 6And preparation method thereof
Technical field
The present invention relates to a kind of Bi with orderly macrostructure 2WO 6And preparation method thereof, belong to field of inorganic materials.
Background technology
In recent years, energy dilemma and problem of environmental pollution more and more cause the great attention of country, research and develop high performancely to have visible-light-responsive photocatalyst and be expected to play a positive role in the Application Areas of environmental purification, thereby have very important meaning.At present, Bi 2WO 6Composite oxides have caused investigators' very big interest with its unique electronic structure, good visible absorption ability and higher organic matter degradation ability, become one of research focus of novel photocatalysis material.
Bi 2WO 6The preparation method of composite oxides has a lot, such as: high temperature solid-state method, liquid-phase precipitation method, ultrasonic synthesis method, hydrothermal method, spray-drying process and sol-gel method etc.The Bi that utilizes method for preparing to obtain 2WO 6Sample mainly exists with the nanometer powder state, and in use can there be a lot of unfavorable drawbacks in powder catalyst, and for example particle is easily reunited, contact efficiency is low with catalyzer is difficult to separate and is easy to run off etc.
Therefore, a kind of immobilization Bi of active development 2WO 6The technology of preparing of composite oxides, the sample of, favorable orientation a large amount of in the hope of obtaining, pattern and controllable structure then more and more receives numerous investigators' concern.
Carbon nano fiber is as a kind of novel raw material of wood-charcoal material, and because it has good central hole structure, higher specific surface area and controlled advantages such as microcosmic nanostructure in order become a kind of efficient and have one of mould material of potential application foreground.Adopt the carbon nano fiber mould plate technique can regulate and control to prepare Bi by the hot method of alcohol 2WO 6Composite oxides, this method can realize Bi simultaneously 2WO 6Composite oxides are solidificated on macroscopical body material of ordered structure, and by optimizing preparation condition, finally can obtain the high-quality ordered structure macroscopic view matrix new function material mutually compound with microscopic particles, such material will have than more excellent photocatalysis performance, can evade the various drawbacks of using the conventional powder catalyzer to bring, thereby have more favourable using value, have not yet to see the report of relevant this respect work.
Summary of the invention
One of the object of the invention provides a kind of Bi with orderly macrostructure 2WO 6
Two of purpose of the present invention provides above-mentioned a kind of Bi with orderly macrostructure 2WO 6The preparation method.
Technical scheme of the present invention
A kind of Bi with orderly macrostructure 2WO 6, be a kind of orderly macroscopical body material and the functional materials that microscopic particulate is composited mutually, namely be approximately the microscopic particulate Bi of 2.0 μ m at surface cure one layer thickness of orderly macroscopical body material 2WO 6, described microscopic particulate Bi 2WO 6Loading on orderly macroscopical body material is weight ratio 100%;
Described orderly macroscopical body material is SiO 2Fiber or honeycomb ceramic body etc.;
Described orderly macroscopical body material SiO 2Fiber is preferably bar-shaped.
Above-mentioned a kind of Bi with orderly macrostructure 2WO 6The preparation method, specifically comprise the steps:
(1), adopt chemical Vapor deposition process to prepare carbon nano fiber at orderly macroscopical body material
In the electroless plating reaction process, be carrier with orderly macroscopical body material, at first orderly macroscopical body material is immersed in ethanol the Ni (NO of 0.3 mol/L that is solvent 3) 2.6H 2O, Fe (NO 3) 3.9H 2O or Co (NO 3) 2.6H 210 min in the O solution carry out vacuum filtration, drying treatment then, put into the flat-temperature zone of crystal reaction tube reaction system then, prepare Fe through 300 ℃ of roastings 2O 3, NiO or Co 2O 3/ orderly macroscopical body material integer catalyzer, control Fe 2O 3, NiO or Co 2O 3It is 5% that the loading of metal oxide on orderly macroscopical body material counted by weight percentage;
Thereupon with the above-mentioned Fe that obtains 2O 3, NiO or Co 2O 3/ orderly macroscopical body material integer catalyzer feeds nitrogen protection and simultaneously reaction system in the crystal reaction tube is risen to 550-600 ℃ by 300 ℃, adopts CH then 4, C 2H 4Or CO gas is controlled CH as carbon source under the normal pressure 4, C 2H 4Or the CO gas flow feeds 15 min N for 200-400 mL/min carries out vapour deposition to carry out carbon nano fiber growth 2-3 h after growth is finished again 2Blow away the CH of surplus 4, C 2H 4Or CO gas, the final reaction system is cooled to room temperature, namely gets the carbon nano fiber that is solidificated on orderly macroscopical body material;
