CN104003448A - [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof - Google Patents
[Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof Download PDFInfo
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- CN104003448A CN104003448A CN201410211704.3A CN201410211704A CN104003448A CN 104003448 A CN104003448 A CN 104003448A CN 201410211704 A CN201410211704 A CN 201410211704A CN 104003448 A CN104003448 A CN 104003448A
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Abstract
The invention discloses [alpha]-phase ferric oxide porous core-shell microspheres and a controllable synthetic preparation method thereof. The [Alpha]-phase ferric oxide microspheres having porous core-shell structures can be prepared through a hydrothermal method with an inorganic soluble ferric salt being a raw material, deionized water and anhydrous alcohol being solvents and at a certain temperature for a certain time. The microspheres are 3 [mu]m in the average diameter. Cores and shells are composed of nano particles, wherein the average diameter of the nano particles is 200 nm and the average thickness of the shells is 100nm. A plurality of pores with pore diameters being 40nm are uniformly distributed on the surface of each shell with of a plurality of pores with pore diameters being 40nm. The preparation method is free of any dispersing agent and surfactant, and subsequent processes are convenient since a template is not needed. The preparation method is simple in technology, short in reaction time, large in output, is environmental-friendly and cheap in raw materials, is beneficial to large scale industrial production and the porous core-shell microspheres can be used for a lithium ion battery electrode material and a gas-sensitive material.
Description
Technical field
The invention belongs to field of nano material preparation, be specifically related to a kind of controlledly synthesis technology of preparing of tool alpha-phase ferricoxide porous core-shell particles.
Background technology
As N-shaped semi-conductor, alpha-phase ferricoxide is E
gthe feature such as that=2.1 eV have is nontoxic, low cost, preparation technology are simple, makes it be widely used at aspects such as coating, plastics, electronics, catalyzer, magnetic recording material, lithium ion battery and gas sensings.Ferric oxide, as lithium ion battery electrode material, has high theoretical capacity, abundant content, good cycle life, cheap and advantages of environment protection, is considered to one of desirable surrogate of commercial graphite-like carbon material.In addition, due to the higher gas sensing property of its tool, ferric oxide also can be used for detecting airborne inflammable gas and toxic gas.
Because the performance of alpha-phase ferricoxide depends on its pattern and structure consumingly, wherein porous nucleocapsid structure has very large specific surface area, and this not only can provide a large amount of chain carriers for electronics and gas molecule but also can shorten the transmission route 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 ferric oxide of bibliographical information, such as: sol-gel method, hydrothermal method and template etc.Wherein, it is comparatively extensive 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 inorganic carbon ball etc., and soft template has tensio-active agent and long chain polymer etc.H. the people such as Qian is at Nanotechnology 2007,18, and 355602 – 355608 have reported that employing carbon ball prepares α-Fe as hard template
2o
3hollow nanospheres.And the people such as Zhong have reported that employing PVP has prepared hollow nucleocapsid Fe as tensio-active agent and by calcining aftertreatment
2o
3microballoon.The drawback of template is that productive rate is lower, production cost is high, template removes structure, the product separation difficulty that in process, may destroy product.These methods often adopt polystep reaction simultaneously, cannot carry out quick adjustment to the particle diameter of product according to actual needs, are unfavorable for suitability for industrialized production.Therefore, need to find a kind of method simple, cost is low, environmental protection, and productive rate is high, and the controlled synthesizing porous nucleocapsid structure α of the method ferric oxide of pattern homogeneous.
Summary of the invention
The object of the present invention is to provide a kind of alpha-phase ferricoxide porous core-shell particles and controlledly synthesis preparation method thereof, with simplified method, reduce environmental pollution, reduce costs, and make the pattern of product porous nucleocapsid structure alpha-phase ferricoxide controlled.
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 microballoon is assembled by nanoparticle, the mean diameter of microballoon is 3 μ m, the nanoparticle that described core and shell are all 200 nm by median size forms, mean thickness 100 nm of described shell, are evenly covered with the aperture that aperture is 40 nm above described core.
According to the controlledly synthesis preparation method of described a kind of alpha-phase ferricoxide porous core-shell particles, comprise the preparation of reaction system, hydro-thermal reaction, separation, washing and drying process to product, characterized by further comprising following step:
Step 1, taking water-soluble trivalent ferric salt as 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's mass ratio is: 1 ~ 10: 0 ~ 74: 59 ~ 0;
Step 2, transfers to described solution A in stainless steel cauldron inner bag, then reactor is put into baking oven, is that under 100 ~ 200 DEG C of conditions, hydro-thermal reaction, after 0.5 ~ 12 hour, naturally cools to room temperature in temperature, obtains product one;
Step 3, enters product one after branch's centrifugal treating, with deionized water and absolute ethanol washing, drier after 24 hours at 70 DEG C, obtain alpha-phase ferricoxide porous core-shell particles.
