CN105514375A - Carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite and preparation method thereof - Google Patents

Carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite and preparation method thereof Download PDF

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CN105514375A
CN105514375A CN201510919993.7A CN201510919993A CN105514375A CN 105514375 A CN105514375 A CN 105514375A CN 201510919993 A CN201510919993 A CN 201510919993A CN 105514375 A CN105514375 A CN 105514375A
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manganese dioxide
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CN105514375B (en
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木士春
张�杰
何婷
张伟
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 relates to a carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite and a preparation method thereof. Na0.55 Mn2O4.1.5H2O has a spherical structure formed by nanorods and is evenly wrapped by an amorphous carbon layer. The preparation method comprises the steps of (1) treating manganese dioxide nanorods by acid to modify the surfaces of the manganese dioxide nanorods, then adding tetraethyl orthosilicate (TEOS) into alcoholic solution of the manganese dioxide nanorods, and hydrolyzing to obtain silica-coated manganese dioxide core-shell structure composite material; (2) enabling the sample obtained in the step (1) to be coated with carbon to obtain carbonized composite material; (3) slowly adding the carbonized composite material powder sample into excess hot sodium hydroxide solution, and stirring for reaction. The carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite has high specific capacity as well as excellent rate performance and cycle performance, thus having wide application prospect in the technical fields of lithium ion battery electrode materials and other electrochemical techniques.

Description

The coated Na of a kind of carbon 0.55mn 2o 41.5H 2o nano composite material and preparation method thereof
Technical field
The invention belongs to manganese base oxysalt field of material preparation, be specifically related to the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material and preparation method thereof.
Background technology
Nowadays, the lithium rechargeable battery as new forms of energy representative has been widely used on the portable electric appts such as mobile communication, notebook computer, miniature camera.In today that electric automobile comes into one's own day by day, lithium ion battery is one of its of paramount importance energy supply material; Meanwhile, also show good application prospect and potential economic benefit power in fields such as satellite, space flight and aviation and Space Militaries, these application make lithium rechargeable battery become one of focus of current scientific and technical research.But be limited to the development of electrode material, cycle life is short, the development of fast charging and discharging ability and shortcoming the hinders lithium ion battery such as cost is higher, lithium ion battery still also has very large room for promotion in energy density and power density.
Current commercialization graphite cathode theoretical specific capacity (~ 372mAh/g) is low, life-span is short, become the bottleneck improving lithium ion battery energy density further, the needs of electrokinetic cell development can not be met, therefore development of new there is high-energy-density, the negative material of power density seems very urgent.In recent years, Mn based material greatly excites the interest of researchers, wherein manganese base oxysalt material is due to its special tunnel or layer structure, be considered to the very potential anode material of lithium battery of one, and apply to some extent in sodium-ion battery, but the application in negative pole is reported very few so far.
In recent years, about the preparation of this type of material still has a lot of relevant report.As document JournalofSolidStateChemistry, 1971,3,1-l1 report a kind of synthesis Na xmn0 2the method of compound, and delivered its Study of Phase Diagram in oxygen, show that this material exists the thing phase of three kinds of layer structures.Document JournalofSolidStateChemistry, has carried out comparatively detailed research to iodine reducing process in 2001,156,331-338, and the method adopts NaMn0 4 .h 20 and NaI be raw material, take the mixing of a certain amount of reactant in proportion, under agitation drip rare HCl adjust ph, stir after 24h, products therefrom is filtered, washing and dry, after at 300 ~ 900 DEG C, calcine 24h obtain Na xmn0 2.
In addition, above-mentioned manganese base oxysalt material directly applies to lithium ion battery negative material, also has some relevant scholars to carry out correlative study.As document J.Chem.Mater, 2005,17, prepare K in 4700 2mn 8o 16this material is also applied to lithium cell negative pole, and under current density 60mA/g, record its first circle charge specific capacity is 505mAh/g.The people such as Irvine report M 2snO 4the cycle performance of this material under low current density (J.PowerSources2001,223,97-98), by Mn 2snO 4with Mg 2snO 4, Co 2snO 4this bi-material contrasts, and finds Mn 2snO 4cycle performance is optimum, Zn in addition 2snO 4the reversible specific capacity of this new material reaches 500mAh/g (SolidStateIonics, 2000,135,163), but cycle performance is not good.