(2), be the get everything ready Bi of orderly macrostructure of the hot legal system of template utilization alcohol to be solidificated in carbon nano fiber on orderly macroscopical body material 2WO 6
To be immersed in total concentration of metal ions be that ethanol-nitric acid of 0.15-0.45 mol/L is in the precursor liquid of Bi+W metal-salt of solvent with the carbon nano fiber on orderly macroscopical body material of being solidificated in of step (1) gained, and change over to it in hydrothermal reaction kettle in the lump, the control temperature carries out taking out behind the hydro-thermal reaction 12-18h at 120-180 ℃, after being 99.7% washing with alcohol 3-5 time with deionized water and mass percent concentration successively, behind vacuum filtration in 120 ℃ of drying treatment 4-6h, at last in air in 650 ℃ of following roastings in order to remove the carbon nano fiber template, finally obtain being solidificated in the Bi on orderly macroscopical body material 2WO 6, the Bi that namely has orderly macrostructure 2WO 6
Ethanol-nitric acid that described total concentration of metal ions is 0.15-0.45 mol/L is that the precursor liquid of the Bi+W metal-salt of solvent prepares by the following method:
At first with Bi(NO 3) 36H 2The O stirring and dissolving adds corresponding WCl then being that 68% nitric acid and concentration are that 99.7% ethanol is that the mixed of 1:14-20 forms in nitric acid-alcohol solvent by concentration 6, continue to stir until dissolving, namely getting total concentration of metal ions is that 0.15-0.45 mol/L ethanol-nitric acid is the precursor liquid of the respective metal salt of solvent;
Above-mentioned used Bi(NO 3) 36H 2O and WCl 6Amount, calculate in molar ratio, i.e. the Bi metal: the W metal is 2:1.
Beneficial effect of the present invention
A kind of Bi with ordered structure of the present invention 2WO 6, be a kind of orderly macroscopical body material new function material mutually compound with microscopic particulate, namely at first can regulate and control the formation of carbon nano fiber template effectively by the condition of control chemical vapour deposition, be that template is with microscopic particulate Bi then with the carbon nano fiber 2WO 6Be solidificated on dissimilar macroscopical body materials, therefore can regulate and control the formation of carbon nano fiber template effectively by the condition of control chemical vapour deposition, and then regulate and control Bi effectively 2WO 6Formation, therefore a kind of Bi with ordered structure of the present invention 2WO 6Have favorable orientation, advantage such as pattern is controlled can be towards application-specific.
Bi with orderly macrostructure of the present invention 2WO 6The preparation method owing at first adopt chemical Vapor deposition process to prepare carbon nano fiber at orderly macroscopical body material, be the get everything ready Bi of orderly macrostructure of the hot legal system of template utilization alcohol then with the carbon nano fiber 2WO 6, it is simple therefore to have preparation technology, the characteristics of low production cost.
Bi with orderly macrostructure of the present invention 2WO 6, be a kind of macroscopical matrix functional materials mutually compound with microcosmic particle, because such matrix material has bigger surface-area and compact structure and porosity characteristic, so it has very strong absorption and catalytic performance, therefore can replace using traditional B i 2WO 6The various drawbacks that the nanometer powder catalyzer brings, for example pressure falls with heat passage problem and contact efficiency is low is difficult to separate etc. with catalyzer, thereby has potential application prospect.
Description of drawings
Fig. 1, orderly macroscopical body material SiO 2Rod-like fibre amplifies 5000 times scanning electron microscope sem figure;
Growth has orderly macroscopical body material SiO of carbon nano fiber after Fig. 2 a, the vapour deposition 2Rod-like fibre amplifies 5000 times scanning electron microscope sem figure;
After Fig. 2 b, the vapour deposition at orderly macroscopical body material SiO 2The carbon nano fiber of growing on the rod-like fibre amplifies 40000 times scanning electron microscope sem figure;
Fig. 3, be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6Amplify 5000 times scanning electron microscope sem figure;
Fig. 4, be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6The XRD figure of X-ray powder diffraction show;
Fig. 5, be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6The ultraviolet-visible light diffuse reflection spectrum.
Embodiment
Below by specific embodiment and by reference to the accompanying drawings to a kind of Bi with orderly macrostructure provided by the invention 2WO 6And preparation method thereof specify, but do not limit the present invention.
All ingredients used in the embodiments of the invention is analytical pure, and company limited provides for Aladdin reagent;
Used ultraviolet-visible pectrophotometer in the embodiments of the invention, model UV-2550, Tianjin, island-GC sales of consumables company;
Used X-ray powder diffraction instrument in the embodiments of the invention, model Bruke Advance D8, Brooker;
Used field emission scanning electron microscope in the embodiments of the invention, model SU-1500, Hitachi.