Described water-soluble trivalent ferric salt be in iron trichloride, iron nitrate or ferric sulfate any.
the present invention has beneficial effect.One invention has superior storage lithium performance and the high susceptibility feature to nitrogen dioxide gas.It is raw material that preparation process notice of the present invention is used inorganic soluble ferric iron salt, taking deionized water and dehydrated alcohol as solvent, directly prepare alpha-phase ferricoxide porous core-shell particles by one step hydro thermal method, thereby do not need to add dispersion agent and tensio-active agent, and without using template to make post-processed convenient, preparation technology is simple, output is large, raw material environmental protection and cheapness, is beneficial to large-scale industrial production, and gained final product has good lithium electricity and air-sensitive performance.When the present invention is used as lithium ion battery electrode material, reversible charge/discharge capacity can reach 728 mAh/g left and right, and has good cycle life; During as gas sensitive, nitrogen dioxide gas is shown to very high susceptibility.
Brief description of the drawings
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 electron-diffraction diagram.
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 storage 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 graph of prepared alpha-phase ferricoxide porous core-shell particles in the embodiment of the present invention 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in further detail.
Embodiment mono-
8.1 g iron trichlorides are dissolved in 50 g deionized waters, after adding again 39.5 g dehydrated alcohols to mix, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing having sealed is put into 200 DEG C of reactions of water heating kettle 12 hours, be cooled to after room temperature, centrifugal, with 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, better dispersed, as shown in Figure 1.After the amplification of single microballoon, as shown in Figure 2, can clearly see the aperture on core surface.The transmission plot of single microballoon as shown in Figure 3, can clearly be seen the hollow structure of comparison of light and shade, and electron-diffraction diagram shows that microballoon is monocrystalline.The XRD figure of prepared microballoon is composed as shown in Figure 4, can find out for the good alpha-phase ferricoxide of crystallinity.Fig. 5 shows, the charge/discharge capacity of five all after date core-shell particles is 875 mAh g
-1with 899 mAh g
-1.Fig. 6 shows all after dates of 60 charge and discharge cycles, and the reversible capacity of core-shell particles is 728 mAh g
-1.Fig. 7 is the selectivity diagram of microballoon to gas, can find out nitrogen peroxide the most responsive.
Embodiment bis-
6 g iron trichlorides are dissolved in 50 g deionized waters, after adding again 39.5 g dehydrated alcohols to mix, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing having sealed is put into 180 DEG C of reactions of water heating kettle 0.5 hour, be cooled to after room temperature, centrifugal, with deionized water and absolute ethanol washing, 70 DEG C dry 24 hours, obtain alpha-phase ferricoxide porous core-shell particles.
Embodiment tri-
2.7 g iron nitrates are dissolved in after 158 g dehydrated alcohols, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing having sealed is put into 150 DEG C of reactions of water heating kettle 8 hours, be cooled to after room temperature, centrifugal, with deionized water and absolute ethanol washing, 70 DEG C are dried 24 hours, obtain alpha-phase ferricoxide porous core-shell particles.
Embodiment tetra-
By 13.5 g ferric sulfate solution after 100 g deionized waters, above-mentioned solution is transferred in polytetrafluoroethylene bushing, the polytetrafluoroethylene bushing having sealed is put into 120 DEG C of reactions of water heating kettle 10 hours, be cooled to after room temperature, centrifugal, with deionized water and absolute ethanol washing, 70 DEG C are dried 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 microballoon is assembled by nanoparticle, the mean diameter of microballoon is 3 μ m, the nanoparticle that described core and shell are all 200 nm by median size forms, mean thickness 100 nm of described shell, are evenly covered with the aperture that aperture is 40 nm above described core.
