CN101037220B - Sheet natrium/lithium-manganese material having high specific surface area and preparation method thereof - Google Patents
Sheet natrium/lithium-manganese material having high specific surface area and preparation method thereof Download PDFInfo
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- CN101037220B CN101037220B CN2007100376024A CN200710037602A CN101037220B CN 101037220 B CN101037220 B CN 101037220B CN 2007100376024 A CN2007100376024 A CN 2007100376024A CN 200710037602 A CN200710037602 A CN 200710037602A CN 101037220 B CN101037220 B CN 101037220B
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Abstract
The present invention relates to a flaky Na/Li-Mn material with a large specific surface area, and a preparation method thereof, which belongs to the mesoporous oxide material field. In the present invention, the flaky Na/Li-Mn material is obtained by hard template replication with a ratio of component of 1 MnO2: (0.001-0.5)Na/Li, wherein MnO2 has a rod shape, the aperture between two rods of the MnO2 rods is 2-5nm, the MnO2 rods having different orientation are interlaced with each other to form the flaky grains, the cumulate aperture between the flaky grains is 10-50 nm, and the flaky grains has an excellent dispersity and a high specific surface area of 80-200 m<2>/g. The flaky Na/Li-Mn material has an excellent application prospect in the fields of adsorbing material, medicine loading, catalyst material, and electrode material of lithium ion battery, sensor, electromagnetism material and environmental protection.
Description
Technical field
The present invention relates to a kind of sheet natrium/lithium-manganese material and preparation method thereof, belong to the mesopore oxide material field with high-specific surface area.
Background technology
The energy and environment are that the mankind stride into two severe problems that 21st century must face, and tap a new source of energy and renewable and clean energy resource is one of material five technical fields of tool in the world economy from now on; And along with economic growth, trade effluent and vehicle exhaust are more serious to the harm of environment, administer or the control disposal of pollutants, have become global protection environment key subjects anxious to be solved.
Since 1992 Kresge.C.T (Nature, 1992,359,710) report mesoporous SiO
2Material and 1998 subsequently adopt the triblock polymer P123 (polyoxyethylene polyoxy third rare multipolymer) of non-ionic type to synthesize the specific surface height under acidic conditions at reports such as Zhao, since the high six side's phase SBA-15 mesoporous materials of the degree of order.People synthesize it and at molecular sieve, catalysis is adsorbed, electrode material of lithium battery, and application facet such as magneticsubstance have been carried out increasingly extensive research.Usually the appearance structure of material has material impact to its practical application.The porous sheet material structure of this hard template assembling not only can increase substantially inside and outside transmission, absorption, the catalytic performance of guest molecule, and more helps improving its chemical property and magnetic performance.Therefore, such sheet meso-hole structure has more wide application prospect as catalyzer, transmitter, Anode of lithium cell material, semiconductor material and magneticsubstance.
At present, about the existing bibliographical information of mesoporous manganese oxide preparation methods.As Tian etc. (Science, 1997,276,926-930) adopting ionic surface active agent CTAB is directed agents, with Mn (OH)
2Colloidal sol be inorganic precursors, obtain the manganese base meso-hole structure material of mixed valence by self-assembly on the organic one inorganic interface and slow oxidation subsequently.This method is difficult to obtain the mesoporous manganese oxide of crystalline state after roasting, repeatability is bad.Owing to utilize the difficulty of organic formwork method synthetic manganese oxide mesoporous material, relevant report never again afterwards.It is template assembling lithium manganese oxide that Jia-Yan Luo (Chem.Mater.Web2006,10.14) adopts KIT-6, but specific surface is low, and capacitance is less.B.J.Aronson (J.Phys.Chem, B2000,104,449-459), J.Xu (Chem.Mater, 1999,11,2928-2936) wait the MCM-41 that adopts six side's phases, the MCM-48 of cube phase is inorganic template, and assembling manganese oxide mesoporous material is compared MCM and duplicated mesoporous material, SBA series SiO
2Template is better than these two kinds, particularly big, the good stability of the SBA-15 degree of order height of six side's phases, aperture, synthetic simple, template is cheap, thereby more paid close attention to.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, mild condition, good dispersity, specific surface area height, the sheet natrium/lithium-manganese mesopore oxide preparation method that the good silicon-based mesoporous hard template of chemical property is duplicated does not still have similar associated materials report at present both at home and abroad.
