CN102259933A - Preparation method and application of rice-grain alpha-iron trioxide - Google Patents
Preparation method and application of rice-grain alpha-iron trioxide Download PDFInfo
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- CN102259933A CN102259933A CN2011101281032A CN201110128103A CN102259933A CN 102259933 A CN102259933 A CN 102259933A CN 2011101281032 A CN2011101281032 A CN 2011101281032A CN 201110128103 A CN201110128103 A CN 201110128103A CN 102259933 A CN102259933 A CN 102259933A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method and application of rice-grain alpha-iron trioxide. In the preparation process, a hydrothermal method is adopted and comprises the following steps of: uniformly dispersing iron salt and a surfactant in deionized water through mechanical stirring to obtain a mixed solution; performing hydrothermal reaction on the mixed solution in a reaction kettle; cleaning and freeze-drying a product to obtain a precursor; and roasting the precursor at the temperature of between 200 and 900DEG C for 1 to 40 hours, cooling to room temperature, and grinding to obtain a red rice-grain iron trioxide powder material. The invention has the advantages that: raw materials are wide in sources, the preparation method is simple, convenient to implement and pollution-free, and the obtained material has high purity, regular appearance and uniform particle size distribution; and when the material is used as a cathode material of a lithium ion battery, the first reversible charge discharge capacity is more than 1,000mAh/g and the lithium ion battery has long cycle life.
Description
Technical field
The present invention relates to a kind of preparation method and application of ferric oxide, particularly a kind of grain of rice shape α-ferric oxide (α-Fe
2O
3) preparation method and application, belong to novel material preparation method and applied technical field.
Background technology
In recent years, the developing rapidly of fields such as power tool, Moped Scooter and electromobile to lithium ion battery provides wide application space, but simultaneously also to the demands for higher performance of lithium ion battery.But the main graphite type material (theoretical capacity is 372mAh/g) that adopts is as negative pole in the lithium ion battery at present, and its lower theoretical capacity is the bottleneck of restriction lithium ion battery as following power cell, thereby is badly in need of seeking the high specific energy electrode materials of a new generation.α-Fe
2O
3Have the theoretical specific capacity up to 1007mAh/g during as lithium ion battery negative material, ferrous material has advantages such as the source is abundant, with low cost, nontoxic, environmental protection simultaneously, thereby is regarded as having the lithium ion battery electrode material of new generation of potentiality.But while α-Fe
2O
3Electroconductibility relatively poor, and take off the bigger volume change of existence in the working cycle, thereby cause α-Fe in the lithium ion embedding
2O
3Particle is efflorescence gradually, and then loses its excellent properties as lithium ion battery negative material.
It has been generally acknowledged that α-Fe
2O
3Particulate size, pattern all can have very big influence to its chemical property, and the α-Fe of preparation different-shape and size
2O
3, be the important method of improving its chemical property.People such as Liu have reported that on Electrochimica Acta 2009 1733-1736 the employing hydrothermal synthesis method has prepared nano bar-shape α-Fe
2O
3, first discharge specific capacity is 1332mAh/g, still has the specific discharge capacity of 753mAh/g after the circulation of 30 weeks.People such as Nuli have reported that on Journal of Power Source 2008 456-461 the oxide compound of spherical iron generally has high specific storage first, and the oxide compound of wire iron then has good cycle performance.Hydrothermal method is a kind of effective ways that prepare the controllable appearance nano material, has particle purity height, good dispersity, production cost is low and advantage such as easy scale operation.Thereby can predict, adopt Hydrothermal Preparation to go out the α-Fe of specific morphology
2O
3, can obtain to be uniformly dispersed, Stability Analysis of Structures and possess good comprehensive electrochemical.And the work of this aspect does not appear in the newspapers at present.
Summary of the invention
The purpose of this invention is to provide a kind of meter granulous α-Fe
2O
3Preparation method and application.The grain of rice shape α-Fe of this method preparation
2O
3Monodispersity is good, and distribution of sizes is concentrated; Prepared grain of rice shape α-Fe
2O
3When being applied to lithium ion battery electrode material, the first charge-discharge reversible capacity reaches 1011mAh/g, and has good cycle performance; It is simple to have preparation technology simultaneously, and material source is extensive, and advantages of environment protection can be carried out scale operation.