Embodiment 1
A kind of Bi with orderly macrostructure 2WO 6, be a kind of orderly macroscopical body material and the functional materials that microscopic particulate is composited mutually, namely be approximately the microscopic particulate Bi of 2.0 μ m at surface cure one layer thickness of orderly macroscopical body material 2WO 6, described microscopic particulate Bi 2WO 6Loading on orderly macroscopical body material is weight ratio 100%;
Described orderly macroscopical body material SiO 2Rod-like fibre.
Above-mentioned a kind of Bi with orderly macrostructure 2WO 6The preparation method, specifically comprise the steps:
(1) at orderly macroscopical body material SiO 2Synthesis of nano carbon fiber on the rod-like fibre
1., at first adopt the orderly macroscopical body material SiO of immersion process for preparing NiO/ 2The rod-like fibre integer catalyzer
With the orderly macroscopical body material SiO of 0.2 g 2Rod-like fibre is immersed in ethanol the Ni (NO of 0.3 mol/L that is solvent 3) 2.6H 210min in the O solution carries out vacuum filtration, 110 ℃ of drying treatment then, in order to remove orderly macroscopical body material SiO 2Superfluous Ni (the NO in rod-like fibre surface 3) 2.6H 2O solution, the flat-temperature zone of putting into the crystal reaction tube reaction system then obtains the orderly macroscopical body material SiO of NiO/ behind 300 ℃ of roasting 30min 2The rod-like fibre integer catalyzer;
2., adopt chemical Vapor deposition process to prepare carbon nano fiber
At the 1. orderly macroscopical body material SiO of NiO/ that obtains of roasting of step 2Feed N behind the rod-like fibre integer catalyzer thereupon 2Protection also rises to 550 ℃ of protection 1h with the temperature of crystal reaction tube reaction system by 300 ℃ simultaneously, and feeding flow under the condition of normal pressure then is the CH of 320 mL/min 4Gas carries out vapour deposition to carry out the growth 2h of carbon nano fiber, feeds 15 min N again after growth is finished 2Blow away the CH of surplus 4Gas, the final reaction system is cooled to room temperature, namely gets to be solidificated in orderly macroscopical body material SiO 2Carbon nano fiber on the rod-like fibre;
Above-mentioned used orderly macroscopical body material SiO 2The scanning electron microscope sem figure that the rod-like fibre amplification is 5000 times can draw its diameter and be about 9.7 μ m as shown in Figure 1 from Fig. 1;
Growth has orderly macroscopical body material SiO of carbon nano fiber after the above-mentioned vapour deposition 2Rod-like fibre amplifies 5000 times scanning electron microscope sem figure shown in Fig. 2 a, and carbon nano fiber evenly and in a large number loads on orderly macroscopical body material SiO as can be seen from Fig. 2 a 2On the rod-like fibre, have filamentary structure and mutually weave in form fine and close orderly carbon nano fiber layer, its thickness is approximately 2.4 μ m;
After the above-mentioned vapour deposition at orderly macroscopical body material SiO 2The carbon nano fiber of growing on the rod-like fibre amplifies 40000 times scanning electron microscope sem figure shown in Fig. 2 b, and the diameter Distribution that can draw carbon nano fiber from Fig. 2 b is about 60-80nm;
(2), to be solidificated in orderly macroscopical body material SiO 2Carbon nano fiber on the rod-like fibre is the get everything ready Bi of orderly macrostructure of the hot legal system of template utilization alcohol 2WO 6
Take by weighing 4.85 g Bi(NO 3) 36H 2O also is dissolved in the C that 25 mL contain 3.5 mL concentrated nitric acids with it 2H 5(adding an amount of concentrated nitric acid is in order to suppress Bi among the OH 3+Hydrolysis), take by weighing 1.98 g WCl simultaneously 6Powder is dissolved in 25 mL C with it 2H 5In the OH solution, under stirring under magnetic stirring apparatus two solution are mixed, ethanol-nitric acid that to obtain jade-green cotton-shaped total concentration of metal ions be 0.3mol/L is the precursor liquid of the corresponding Bi+W metal-salt of solvent;