What the present invention relates to is that the sheet natrium/lithium-manganese mesopore oxide material that hard template is duplicated has following characteristics with the silicon-based mesoporous material: the natrium/lithium-manganese mesopore oxide material has mesoporous and sheet structure, and its component ratio (amount of substance ratio) is 1MnO
2: (0.001～0.5) Na or Li, MnO
2Bar-shapedly from the template duct, duplicate out, clean MnO through sodium hydroxide/lithium
2The aperture is 2～5nm between rod and the rod, the rod of different orientation is staggered in and forms platy shaped particle together, building long-pending aperture between platy shaped particle is 10～50nm, by the washing time and the concentration of control sodium hydroxide/lithium solution, can form the stratiform natrium/lithium-manganese mesopore oxide of different sheet structures.
The height ratio that hard template provided by the invention is duplicated is to prepare by technological process shown in Figure 1 than area sheet natrium/lithium-manganese mesopore oxide material preparation method, now selects its significant process and comments as follows:
(1) chooses mesopore silicon oxide, contain mn ion compound (50wt% manganous nitrate or manganous oxalate or nitrous acid manganese or potassium permanganate), 1.5 the alkaline solution of～3.5M (NaOH or LiOH or KOH) is a raw material, by weight (0.2～10) mesopore silicon oxide: (3.5～200) contain manganic compound: (0.4～20) alkaline solution: (5～250) H
2The O proportioning;
(2) in the mesopore silicon oxide template that has prepared, add the compound that contains mn ion;
(3) stir 3～24 hours, filter, under the room temperature dry 3～10 hours, 10～450 ℃ of air were dry 1～24 hour down again;
(4) add alkaline solution;
(5) stir 2～8 hours, after left standstill 1～10 hour;
With deionized water or washing with alcohol several, filter at last, drying is 4～12 hours under 25～550 ℃ of air.
What the present invention relates to is that sheet natrium/lithium-manganese mesopore oxide of duplicating of hard template and preparation method thereof has following characteristics with the silicon-based mesoporous material:
(1) this mesoporous sheet structure helps the inside and outside transmission of large and small guest molecule, improves exchange capacity, the catalytic performance of guest molecule, and strengthens electromagnetic performance.
(2) prepared dispersion of materials is good, and the specific surface area height can reach 80～200m
2/ g.
(3) this preparation method utilizes mesopore silicon oxide can a step realize that need not subsequent heat treatment, preparation technology is simple, mild condition for hard template under the normal temperature and pressure aqueous solution state.
(4) this mesoporous sheet structure material has outstanding chemical property, its specific capacitance reaches 100～400F/g, the preparation technology who is adopted is to improving electrode material of lithium battery structure such as lithium manganese oxide, lithium cobalt oxide, and lithium nickel oxides etc. are significant, thereby this material preparation method is at sorbing material, medicine loads, catalytic material, lithium ion battery electrode material, transmitter, electromagnetic material and environmental protection field have a good application prospect.
Description of drawings
Fig. 1 is the technical process of the natrium/lithium-manganese mesopore oxide material of high specific surface area platy provided by the invention.
Fig. 2 is that the stereoscan photograph (a)-(b) of high specific surface area platy natrium/lithium-manganese mesopore oxide material provided by the invention is the low power of embodiment one and high power electromicroscopic photograph, illustrates to have formed porous flake sodium manganese mesopore oxide; (c) be the electromicroscopic photograph of embodiment five, illustrate and use the lithium manganese mesopore oxide that can obtain sheet structure with sampling technology.
Fig. 3 is that the transmission electron microscope photo (a) of high specific surface area platy natrium/lithium-manganese mesopore oxide material provided by the invention under different condition is embodiment one photo, and bar-shaped the overlapping on together of duplicating as can be seen forms porous flake; (b) be the photo of embodiment two, (c) be the photo of embodiment five, illustrating has on the sheet much by duplicating the vermiform mesopore orbit that forms, this sheet meso-hole structure lithium manganese oxide specific surface area height, more help lithium ion transmission, the chemical property of strongthener with respect to common process synthetic lithium manganese oxide.
Fig. 4 the invention provides the high specific surface area platy natrium/lithium-manganese mesopore oxide material N of (embodiment one)
2Adsorption curve and corresponding pore size distribution curve (illustration) illustrate this flaky material mesopore orbit at 3nm, the duct 35.06nm that has intergranular accumulation to form simultaneously.
The XRD figure spectrum of Fig. 5 high specific surface area platy natrium/lithium-manganese provided by the invention mesopore oxide material under different synthesis conditions, (c ~ d) is embodiment one and two, illustrates that its collection of illustrative plates is indicated as typical quadrature phase structure; (b) be embodiment three, illustrate that sodium Mn oxide generation crystal formation changes, lamellar phase structure fades away, and crystal transition is the body-centered teteragonal phase; (a) be embodiment four, illustrate that the sodium Mn oxide is still non-crystallized complete, suitable drying temperature is described, the crystallization degree that improves the sodium Mn oxide is played an important role.