Realize that technical scheme of the present invention is: be raw material with the molysite, add suitable tensio-active agent, mix, adopt the hydro-thermal reaction legal system to get α-Fe then by mechanical stirring
2O
3Presoma obtains grain of rice shape α-Fe through after the roasting again
2O
3Material.Its concrete steps are:
(1) molysite and the tensio-active agent with a ratio is dissolved in the deionized water, and mechanical stirring is even;
(2) above-mentioned mixed solution is transferred to hydrothermal reaction kettle, 90～250 ℃ were reacted 1～40 hour down;
(3) will react resultant product and clean repeatedly for several times with deionized water and dehydrated alcohol respectively, obtain α-Fe after the vacuum lyophilization
2O
3Presoma;
(4) with α-Fe
2O
3Presoma naturally cools to room temperature at 200～900 ℃ of following roasting 1～24h, obtains red grain of rice shape α-Fe
2O
3
Said molysite in the step (1) can be a ferric sulfate, iron(ic) chloride, the composition of one or several in the salt hydrate of iron nitrate and ironic oxalate; Said tensio-active agent in the step (1) comprises different molecular weight polyethylene glycol, citric acid, Whitfield's ointment; The said purging method of step (3) comprises two kinds of methods of filtration method and centrifuging.
Characteristics of the present invention are by mechanical stirring, earlier with the raw material uniform mixing, utilize one step of hydro-thermal reaction to make α-Fe then
2O
3Presoma, last roasting obtains grain of rice shape α-Fe
2O
3Material.Its advantage is that raw material commonly is easy to get, low production cost, preparation technology is safe and simple, the product Modulatory character strong, each step does not produce hazardous and noxious substances in the preparation process; The material structure purity height of gained, pattern rule, centralized particle diameter.Grain of rice shape α-Fe
2O
3Material has good comprehensive electrochemical when being used as lithium ion battery negative material.
Description of drawings
Fig. 1 is by example 1 (a figure) and the prepared grain of rice shape α-Fe of example 2 (b figure)
2O
3X-ray diffraction (XRD) collection of illustrative plates.
Fig. 2 and Fig. 3 are by the prepared grain of rice shape α-Fe of example 1
2O
3The pattern that observation obtains under scanning electron microscope.
Fig. 4 is by the prepared grain of rice shape α-Fe of example 1
2O
3Stable circulation linearity curve in the 150mA/g current density.
Fig. 5 and Fig. 6 are by the prepared grain of rice shape α-Fe of example 2
2O
3The pattern that observation obtains under scanning electron microscope.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition and do not deviate from spirit and scope of the invention the present invention is carried out various changes and modifications all is conspicuous for a person skilled in the art that these equivalent form of values fall within the application equally and say attached claims institute restricted portion.
Embodiment one:
6.75g six Ferric Chloride Hydrateds and 3.75g polyoxyethylene glycol are added in the 200ml deionized water, and mechanical stirring obtained even mixed solution in 0.5 hour.At the bottom of this mixing solutions transferred to hydrothermal reaction kettle, 160 ℃ of reactions 12 hours down.Hydrothermal product is used deionized water and dehydrated alcohol eccentric cleaning respectively for several times, after the vacuum lyophilization, obtain α-Fe
2O
3Presoma.The material that obtains 300 ℃ of following roastings 2 hours, is cooled to room temperature, obtains grain of rice shape α-Fe
2O
3Material.
Fig. 1 a is grain of rice shape α-Fe that embodiment 1 obtains
2O
3X-ray diffraction (XRD) collection of illustrative plates.
Fig. 2 and Fig. 3 are the prepared grain of rice shape α-Fe of embodiment 1
2O
3The pattern that observation obtains under scanning electron microscope.
The research electrode is pressed grain of rice shape α-Fe of 40%
2O
3The mass percent of active material, 20% carbon black, 20% graphite and 20% polyvinylidene difluoride (PVDF) tackiness agent is formed; Electrolytic solution is 1mol/L LiPF
6-EC (NSC 11801)+DEC (diethyl carbonate)+DMC (methylcarbonate) (mass ratio is 1: 1: 1) is assembled into button cell.Discharge and recharge experiment and finish in 2032 type button cells, metallic lithium is as counter electrode; Barrier film is Celgard 2300.