2. the controlledly synthesis preparation method of a kind of alpha-phase ferricoxide porous core-shell particles according to claim 1, comprises the preparation of reaction system, hydro-thermal reaction, and separation, washing and drying process to product, characterized by further comprising following step:
Step 1, taking water-soluble trivalent ferric salt as 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's mass ratio is: 1 ~ 10: 0 ~ 74: 59 ~ 0;
Step 2, transfers to described solution A in stainless steel cauldron inner bag, then reactor is put into baking oven, is that under 100 ~ 200 DEG C of conditions, hydro-thermal reaction, after 0.5 ~ 12 hour, naturally cools to room temperature in temperature, obtains product one;
Step 3, enters product one after branch's centrifugal treating, with deionized water and absolute ethanol washing, drier after 24 hours at 70 DEG C, obtain 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, is characterized in that: described water-soluble trivalent ferric salt be in iron trichloride, iron nitrate or ferric sulfate any.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829425A (en) * | 2015-04-14 | 2015-08-12 | 浙江师范大学 | Mono-dispersed fusiform nano-sheets and preparation method thereof |
| CN104841433A (en) * | 2015-05-23 | 2015-08-19 | 吉林大学 | Hematite photocatalyst with twin-crystal structure and preparation method thereof |
| CN106093137A (en) * | 2016-06-20 | 2016-11-09 | 吉林大学 | A kind of based on α Fe2o3acetone gas sensor of multi-pore micron flower sensitive material and preparation method thereof |
| CN106587166A (en) * | 2016-12-22 | 2017-04-26 | 中国工程物理研究院材料研究所 | Ferric oxide mesocrystal nano particle as well as synthesis method and application method thereof |
| CN106830095A (en) * | 2017-02-17 | 2017-06-13 | 中国市政工程中南设计研究总院有限公司 | A kind of meso-porous hollow iron oxide microballoon and preparation method thereof |
| CN107098396A (en) * | 2017-05-16 | 2017-08-29 | 合肥学院 | A kind of method of utilization cattail suede controllable preparation ferric oxide powder |
| CN107456968A (en) * | 2017-08-01 | 2017-12-12 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of core shell structure iron oxide and products thereof and application |
| CN107946590A (en) * | 2017-11-09 | 2018-04-20 | 湖南友能高新技术有限公司 | A kind of pomegranate type structure di-iron trioxide and preparation method thereof and the application as lithium-ion negative pole 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 |
| CN108428887A (en) * | 2018-04-13 | 2018-08-21 | 湖北工程学院 | The preparation method and battery electrode material iron oxide and lithium ion battery of battery electrode material iron oxide |
| CN108499520A (en) * | 2017-05-16 | 2018-09-07 | 新疆德安环保科技股份有限公司 | Alpha-type ferric oxide-sodium bentonite sorbent preparation method for water process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0859398A (en) * | 1994-08-23 | 1996-03-05 | Sakai Chem Ind Co Ltd | Alpha-ferric oxide and its production |
| 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 |
-
2014
- 2014-05-20 CN CN201410211704.3A patent/CN104003448B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0859398A (en) * | 1994-08-23 | 1996-03-05 | Sakai Chem Ind Co Ltd | Alpha-ferric oxide and its production |
| 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 |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829425A (en) * | 2015-04-14 | 2015-08-12 | 浙江师范大学 | Mono-dispersed fusiform nano-sheets and preparation method thereof |
| CN104841433A (en) * | 2015-05-23 | 2015-08-19 | 吉林大学 | Hematite photocatalyst with twin-crystal structure and preparation method thereof |
| CN104841433B (en) * | 2015-05-23 | 2017-03-08 | 吉林大学 | A kind of bloodstone photochemical catalyst with twin structure and preparation method thereof |
| CN106093137A (en) * | 2016-06-20 | 2016-11-09 | 吉林大学 | A kind of based on α Fe2o3acetone gas sensor of multi-pore micron flower sensitive material and preparation method thereof |
| 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 |
| CN106587166A (en) * | 2016-12-22 | 2017-04-26 | 中国工程物理研究院材料研究所 | Ferric oxide mesocrystal nano particle as well as synthesis method and application method thereof |
| CN106830095A (en) * | 2017-02-17 | 2017-06-13 | 中国市政工程中南设计研究总院有限公司 | A kind of meso-porous hollow iron oxide microballoon and preparation method thereof |
| CN106830095B (en) * | 2017-02-17 | 2018-08-24 | 中国市政工程中南设计研究总院有限公司 | A kind of meso-porous hollow iron oxide microballoon and preparation method thereof |
| CN107098396A (en) * | 2017-05-16 | 2017-08-29 | 合肥学院 | A kind of method of utilization cattail suede controllable preparation ferric oxide powder |
| CN108499520A (en) * | 2017-05-16 | 2018-09-07 | 新疆德安环保科技股份有限公司 | Alpha-type ferric oxide-sodium bentonite sorbent preparation method for water process |
| CN108499520B (en) * | 2017-05-16 | 2021-05-14 | 新疆德安环保科技股份有限公司 | Preparation method of alpha-ferric oxide-sodium bentonite adsorbent for water treatment |
| CN107456968A (en) * | 2017-08-01 | 2017-12-12 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of core shell structure iron oxide and products thereof and application |
| CN107946590A (en) * | 2017-11-09 | 2018-04-20 | 湖南友能高新技术有限公司 | A kind of pomegranate type structure di-iron trioxide and preparation method thereof and the application as lithium-ion negative pole 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 |
| CN108428887A (en) * | 2018-04-13 | 2018-08-21 | 湖北工程学院 | The preparation method and battery electrode material iron oxide and lithium ion battery of battery electrode material iron oxide |
| 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 |
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