CN104003448B - A kind of alpha-phase ferricoxide porous core-shell particles and controlledly synthesis preparation method thereof - Google Patents
A kind of alpha-phase ferricoxide porous core-shell particles and controlledly synthesis preparation method thereof Download PDFInfo
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- CN104003448B CN104003448B CN201410211704.3A CN201410211704A CN104003448B CN 104003448 B CN104003448 B CN 104003448B CN 201410211704 A CN201410211704 A CN 201410211704A CN 104003448 B CN104003448 B CN 104003448B
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Abstract
The invention discloses a kind of alpha-phase ferricoxide porous core-shell particles and controlledly synthesis preparation method thereof, with inorganic soluble iron salt for raw material, with deionized water and dehydrated alcohol for solvent, by hydro-thermal method at certain temperature and time, it is possible to obtain the alpha-phase ferricoxide microsphere with porous nucleocapsid structure. The average diameter of microsphere is 3 ��m, and core and shell are made up of the nanoparticle of mean diameter 200nm, and the average thickness 100nm of shell is uniformly covered with the aperture that many apertures are 40nm above core. The present invention need not add dispersant and surfactant and convenient without using template to make the later stage process, preparation technology is simple, the response time is short, yield is big, raw material environmental protection and cheap, it is beneficial to large-scale industrial production, can be applicable to lithium ion battery electrode material and gas sensitive.
Description
Technical field
The invention belongs to field of nano material preparation, be specifically related to a kind of controlledly synthesis technology of preparing having alpha-phase ferricoxide porous core-shell particles.
Background technology
As n-type semiconductor, alpha-phase ferricoxide and Eg=2.1eV has the features such as nontoxic, low cost, preparation technology are simple so that it is be widely used in coating, plastics, electronics, catalyst, magnetic recording material, lithium ion battery and gas sensing etc. Iron sesquioxide, as lithium ion battery electrode material, has high theoretical capacity, abundant content, good cycle life, cheap and advantages of environment protection, it is believed that be one of the ideal substitute of commercial graphite-like material with carbon element. Further, since the gas sensing property that its tool is higher, iron sesquioxide can be additionally used in the fuel gas in detection air and toxic gas.
Owing to the performance of alpha-phase ferricoxide is strongly dependent on its pattern and structure, wherein porous nucleocapsid structure has very big specific surface area, and this is possible not only to provide substantial amounts of chain carrier for electronics and gas molecule but also can shorten the transmission path of electronics and gas molecule. Improve lithium ion storage volume and air-sensitive performance.
The pattern of material and structure are closely bound up with preparation method again. Recently there are the various synthetic methods of the hud typed iron sesquioxide of bibliographical information, such as: sol-gal process, hydro-thermal method and template etc. Wherein, it is relatively broad that template is applied, and template is divided into again hard template method and soft template method. Conventional hard template has mesoporous silicon oxide and DIC ball etc., and soft template has surfactant and long-chain polymer etc. H.Qian et al. reports employing carbon ball at Nanotechnology2007,18,355602 355608 and prepares ��-Fe as hard template2O3Hollow nanospheres. And Zhong et al. report employing PVP as surfactant and by calcining post processing be prepared for hollow nucleocapsid Fe2O3Microsphere.The drawback of template is that productivity is relatively low, production cost is high, template removes and may destroy the structure of product, product separation difficulty in process. These methods often adopt multistep reaction simultaneously, it is impossible to according to actual needs the particle diameter of product is quickly regulated, be unfavorable for industrialized production. It is, thus, sought for a kind of method is simple, cost is low, environmental protection, and productivity is high, and the synthesizing porous nucleocapsid structure �� iron sesquioxide of the homogeneous controlled method of pattern.
Summary of the invention
It is an object of the invention to provide a kind of alpha-phase ferricoxide porous core-shell particles and controlledly synthesis preparation method thereof, with method for simplifying, reduce environmental pollution, reduction cost, and make the morphology controllable of product porous nucleocapsid structure alpha-phase ferricoxide.
In order to solve above technical problem, the concrete technical scheme that the present invention adopts is as follows:
A kind of alpha-phase ferricoxide porous core-shell particles, it is characterized in that: described microsphere is assembled by nanoparticle, the average diameter of microsphere is 3 ��m, described core and shell are all made up of the nanoparticle that mean diameter is 200nm, the average thickness 100nm of described shell, the above of described core is uniformly covered with the aperture that aperture is 40nm.