But the manganese system oxysalt material mentioned in most of document or patent is tunnel or the layer structure of birnessite, synthetic method cost is higher in addition, production efficiency is low, the material conductivity of synthesis is poor, cycle performance is unsatisfactory, thus affect the application and development of above-mentioned material in lithium ion battery, therefore, the present invention is intended to manganese base oxysalt material seeking a kind of novelty and preparation method thereof.
Summary of the invention
The object of the invention is to the deficiency for existing manganese base oxysalt material and defect, provide a kind of carbon of novelty coated Na 0.55mn 2o 4 .1.5H 2o nano composite material and preparation method thereof.
For achieving the above object, the present invention adopts following technical scheme:
There is provided carbon coated Na 0.55mn 2o 4 .1.5H 2o nano composite material, Na 0.55mn 2o 4 .1.5H 2o is the spherical structure be made up of nanometer rods, and is wrapped in uniformly in amorphous carbon layer.
There is provided a kind of carbon coated Na 0.55mn 2o 4 .1.5H 2the preparation method of O nano composite material, comprises the steps:
(1) manganese dioxide nano-rod after acid treatment surface modification is scattered in alcohol or alcohol-water mixture, add tetraethyl orthosilicate and tetraethyl orthosilicate hydrolytic accelerating agent, stir, make the coated with silica of surface band negative electrical charge on the manganese dioxide nano-rod of surface band positive charge, then also dry through deionized water centrifuge washing, obtain coated with silica manganese dioxide nano-rod;
(2) carbon carries out to the sample in step (1) coated: carbon source added in alcohol or alcohol-water mixture, then gained nucleocapsid coated with silica manganese dioxide nano-rod in step (1) is scattered in this solution, ultrasonic, after stirring a period of time, dry through deionized water centrifuge washing; Then gained compound is carried out high-temperature heat treatment under reproducibility or inert atmosphere, naturally cool, obtain the composite material after carbonization;
(3) the coated Na of carbon 0.55mn 2o 4 .1.5H 2the preparation of O nano composite material: the composite powder sample after the carbonization in step (2) is slowly added in the sodium hydroxide solution of excessive heat, stirring reaction, dry finally by deionized water centrifuge washing, obtain the coated Na of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Further, the mixing time in step (1) is 3-5h; The mixing time of step (2) is 12-24h; The mixing time of step (3) is 18-24h.
Further, the surface modification described in step (1) is: added by manganese dioxide nano-rod in the solution containing acid, ultrasonicly make it disperse, then dry through deionized water centrifuge washing.
Further, the acid described in step (1) is inorganic acid hydrochloric acid, sulfuric acid, perchloric acid, nitric acid, and any one of organic acid dodecyl sodium sulfonate, phytic acid, oxalic acid, citric acid, DBSA, camphorsulfonic acid and naphthalene sulfonic acids.
Further, the volume of the acid described in step (1) and the amount ratio of manganese dioxide nano-rod are 200 ~ 900 μ L:0.087 ~ 0.435g.
Further, the tetraethyl orthosilicate described in step (1) and the amount ratio of manganese dioxide nano-rod are 0.1868-0.7472g:0.087 ~ 0.435g.
Further, the hydrolytic accelerating agent described in step (1) is ammoniacal liquor, and the volume of ammoniacal liquor and the amount ratio of tetraethyl orthosilicate are 1ml:0.1868-0.7472g.
Further, the alcohol described in step (1) is any one or more than one the combination in ethanol, ethylene glycol, isopropyl alcohol, polyalcohol; The mixing of alcohol-water mixture to be any one or more than one combination in ethanol, ethylene glycol, isopropyl alcohol, polyalcohol and deionized water with volume ratio be 1:4 ~ 4:1.
Further, the carbon source described in step (2) is the one in citric acid, sucrose, shitosan.
Further, in step (2), the mass ratio of carbon source and nucleocapsid coated with silica manganese dioxide powder is: 0.1 ~ 0.5g:40 ~ 160mg.
Further, the reducing atmosphere described in step (2) is be the mist of nitrogen containing 5% hydrogen, remaining gas, and inert atmosphere is nitrogen, argon gas atmosphere.
Further, the high-temperature heat treatment described in step (2) refers in the tube furnace being full of above-mentioned gas wherein a kind of gas, with 5 ~ 15 DEG C/min heating rate, to be raised to after 450 ~ 750 DEG C of target temperatures insulation 5 ~ 10 hours.