Fig. 4 is the circulation stability curve that at room temperature with the current density of 150mA/g battery is carried out charge-discharge test in 3～0.005V scope.As seen from the figure, grain of rice shape α-Fe of making of the present invention
2O
3Material has the initial charge capacity near 1340mAh/g during as the lithium ion cell electrode active material, and after 24 weeks of circulating, also has near the 1047mAh/g charging capacity.
Embodiment two:
6.75g six Ferric Chloride Hydrateds and 6g polyoxyethylene glycol are added in the 400ml deionized water, and mechanical stirring obtained even mixed solution in 2 hours.At the bottom of above-mentioned mixing solutions transferred to hydrothermal reaction kettle, 180 ℃ of reactions 24 hours down.Hydrothermal product is used deionized water and dehydrated alcohol eccentric cleaning respectively for several times, after the vacuum lyophilization, obtain α-Fe
2O
3Presoma.The material that obtains 500 ℃ of following roastings 4 hours, is cooled to room temperature, obtains grain of rice shape α-Fe
2O
3Material.
Fig. 1 b is grain of rice shape α-Fe that embodiment 2 obtains
2O
3X-ray diffraction (XRD) collection of illustrative plates.
Fig. 5 and Fig. 6 are the prepared grain of rice shape α-Fe of embodiment 2
2O
3The pattern that observation obtains under scanning electron microscope.
Claims (6)
1. grain of rice shape α-ferric oxide material is characterized in that by the following steps preparation and gets:
(1) molysite and tensio-active agent are added to the water mechanical stirring forms even mixed solution;
(3) above-mentioned mixed solution is transferred to reactor and carries out hydro-thermal reaction;
(4) reaction finishes, and with resultant product cleaning, the precursor that obtains after the drying finally obtains grain of rice shape α-ferric oxide material after roasting.
2. a kind of grain of rice shape α according to claim 1-ferric oxide material is characterized in that: the ratio of water and the consumption of iron(ic) chloride 1: 1～2000: 1, the mass ratio of iron(ic) chloride (by Iron(III) chloride hexahydrate) and tensio-active agent 3: 1～1: 3.
3. a kind of grain of rice shape α according to claim 1-ferric oxide material, it is characterized in that: the temperature range of hydro-thermal reaction is between 90～250 ℃, and the reaction times is between 1～40 hour.
4. a kind of grain of rice shape α according to claim 1-ferric oxide material is characterized in that: described drying process is to adopt vacuum freeze-drying method, and the exsiccant temperature is between-60～10 ℃, and pressure is between 0～101kPa, and the time is at 6～72h.
5. a kind of grain of rice shape α according to claim 1-ferric oxide material, it is characterized in that: the precursor that obtains after the hydro-thermal reaction is heat-treated, heat treated temperature is between 200～900 ℃, and the time, temperature rise rate was between 0.1～20 ℃/min between 1～24h.