Controlledly synthesis preparation method according to described a kind of alpha-phase ferricoxide porous core-shell particles, including the preparation of reaction system, hydro-thermal reaction, to the separation of product, washing and dry run, it is characterised in that include following step:
Step one, with water-soluble trivalent ferric salt for source of iron, deionized water and dehydrated alcohol are solvent, form uniform solution A under room temperature; Described water-soluble trivalent ferric salt, deionized water, dehydrated alcohol three mass ratio be: 1��10:0��74:59��0;
Step 2, transfers to described solution A in stainless steel cauldron inner bag, then puts in baking oven by reactor, is under 100��200 DEG C of conditions in temperature, and hydro-thermal reaction, after 0.5��12 hour, naturally cools to room temperature, obtains product one;
Step 3, after product one enters branch's centrifugal treating, with deionized water and absolute ethanol washing, then at 70 DEG C after dry 24 hours, obtains alpha-phase ferricoxide porous core-shell particles.
Described water-soluble trivalent ferric salt is any one in ferric chloride, ferric nitrate or iron sulfate.
The present invention has beneficial effect. Invention has superior storage lithium performance and the high susceptibility feature to nitrogen dioxide gas. Preparation process of the present invention notice uses inorganic soluble iron salt to be raw material, with deionized water and dehydrated alcohol for solvent, alpha-phase ferricoxide porous core-shell particles is directly prepared by one step hydro thermal method, from without adding dispersant and surfactant, and it is convenient without using template to make the later stage process, preparation technology is simple, yield is big, raw material environmental protection and cheap, is beneficial to large-scale industrial production, and gained end product has excellent lithium electricity and air-sensitive performance. When the present invention is used as lithium ion battery electrode material, reversible charge/discharge capacity is up to about 728mAh/g, and has good cycle life; During as gas sensitive, nitrogen dioxide gas is shown significantly high sensitivity.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Fig. 2 is the scanning enlarged photograph of the single ball of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope photo of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1, and embedded figure is electronogram.
Fig. 4 is the XRD figure of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Fig. 5 is the first five cycle charging/discharging voltage-specific capacity graph of relation of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Fig. 6 is 60 loop cycle electrical property figure of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Fig. 7 is the air-sensitive selectivity bar diagram of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme is described in further detail.
Embodiment one
8.1g ferric chloride is dissolved in 50g deionized water, after adding 39.5g dehydrated alcohol mix homogeneously, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing closed is put in water heating kettle 200 DEG C react 12 hours, after being cooled to room temperature, being centrifuged, use deionized water and absolute ethanol washing, 70 DEG C dry 24 hours, obtain alpha-phase ferricoxide porous core-shell particles. Prepared alpha-phase ferricoxide is nucleocapsid structure, and dispersibility is better, as shown in Figure 1. After the amplification of single microsphere as shown in Figure 2, it can be clearly seen that the aperture on core surface. The transmission plot of single microsphere is as it is shown on figure 3, it is clear that the hollow structure of comparison of light and shade, electronogram shows that microsphere is monocrystalline. The XRD figure of obtained microsphere is composed as shown in Figure 4, it can be seen that for the good alpha-phase ferricoxide of crystallinity. Fig. 5 shows, the charge/discharge capacity of five all after date core-shell particles is 875mAhg-1And 899mAhg-1. Fig. 6 show 60 charge and discharge cycles week after date, the reversible capacity of core-shell particles is 728mAhg-1. Fig. 7 is the microsphere selectivity figure to gas, it can be seen that nitrogen dioxide is most sensitive.
Embodiment two
6g ferric chloride is dissolved in 50g deionized water, after adding 39.5g dehydrated alcohol mix homogeneously, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing closed is put in water heating kettle 180 DEG C react 0.5 hour, after being cooled to room temperature, being centrifuged, use deionized water and absolute ethanol washing, 70 DEG C dry 24 hours, obtain alpha-phase ferricoxide porous core-shell particles.
Embodiment three
After 2.7g ferric nitrate is dissolved in 158g dehydrated alcohol, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing closed is put in water heating kettle 150 DEG C react 8 hours, after being cooled to room temperature, it is centrifuged, uses deionized water and absolute ethanol washing, 70 DEG C dry 24 hours, obtain alpha-phase ferricoxide porous core-shell particles.