Further, the heating bath temperature described in step (3) is 40 ~ 90 DEG C.
Further, baking temperature is 60 ~ 80 DEG C.
Compared with prior art, beneficial effect of the present invention is:
1) the present invention utilizes manganese dioxide and silicon dioxide at high temperature sintered characteristic dexterously, using silicon dioxide as template, reacts after first manganese dioxide and silicon dioxide being sintered with NaOH again, generates Na 0.55mn 2o 4 .1.5H 2o; Technique is simply controlled, with low cost, is easy to realize industrialization.
2) the coated Na of carbon provided by the invention 0.55mn 2o 4 .1.5H 2na in O nano composite material 0.55mn 2o 4 .1.5H 2o is the spherical structure of nanometer rods composition, and is wrapped in amorphous carbon layer uniformly.The present invention passes through to introduce carbon-coating, and by Na 0.55mn 2o 4 .1.5H 2o amorphous carbon layer effectively wraps up and isolates, and can promote material conductivity, overcome Na 0.55mn 2o 4 .1.5H 2the structural deterioration that O causes because embedding lithium causes volumetric expansion in charge and discharge process, efflorescence, reunion and the problem causing capacity to be decayed rapidly.Therefore, electrode material made by prepared composite material, and capacity is high, has excellent structural stability, cyclical stability and high rate performance, has huge application potential in electrode material of secondary lithium ion battery field.
Accompanying drawing illustrates:
Fig. 1 is the XRD photo of embodiment 1 products obtained therefrom;
Fig. 2 is the TEM photo of embodiment 1 products obtained therefrom;
Fig. 3 is the cycle performance photo of simulated battery prepared by embodiment 1 products obtained therefrom;
Fig. 4 is the high rate performance photo of simulated battery prepared by embodiment 1 products obtained therefrom.
Embodiment:
With concrete case study on implementation, technical scheme of the present invention is described further below, but the present invention obtains protection range is not limited thereto.
Embodiment 1
1) manganese dioxide (MnO prepared by 0.1g hydro thermal method is taken 2) nanometer rods, measure the hydrochloric acid (HCl) of 400 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 30 minutes, dry through deionized water centrifuge washing 3 times and at 80 DEG C; By above-mentioned powder dispersion in 100mL ethanolic solution (alcohol water is than being 4:1), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.4mL respectively, magnetic agitation is after 3 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
Manganese dioxide nano-rod hydro thermal method preparation and pre-treatment step as follows: take 1.35g manganese sulfate monohydrate (MnSO respectively 4h 2and 1.83g ammonium persulfate ((NH O) 4) 2s 2o 8) be dissolved in 70mL water, stir after 30 minutes and proceed in 100mL polytetrafluoroethylene reactor, hydro-thermal reaction 12 hours at 140 DEG C, after deionized water centrifuge washing 3 times, dry, stand-by.
2) citric acid (CA) of 0.2g is added in 10mL ethanolic solution (alcohol water is than being 4:1), then the powder-like taking preparation in the step (1) of 40mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 30 minutes, magnetic agitation 24 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C; Gained compound is placed in the tube furnace being full of nitrogen, with the heating rate of 5 DEG C/min, at 650 DEG C, is incubated 5 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.8g is added in 20mL deionized water, after heating water bath to 90 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 18 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C, obtain powder and be the coated Na of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.Fig. 1 is X-ray diffraction (XRD) figure of this material, contrasts with standard card, and products therefrom is Na 0.55mn 2o 4 .1.5H 2o, material with carbon element fails to demonstrate diffraction maximum due to partial amorphism, and does not have other impurity; Fig. 2 is transmission electron microscope (TEM) photo of this product, can be found to be Na 0.55mn 2o 4 .1.5H 2o is the spherical structure be made up of nanometer rods, and is wrapped in uniformly in amorphous carbon layer.