Fig. 6 the invention provides the cyclic voltammetry curve of high specific surface area platy natrium/lithium-manganese mesopore oxide material under 2my/s speed of (embodiment five).
Embodiment
Embodiment 1
The manganese source is manganous nitrate Mn (NO
3)
2Mesoporous hard template is silicon oxide SBA-15; After the SBA-15 template is injected in the manganese source, remove template silicon with sodium hydroxide.According to formula rate (weight ratio): 2SiO
2-SBA15: 38.38Mn (NO
3)
2: 4NaOH: 50H
2O; Behind the mixing material, magnetic agitation 4 hours, mn ion is assembled in the silicon oxide SBA-15 duct, drying at room temperature 10 hours, 100 ℃ of air dryings 3 hours, sample was become brown by white powder afterwards, and manganous nitrate progressively is decomposed into manganese oxide; Then above-mentioned powder is scattered in the sodium hydroxide solution, magnetic agitation 3 hours, the silicon oxide template is removed in ageing 7 hours, and unnecessary sodium ion is doped into manganese oxide, with deionized water wash for several times at last, filters at last 100 ℃ of air dryings 12 hours.Its typical scan electromicroscopic photograph low power and high power shown in Fig. 2 a ~ 2b, transmission electron microscope photo shown in Fig. 3 a, N
2Adsorption analysis and pore size distribution such as Fig. 4, the XRD diffracting spectrum is shown in Fig. 5 c.
Formula rate is constant, press embodiment 1 raw material mix and drying at room temperature after, the manganese silicon compound press embodiment one enforcement afterwards again 100 ℃ of air dryings 12 hours.Its transmission electron microscope photo of gained material is shown in Fig. 3 b, and the XRD diffracting spectrum is shown in Fig. 5 d.
Embodiment 3
Formula rate and other conditions are constant, through 250 ℃ of air dryings 12 hours, obtain final sample, and the XRD diffracting spectrum is shown in Fig. 5 b.
Embodiment 4
Formula rate is constant, and experiment condition is with embodiment 1, sample is last filter after, (25 ℃) sample of dry 10 hours at room temperature, the XRD diffracting spectrum is shown in Fig. 5 a.
Embodiment 5
Formula rate is constant, and inorganic sources changes LiOH into, typical scan electromicroscopic photograph such as Fig. 2 c, cyclic voltammetry curve such as Fig. 6, transmission electron microscope photo such as Fig. 3 c.
Claims (3)
1. the preparation method with sheet natrium/lithium-manganese material of high-specific surface area comprises the steps:
(1) choose mesopore silicon oxide, contain the mn ion compound, the alkaline solution of 1.5～3.5M is a raw material, by weight (0.2～10) mesopore silicon oxide: (3.5～200) contain manganic compound: (0.4～20) alkaline solution: (5～250) H
2The O proportioning;
(2) in the mesopore silicon oxide template that has prepared, add the compound that contains mn ion;
(3) stir 3～24 hours, filter, under the room temperature dry 3～10 hours, 10～450 ℃ of air were dry 1～24 hour down again;
(4) add alkaline solution;
(5) stir 2～8 hours, after left standstill 1～10 hour;
(6) at last with deionized water or washing with alcohol several, filter, drying is 4～12 hours under 25～550 ℃ of air.
2. a kind of preparation method with sheet natrium/lithium-manganese material of high-specific surface area as claimed in claim 1 is characterized in that the described mn ion compound that contains is 50wt% manganous nitrate or manganous oxalate or nitrous acid manganese or potassium permanganate.
3. a kind of preparation method with sheet natrium/lithium-manganese material of high-specific surface area as claimed in claim 1 is characterized in that described alkaline solution is NaOH or LiOH or KOH.
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|---|---|---|---|
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| CN101037220B true CN101037220B (en) | 2011-06-01 |
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| CN102496717B (en) * | 2011-12-20 | 2013-11-06 | 北京理工大学 | Preparation method of lithium manganous silicate cathode material with mesoporous structure |
| JP6785856B2 (en) * | 2016-06-30 | 2020-11-18 | タツタ電線株式会社 | Biological electrodes and methods for forming bioelectrodes |
| CN115072784A (en) * | 2022-05-10 | 2022-09-20 | 五邑大学 | Sodium-doped manganese oxide material, and preparation and application thereof |
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Non-Patent Citations (1)
| Title |
|---|
| Hangrong Chen et al..Templated synthesis of hierarchically porousmanganeseoxidewith a crystalline nanorod framework anditshighelectrochemical performance.Journal of Materials Chemistry17.2007,17855-860. * |
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