6. lithium ion battery negative material grain of rice shape α-ferric oxide material, it is characterized in that: described lithium ion battery negative material grain of rice shape α-ferric oxide material is by being prepared from according to the arbitrary described preparation method of claim 1-5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583574A (en) * | 2012-03-09 | 2012-07-18 | 四川大学 | Cathode material, alpha-Fe2O3, of high-capacity lithium ion battery and preparation method for material |
| CN103043726A (en) * | 2012-12-03 | 2013-04-17 | 云南云天化股份有限公司 | Preparation method of ellipsoidal particle size-controllable alpha-Fe2O3 nano particle |
| WO2015051627A1 (en) * | 2013-10-12 | 2015-04-16 | 安泰科技股份有限公司 | Rod-shaped nano iron oxide electrode material, and preparation method therefor and application thereof |
| CN104755429A (en) * | 2013-01-25 | 2015-07-01 | 株式会社Lg化学 | Trimanganese tetraoxide and method for producing same |
| CN106328930A (en) * | 2016-10-13 | 2017-01-11 | 河南理工大学 | Preparation method of high-capacity lithium ion battery negative pole material alpha-Fe2O3 |
| CN110389218A (en) * | 2018-04-16 | 2019-10-29 | 王艺达 | A kind of Fe2O3@SiO2The preparation of-APTS nanometer magnetic bead and characterizing method |
| CN111193026A (en) * | 2020-01-08 | 2020-05-22 | 河南城建学院 | Preparation method of fusiform iron oxide single crystal nano material |
| CN113184914A (en) * | 2021-04-20 | 2021-07-30 | 广东工业大学 | Porous capsule-shaped Fe2O3Nano material and preparation method and application thereof |
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| CN1817801A (en) * | 2006-01-19 | 2006-08-16 | 清华大学 | Synthesis of oliver alpha-ferric oxide nanometer particles |
| CN101037232A (en) * | 2007-04-26 | 2007-09-19 | 安徽工业大学 | Method for preparing radius-controllable ferric oxide hollow ball |
| CN101293674A (en) * | 2008-06-12 | 2008-10-29 | 浙江大学 | Method for preparing spindle shaped alpha-Fe2O3 powder |
| CN101314483A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | Method for synthesizing alpha-Fe2O3 nano-particle with controllable shape size |
| CN101698515A (en) * | 2009-10-30 | 2010-04-28 | 江苏大学 | Method for preparing alpha-phase ferricoxide nanospheres |
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Patent Citations (5)
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| CN1817801A (en) * | 2006-01-19 | 2006-08-16 | 清华大学 | Synthesis of oliver alpha-ferric oxide nanometer particles |
| CN101037232A (en) * | 2007-04-26 | 2007-09-19 | 安徽工业大学 | Method for preparing radius-controllable ferric oxide hollow ball |
| CN101293674A (en) * | 2008-06-12 | 2008-10-29 | 浙江大学 | Method for preparing spindle shaped alpha-Fe2O3 powder |
| CN101314483A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | Method for synthesizing alpha-Fe2O3 nano-particle with controllable shape size |
| CN101698515A (en) * | 2009-10-30 | 2010-04-28 | 江苏大学 | Method for preparing alpha-phase ferricoxide nanospheres |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583574A (en) * | 2012-03-09 | 2012-07-18 | 四川大学 | Cathode material, alpha-Fe2O3, of high-capacity lithium ion battery and preparation method for material |
| CN103043726A (en) * | 2012-12-03 | 2013-04-17 | 云南云天化股份有限公司 | Preparation method of ellipsoidal particle size-controllable alpha-Fe2O3 nano particle |
| CN103043726B (en) * | 2012-12-03 | 2015-01-14 | 云南云天化股份有限公司 | Preparation method of ellipsoidal particle size-controllable alpha-Fe2O3 nano particle |
| CN104755429A (en) * | 2013-01-25 | 2015-07-01 | 株式会社Lg化学 | Trimanganese tetraoxide and method for producing same |
| WO2015051627A1 (en) * | 2013-10-12 | 2015-04-16 | 安泰科技股份有限公司 | Rod-shaped nano iron oxide electrode material, and preparation method therefor and application thereof |
| CN106328930A (en) * | 2016-10-13 | 2017-01-11 | 河南理工大学 | Preparation method of high-capacity lithium ion battery negative pole material alpha-Fe2O3 |
| CN106328930B (en) * | 2016-10-13 | 2019-06-07 | 河南理工大学 | Cathode material for high capacity lithium ion battery α-Fe2O3Preparation method |
| CN110389218A (en) * | 2018-04-16 | 2019-10-29 | 王艺达 | A kind of Fe2O3@SiO2The preparation of-APTS nanometer magnetic bead and characterizing method |
| CN111193026A (en) * | 2020-01-08 | 2020-05-22 | 河南城建学院 | Preparation method of fusiform iron oxide single crystal nano material |
| CN113184914A (en) * | 2021-04-20 | 2021-07-30 | 广东工业大学 | Porous capsule-shaped Fe2O3Nano material and preparation method and application thereof |
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Application publication date: 20111130 |