Ethanol-the nitric acid of measuring the above-mentioned total concentration of metal ions of 40 mL and be 0.3mol/L is that the precursor liquid of the corresponding Bi+W metal-salt of solvent is transferred in the tetrafluoroethylene stainless steel autoclave of 50 mL, and is solidificated in orderly macroscopical matrix material material SiO with what step (1) obtained 2Carbon nano fiber on the rod-like fibre is immersed in wherein, sealing, be placed on then in 180 ℃ of loft drier and carry out being cooled to room temperature behind the hydro-thermal reaction 12h, open reactor, take out response sample, use deionized water and washing with alcohol 3 times respectively, behind vacuum filtration in 120 ℃ of following drying treatment 5h, at last in air in 650 ℃ of following roasting 5h in order to removing the carbon nano fiber template, thereby obtain being solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6, the Bi that namely has orderly macrostructure 2WO 6
The above-mentioned Bi with orderly macrostructure that obtains 2WO 6Namely be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6Amplify 5000 times scanning electron microscope sem figure as shown in Figure 3, after as can be seen from Figure 3 the carbon nano fiber template is removed, Bi 2WO 6Coating loads on orderly macroscopical body material SiO relatively uniformly 2On the rod-like fibre, and the Bi of formation compact structure and porous 2WO 6Layer, the about 2.0 μ m of its thickness, so gained be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6The Bi that namely has orderly macrostructure 2WO 6Be a kind of macroscopical body material SiO 2Rod-like fibre and microscopic particulate Bi 2WO 6Mutually compound material, wherein microscopic particulate Bi 2WO 6At orderly macroscopical body material SiO 2It is 100% that loading on the rod-like fibre is counted by weight percentage, and further it can also be seen that from Fig. 3, the above-mentioned Bi with orderly macrostructure that obtains 2WO 6Has bigger surface-area;
The above-mentioned Bi with orderly macrostructure that obtains 2WO 6Namely be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6X-ray powder diffraction figure (XRD) as shown in Figure 4, as can be seen from Figure 4, the Bi with orderly macrostructure of gained 2WO 6Has Bi clearly 2WO 6The crystal characteristic peak, this shows the Bi with orderly macrostructure of above-mentioned gained 2WO 6Relative purity higher.
The above-mentioned Bi with orderly macrostructure that obtains 2WO 6Namely be solidificated in orderly macroscopical body material SiO 2Bi on the rod-like fibre 2WO 6The ultraviolet-visible diffuse reflection spectrum as shown in Figure 5, the as can be seen from Figure 5 Bi with orderly macrostructure of gained 2WO 6Have certain photoresponse scope at visible region, and have visible absorption ability preferably, show that thus this has the Bi of orderly macrostructure 2WO 6Be expected in the visible light catalytic reaction, show more excellent catalytic performance.
Can show by above-described embodiment, be that template utilizes pure hot method with Bi with the carbon nano fiber that is solidificated on orderly macroscopical body material 2WO 6Be solidificated on dissimilar macroscopical body materials, finally obtain having the Bi with orderly macrostructure of bigger surface-area and compact structure and porosity characteristic 2WO 6
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (5)

1. Bi with orderly macrostructure 2WO 6, it is characterized in that described Bi with orderly macrostructure 2WO 6The functional materials that to be a kind of orderly macroscopical body material be composited mutually with microscopic particulate, namely surface cure one layer thickness at orderly macroscopical body material is the microscopic particulate Bi of 2.0 μ m 2WO 6
Described orderly macroscopical body material is SiO 2Fiber or honeycomb ceramic body.
2. a kind of Bi with orderly macrostructure as claimed in claim 1 2WO 6, it is characterized in that described microscopic particulate Bi 2WO 6It is 100% that loading on orderly macroscopical body material is counted by weight percentage;
Described orderly macroscopical body material is SiO 2Fiber.
3. a kind of Bi with orderly macrostructure as claimed in claim 2 2WO 6, it is characterized in that described orderly macroscopical body material SiO 2Fiber is bar-shaped.