With the coated Na of a kind of carbon of embodiment 1 gained 0.55mn 2o 4 .1.5H 2o nano composite material makes electrode as follows:
The coated Na of carbon is taken respectively with the mass ratio of 7:2:1 0.55mn 2o 4 .1.5H 2o nano composite material: acetylene black: polytetrafluoroethylene (PVDF), after grinding, add the ultrasonic process of 1-METHYLPYRROLIDONE (NMP) 1 hour of designated volume, be evenly coated on Copper Foil and make electrode, employing metal lithium sheet is positive pole, and electrolyte is 1mol/LLiPF 6/ EC-DMC (volume ratio is 1:1), polypropylene micropore diaphragm is barrier film (Celgard2300), is assembled into half-cell.Fig. 3 is the long-time cyclic curve of battery under the current density of 1A/g in 0.01 ~ 3.0V voltage range that this composite material is assembled into, and can find that the specific capacity of this combination electrode material is obvious growth trend, have extraordinary cyclical stability; As can be seen from Figure 4, this combination electrode material has good high rate performance, even if the discharge and recharge of experience high current density, when returning to low current density, its charge specific capacity can recover substantially.
Embodiment 2
1) 0.1g manganese dioxide (MnO is taken 2) nanometer rods, measure the sulfuric acid of 200 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 20 minutes, dry through deionized water centrifuge washing 3 times and at 60 DEG C; By above-mentioned powder dispersion in 80mL ethylene glycol solution (alcohol water is than being 2:1), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.2mL respectively, magnetic agitation is after 5 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) sucrose of 0.1g is added in 20mL ethylene glycol solution (alcohol water is than being 2:1), then the powder-like taking preparation in the step (1) of 40mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 20 minutes, magnetic agitation 22 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C; Gained compound is placed in the tube furnace being full of argon gas, with the heating rate of 10 DEG C/min, at 450 DEG C, is incubated 8 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.14g is added in 30mL deionized water, after heating water bath to 40 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 20 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 3
1) 0.087g manganese dioxide (MnO is taken 2) nanometer rods, measure the oxalic acid of 500 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 10 minutes, dry through deionized water centrifuge washing 3 times and at 70 DEG C; By above-mentioned powder dispersion in 90mL aqueous isopropanol (alcohol water is than being 1:1), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.2mL respectively, magnetic agitation is after 4 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) shitosan of 0.3g is added in 30mL aqueous isopropanol (alcohol water is than being 1:1), then the powder-like taking preparation in the step (1) of 80mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 10 minutes, magnetic agitation 20 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C; Gained compound is placed in the tube furnace being full of hydrogen, with the heating rate of 5 DEG C/min, at 550 DEG C, is incubated 5 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.3g is added in 40mL deionized water, after heating water bath to 60 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 22 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 4
1) 0.087g manganese dioxide (MnO is taken 2) nanometer rods, measure the hydrochloric acid (HCl) of 200 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 20 minutes, dry through deionized water centrifuge washing 3 times and at 80 DEG C; By above-mentioned powder dispersion in 100mL glycerin solution (alcohol water is than being 1:2), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.4mL respectively, magnetic agitation is after 3 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) sucrose of 0.2g is added in 10mL glycerin solution (alcohol water is than being 1:2), then the powder-like taking preparation in the step (1) of 80mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 10 minutes, magnetic agitation 18 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C; Gained compound is placed in the tube furnace being full of nitrogen, with the heating rate of 15 DEG C/min, at 750 DEG C, is incubated 10 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.5g is added in 40mL deionized water, after heating water bath to 90 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 24 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 5
1) 0.2g manganese dioxide (MnO is taken 2) nanometer rods, measure the sulfuric acid of 500 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 30 minutes, dry through deionized water centrifuge washing 3 times and at 70 DEG C; By above-mentioned powder dispersion in 80mL ethanolic solution (alcohol water is than being 1:4), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.4mL respectively, magnetic agitation is after 4 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) shitosan of 0.1g is added in 30mL ethanolic solution (alcohol water is than being 1:4), then the powder-like taking preparation in the step (1) of 40mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 30 minutes, magnetic agitation 20 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C; Gained compound is placed in the tube furnace being full of argon gas, with the heating rate of 15 DEG C/min, at 550 DEG C, is incubated 5 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.3g is added in 20mL deionized water, after heating water bath to 40 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 18 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 6