Embodiment four
By 13.5g ferric sulfate solution after 100g deionized water, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing closed is put in water heating kettle 120 DEG C react 10 hours, after being cooled to room temperature, it is centrifuged, uses deionized water and absolute ethanol washing, 70 DEG C dry 24 hours, obtain alpha-phase ferricoxide porous core-shell particles.
Claims (3)
1. an alpha-phase ferricoxide porous core-shell particles, it is characterized in that: described microsphere is assembled by nanoparticle, the average diameter of microsphere is 3 ��m, described core and shell are all made up of the nanoparticle that mean diameter is 200nm, the average thickness 100nm of described shell, the above of described core is uniformly covered with the aperture that aperture is 40nm.
2. the controlledly synthesis preparation method of a kind of alpha-phase ferricoxide porous core-shell particles according to claim 1, including the preparation of reaction system, hydro-thermal reaction, to the separation of product, washing and dry run, it is characterised in that include following step:
Step one, with water-soluble trivalent ferric salt for source of iron, deionized water and dehydrated alcohol are solvent, form uniform solution A under room temperature;Described water-soluble trivalent ferric salt, deionized water, dehydrated alcohol three mass ratio be: 1 ~ 6:50-74:59 ~ 39.5;
Step 2, transfers to described solution A in stainless steel cauldron inner bag, then puts in baking oven by reactor, is under 100 ~ 200 DEG C of conditions in temperature, and hydro-thermal reaction, after 0.5 ~ 12 hour, naturally cools to room temperature, obtains product one;
Step 3, after product one enters branch's centrifugal treating, with deionized water and absolute ethanol washing, then at 70 DEG C after dry 24 hours, obtains alpha-phase ferricoxide porous core-shell particles.
3. the controlledly synthesis preparation method of a kind of alpha-phase ferricoxide porous core-shell particles according to claim 2, it is characterised in that: described water-soluble trivalent ferric salt is any one in ferric chloride, ferric nitrate or iron sulfate.
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| CN106587166B (en) * | 2016-12-22 | 2018-02-02 | 中国工程物理研究院材料研究所 | A kind of iron oxide mesomorphic nano-particle and its synthetic method and methods for using them |
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| CN107946590B (en) * | 2017-11-09 | 2020-01-07 | 湖南友能高新技术有限公司 | Pomegranate-type structure ferric oxide, preparation method thereof and application of pomegranate-type structure ferric oxide as lithium ion negative electrode active material |
| CN108288712A (en) * | 2017-12-21 | 2018-07-17 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery negative material Fe2O3Preparation method |
| CN108428887B (en) * | 2018-04-13 | 2020-07-31 | 湖北工程学院 | Preparation method of battery electrode material ferric oxide, battery electrode material ferric oxide and lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514282A (en) * | 2009-03-31 | 2009-08-26 | 哈尔滨工程大学 | Porous Fe3O4/Fe/SiO2 core-shell nanorod absorbing high-frequency electromagnetic waves and a preparation method |
| CN101698515A (en) * | 2009-10-30 | 2010-04-28 | 江苏大学 | Method for preparing alpha-phase ferricoxide nanospheres |
| CN101767835A (en) * | 2010-03-23 | 2010-07-07 | 青岛科技大学 | Method for preparing alpha-Fe2O3 mesomorphic microballoon with high coercivity |
| CN103432969A (en) * | 2013-09-09 | 2013-12-11 | 青岛科技大学 | Preparation method of alpha-Fe2O3/FeOOH core-shell structure composite microspheres |
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| JP2827917B2 (en) * | 1994-08-23 | 1998-11-25 | 堺化学工業株式会社 | Method for producing α-ferric oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514282A (en) * | 2009-03-31 | 2009-08-26 | 哈尔滨工程大学 | Porous Fe3O4/Fe/SiO2 core-shell nanorod absorbing high-frequency electromagnetic waves and a preparation method |
| CN101698515A (en) * | 2009-10-30 | 2010-04-28 | 江苏大学 | Method for preparing alpha-phase ferricoxide nanospheres |
| CN101767835A (en) * | 2010-03-23 | 2010-07-07 | 青岛科技大学 | Method for preparing alpha-Fe2O3 mesomorphic microballoon with high coercivity |
| CN103432969A (en) * | 2013-09-09 | 2013-12-11 | 青岛科技大学 | Preparation method of alpha-Fe2O3/FeOOH core-shell structure composite microspheres |
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