4. as claim 1,2 or 3 described a kind of Bi with orderly macrostructure 2WO 6The preparation method, it is characterized in that specifically comprising the steps:
(1), adopt chemical Vapor deposition process to prepare carbon nano fiber at orderly macroscopical body material
In the electroless plating reaction process, be carrier with orderly macroscopical body material, at first orderly macroscopical body material is immersed in ethanol the Ni (NO of the 0.3mol/L that is solvent 3) 2.6H 2O, Fe (NO 3) 3.9H 2O or Co (NO 3) 2.6H 210 min in the O solution carry out vacuum filtration, drying treatment then, and the 300 ℃ of roastings in flat-temperature zone of putting into the crystal reaction tube reaction system then prepare Fe 2O 3, NiO or Co 2O 3/ orderly macroscopical body material integer catalyzer, control Fe 2O 3, NiO or Co 2O 3It is 5% that loading on orderly macroscopical body material is counted by weight percentage;
Thereupon with the above-mentioned Fe that obtains 2O 3, NiO or Co 2O 3/ orderly macroscopical body material integer catalyzer feeds nitrogen protection and simultaneously 300 ℃ of reaction systems in the crystal reaction tube is risen to 550-600 ℃, adopts CH then 4, C 2H 4Or CO gas is controlled CH as carbon source under the normal pressure 4, C 2H 4Or the flow of CO gas namely gets the carbon nano fiber that is solidificated on orderly macroscopical body material for 200-400 mL/min carries out vapour deposition to carry out the growth 2-3 h of carbon nano fiber;
(2), be the get everything ready Bi of orderly macrostructure of the hot legal system of template utilization alcohol to be solidificated in carbon nano fiber on orderly macroscopical body material 2WO 6
To be immersed in total concentration of metal ions be that ethanol-nitric acid of 0.15-0.45 mol/L is in the precursor liquid of Bi+W metal-salt of solvent with the carbon nano fiber template on orderly macroscopical body material of being solidificated in of step (1) gained, and change over to it in hydrothermal reaction kettle in the lump, the control temperature carries out taking out behind the hydro-thermal reaction 12-18h at 120-180 ℃, after being 99.7% washing with alcohol 3-5 time with deionized water and mass percent concentration successively, behind vacuum filtration in 120 ℃ of drying treatment 4-6h, at last in air in 650 ℃ of following roastings in order to remove the carbon nano fiber template, finally obtain being solidificated in the Bi on orderly macroscopical body material 2WO 6, the Bi that namely has orderly macrostructure 2WO 6
5. a kind of Bi with orderly macrostructure as claimed in claim 4 2WO 6The preparation method, it is characterized in that ethanol-nitric acid that described total concentration of metal ions is 0.15-0.45mol/L is that the precursor liquid of the Bi+W metal-salt of solvent prepares by the following method;
At first with Bi(NO 3) 36H 2The O stirring and dissolving adds corresponding WCl then being that 68% nitric acid and concentration are that 99.7% ethanol is that the mixed of 1:14-20 forms in nitric acid-alcohol solvent by concentration 6, continue to stir until dissolving, namely getting total concentration of metal ions is that 0.15-0.45 mol/L ethanol-nitric acid is the precursor liquid of the respective metal salt of solvent;
Above-mentioned used Bi(NO 3) 36H 2O and WCl 6Amount, calculate in molar ratio, i.e. the Bi metal: the W metal is 2:1.
CN2013102614412A 2013-06-27 2013-06-27 Bi2WO6 with ordered macrostructure and preparation method thereof Pending CN103342389A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105642275A (en) * 2016-03-08 2016-06-08 济南大学 CeO2/Bi2WO6/MgAl-LDH composite photo-catalyst and preparation method and application thereof
CN106207251A (en) * 2016-08-24 2016-12-07 河北工业大学 A kind of carbon method for coating of hydro-thermal method LiFePO4
CN110124749A (en) * 2019-04-18 2019-08-16 江门职业技术学院 One kind having photocatalysis performance complex fiber material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101623630A (en) * 2009-07-24 2010-01-13 中国科学院上海硅酸盐研究所 Bi*WO*/oxide fiber cloth with multistage heterogeneous structure, method and application
CN103145186A (en) * 2013-04-08 2013-06-12 上海电力学院 Nanoporous BiVO4 with ordered macrostructure, and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101623630A (en) * 2009-07-24 2010-01-13 中国科学院上海硅酸盐研究所 Bi*WO*/oxide fiber cloth with multistage heterogeneous structure, method and application
CN103145186A (en) * 2013-04-08 2013-06-12 上海电力学院 Nanoporous BiVO4 with ordered macrostructure, and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105642275A (en) * 2016-03-08 2016-06-08 济南大学 CeO2/Bi2WO6/MgAl-LDH composite photo-catalyst and preparation method and application thereof
CN105642275B (en) * 2016-03-08 2018-03-23 济南大学 A kind of CeO2/Bi2WO6/ MgAl LDH composite photo-catalysts and its preparation method and application
CN106207251A (en) * 2016-08-24 2016-12-07 河北工业大学 A kind of carbon method for coating of hydro-thermal method LiFePO4
CN106207251B (en) * 2016-08-24 2022-03-08 河北工业大学 Carbon coating method of hydrothermal lithium iron phosphate
CN110124749A (en) * 2019-04-18 2019-08-16 江门职业技术学院 One kind having photocatalysis performance complex fiber material and preparation method thereof

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Application publication date: 20131009