1) 0.2g manganese dioxide (MnO is taken 2) nanometer rods, measure the hydrochloric acid (HCl) of 600 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 10 minutes, dry through deionized water centrifuge washing 3 times and at 60 DEG C; By above-mentioned powder dispersion in 100mL aqueous isopropanol (alcohol water is than being 4:1), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.6mL respectively, magnetic agitation is after 5 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) citric acid (CA) of 0.1g is added in 20mL aqueous isopropanol (alcohol water is than being 4:1), then the powder-like taking preparation in the step (1) of 120mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 10 minutes, magnetic agitation 22 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C; Gained compound is placed in the tube furnace being full of hydrogen, with the heating rate of 5 DEG C/min, at 450 DEG C, is incubated 10 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.14g is added in 30mL deionized water, after heating water bath to 90 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 20 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 7
1) 0.3g manganese dioxide (MnO is taken 2) nanometer rods, measure the oxalic acid of 200 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 30 minutes, dry through deionized water centrifuge washing 3 times and at 80 DEG C; By above-mentioned powder dispersion in 90mL ethylene glycol solution (alcohol water is than being 1:4), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.6mL respectively, magnetic agitation is after 3 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) sucrose of 0.3g is added in 30mL ethylene glycol solution (alcohol water is than being 1:4), then the powder-like taking preparation in the step (1) of 120mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 30 minutes, magnetic agitation 24 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C; Gained compound is placed in the tube furnace being full of nitrogen, with the heating rate of 10 DEG C/min, at 450 DEG C, is incubated 10 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.3g is added in 20mL deionized water, after heating water bath to 90 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 22 hours, dry through deionized water centrifuge washing 3 times and at 80 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 8
1) 0.3g manganese dioxide (MnO is taken 2) nanometer rods, measure the sulfuric acid of 900 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 10 minutes, dry through deionized water centrifuge washing 3 times and at 60 DEG C; By above-mentioned powder dispersion in 100mL glycerin solution (alcohol water is than being 1:2), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.2mL respectively, magnetic agitation is after 4 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) shitosan of 0.4g is added in 30mL glycerin solution (alcohol water is than being 1:2), then the powder-like taking preparation in the step (1) of 120mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 10 minutes, magnetic agitation 12 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C; Gained compound is placed in the tube furnace being full of argon gas, with the heating rate of 5 DEG C/min, at 750 DEG C, is incubated 8 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.5g is added in 40mL deionized water, after heating water bath to 40 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 20 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 9
1) 0.435g manganese dioxide (MnO is taken 2) nanometer rods, measure the oxalic acid of 900 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 20 minutes, dry through deionized water centrifuge washing 3 times and at 70 DEG C; By above-mentioned powder dispersion in 90mL ethanol and isopropyl alcohol mixture (ratio is 1:1), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.8mL respectively, magnetic agitation is after 5 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) citric acid (CA) of 0.5g is added in 10mL ethanol and isopropyl alcohol mixture (ratio is 1:1), then the powder-like taking preparation in the step (1) of 160mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 20 minutes, magnetic agitation 16 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C; Gained compound is placed in the tube furnace being full of hydrogen, with the heating rate of 10 DEG C/min, at 750 DEG C, is incubated 8 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.8g is added in 30mL deionized water, after heating water bath to 40 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 22 hours, dry through deionized water centrifuge washing 3 times and at 70 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.
Embodiment 10
1) 0.435g manganese dioxide (MnO is taken 2) nanometer rods, measure the hydrochloric acid (HCl) of 900 μ L, add in 50mL deionized water respectively, with the ultrasonic process of ultrasonic cleaner after 30 minutes, dry through deionized water centrifuge washing 3 times and at 60 DEG C; By above-mentioned powder dispersion in 80mL isopropyl alcohol and ethylene glycol mixed solution (alcohol water is than being 3:1), add the ammonia spirit of 1mL and the tetraethyl orthosilicate of 0.8mL respectively, magnetic agitation is after 3 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain nucleocapsid structure coated with silica manganese dioxide nano-rod;
2) shitosan of 0.5g is added in 30mL isopropyl alcohol and ethylene glycol mixed solution (alcohol water is than being 3:1), then the powder-like taking preparation in the step (1) of 160mg is scattered in this solution, with the ultrasonic process of ultrasonic cleaner after 30 minutes, magnetic agitation 18 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C; Gained compound is placed in the tube furnace being full of nitrogen, with the heating rate of 15 DEG C/min, at 550 DEG C, is incubated 5 hours, treats that tube furnace cools naturally, obtain black powder;
3) NaOH (NaOH) of 0.8g is added in 40mL deionized water, after heating water bath to 90 DEG C, the black powder of preparation in step (3) is slowly added, magnetic agitation is after 20 hours, dry through deionized water centrifuge washing 3 times and at 60 DEG C, obtain powder and be the coated Na of a kind of carbon 0.55mn 2o 4 .1.5H 2o nano composite material.

Claims (10)

1. the coated Na of carbon 0.55mn 2o 4.1.5H 2o nano composite material, is characterized in that: Na 0.55mn 2o 4.1.5H 2o is the spherical structure be made up of nanometer rods, and is wrapped in uniformly in amorphous carbon layer.
2. the coated Na of carbon according to claim 1 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: comprise the steps:
(1) manganese dioxide nano-rod after acid treatment surface modification is scattered in alcohol or alcohol-water mixture, add tetraethyl orthosilicate and tetraethyl orthosilicate hydrolytic accelerating agent, stir, make the coated with silica of surface band negative electrical charge on the manganese dioxide nano-rod of surface band positive charge, then also dry through deionized water centrifuge washing, obtain coated with silica manganese dioxide nano-rod;
(2) it is coated that the sample obtained step (1) carries out carbon: carbon source added in alcohol or alcohol-water mixture, then gained nucleocapsid coated with silica manganese dioxide nano-rod in step (1) is scattered in this solution, ultrasonic, after stirring a period of time, dry through deionized water centrifuge washing; Then gained compound is carried out high-temperature heat treatment under reproducibility or inert atmosphere, naturally cool, obtain the composite material after carbonization;
(3) the coated Na of carbon 0.55mn 2o 4.1.5H 2the preparation of O nano composite material: the composite powder sample after the carbonization in step (2) is slowly added in the sodium hydroxide solution of excessive heat, stirring reaction, dry finally by deionized water centrifuge washing, obtain the coated Na of carbon 0.55mn 2o 4.1.5H 2o nano composite material.
3. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the mixing time in step (1) is 3-5h; The mixing time of step (2) is 12-24h; The mixing time of step (3) is 18-24h.
4. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the surface modification described in step (1) is: added by manganese dioxide nano-rod in the solution containing acid, ultrasonicly make it disperse, then dry through deionized water centrifuge washing; Described acid is inorganic acid hydrochloric acid, sulfuric acid, perchloric acid, nitric acid, and any one of organic acid dodecyl sodium sulfonate, phytic acid, oxalic acid, citric acid, DBSA, camphorsulfonic acid and naphthalene sulfonic acids; The volume of the acid described in step (1) and the amount ratio of manganese dioxide nano-rod are 200 ~ 900 μ L:0.087 ~ 0.435g.
5. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the tetraethyl orthosilicate described in step (1) and the amount ratio of manganese dioxide nano-rod are 0.1868-0.7472g:0.087 ~ 0.435g;
In step (2), the amount ratio of carbon source and nucleocapsid coated with silica manganese dioxide powder is: 0.1 ~ 0.5g:40 ~ 160mg;
Hydrolytic accelerating agent described in step (1) is ammoniacal liquor, and the volume of ammoniacal liquor and the amount ratio of tetraethyl orthosilicate are 1ml:0.1868-0.7472g.
6. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the alcohol described in step (1) is any one or more than one the combination in ethanol, ethylene glycol, isopropyl alcohol, polyalcohol; The mixing of alcohol-water mixture to be any one or more than one combination in ethanol, ethylene glycol, isopropyl alcohol, polyalcohol and deionized water with volume ratio be 1:4 ~ 4:1.
7. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the carbon source described in step (2) is the one in citric acid, sucrose, shitosan.
8. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the reducing atmosphere described in step (2) is be the mist of nitrogen containing 5% hydrogen, remaining gas, and inert atmosphere is nitrogen, argon gas atmosphere.
9. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, it is characterized in that: the high-temperature heat treatment described in step (2) refers in the tube furnace being full of above-mentioned gas wherein a kind of gas, with 5 ~ 15 DEG C/min heating rate, after being raised to 450 ~ 750 DEG C of target temperatures, be incubated 5 ~ 10 hours.
10. the coated Na of carbon according to claim 2 0.55mn 2o 4.1.5H 2the preparation method of O nano composite material, is characterized in that: the heating bath temperature described in step (3) is 40 ~ 90 DEG C.
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