CN105470481A - Nitrogen-doped carbon-coated manganese monoxide composite material with one-dimensional porous core-shell structure and preparation method of nitrogen-doped carbon-coated manganese monoxide composite material - Google Patents

Nitrogen-doped carbon-coated manganese monoxide composite material with one-dimensional porous core-shell structure and preparation method of nitrogen-doped carbon-coated manganese monoxide composite material Download PDF

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CN105470481A
CN105470481A CN201510863458.4A CN201510863458A CN105470481A CN 105470481 A CN105470481 A CN 105470481A CN 201510863458 A CN201510863458 A CN 201510863458A CN 105470481 A CN105470481 A CN 105470481A
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composite material
nitrogen
manganese monoxide
doped carbon
coated
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木士春
张伟
何婷
胡林
张�杰
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 nitrogen-doped carbon-coated manganese monoxide composite material with a one-dimensional porous core-shell structure and a preparation method of the nitrogen-doped carbon-coated manganese monoxide composite material. The composite material is doped with nitrogen, is in a one-dimensional porous carbon-coated manganese monoxide core-shell structure; manganese monoxide is in a nano rodlike structure; and an outer layer of a manganese monoxide nanorod is coated with an amorphous carbon layer. The nitrogen-doped carbon-coated manganese monoxide composite material is obtained by an in-situ polymer coating method accompanied by burning. The preparation method of the composite material is simple and novel, and high in adjustability; and meanwhile, nitrogen-doped carbon can store lithium ions. Due to the ingenious design, the specific capacity of the composite material exceeds the theoretical specific capacity of the manganese monoxide; furthermore, according to the composite material, the problems of low capacity and fast attenuation caused by poor conductivity and high volumetric strain of a pure manganese monoxide material are solved; and the composite material has excellent electrochemical properties, cycle lifetime and structural stability.

Description

The coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon and preparation method
Technical field
The invention belongs to new forms of energy nanometer energy storage material, be specifically related to the coated manganese monoxide composite material of a kind of one dimension porous nucleocapsid structure nitrogen-doped carbon, preparation method and application thereof.
Background technology
Widely using of portable electric appts, electric automobile and electrical network energy-storage system equal energy source storage facilities, has greatly promoted the high speed development of the lithium ion battery as new forms of energy energy storage outstanding representative.As conventional commercial lithium ion battery negative material, graphite is due to theoretical capacity low (372mAh/g), and the reasons such as cycle life is lower, significantly limit further developing of lithium ion battery.Therefore, developing the lithium ion battery negative material that a kind of specific capacity is high, cycle performance is excellent, using field to be significant for widening lithium ion battery.
Compared with the transition metal oxide negative material that other are common, charging potential platform (~ 1.2V, vs.Li/Li that manganese monoxide tool is relatively low +), operating voltage and the energy density of full battery can be improved, its abundance, cheap, environmental protection simultaneously, especially, manganese monoxide has higher theoretical specific capacity (756mAh/g), fail safe is good, be considered to a kind of negative material of great potential, and be widely studied.But in practical application, mainly face two problems: on the one hand, manganese monoxide electronic conductivity is low, cause that its high rate performance is poor, reversible capacity is low; On the other hand, manganese monoxide is in electrochemistry cyclic process, and bulk strain is large, thus causes material to reunite and efflorescence, capacity rapid decay.These defects, seriously hinder manganese monoxide applying in lithium ion battery negative material.
In recent years, domestic and international researcher can effectively improve its chemical property mainly through the manganese monoxide electrode material of preparation porous or carbon compound.As people (GuoS such as Shandong University Guo, LuG, QiuS, etal.Carbon-coatedMnOmicroparticulateporousnanocomposite sservingasanodematerialswithenhancedelectrochemicalperfo rmances [J] .NanoEnergy, 2014, 9:41-49.) obtain carbon coated manganese monoxide multi-pore micron ball composite material by hydro thermal method, pure sample excellent performance compared by gained composite material, under 100mA/g, first circle capacity is 590.6mAh/g, after circulation 100 circle, capacity still has 525.4mAh/g, when current density is 800mA/g, capacity can reach 238.2mAh/g, people (the LiuH such as Zhongshan University Liu, LiZ, LiangY, etal.FacilesynthesisofMnOmulti-corenitrogen-dopedcarbons hellnanoparticlesforhighperformancelithium-ionbatteryano des [J] .Carbon, 2015, 84:419-425.) prepare the manganese monoxide nanosphere composite material of the coated coenocytism of a kind of carbon, chemical property be improved significantly, under 100mA/g, first circle capacity is 799mAh/g, 608mAh/g is dropped to after circulation 5 circle, through 60 circles, capacity still has 578mAh/g, under 1000mA/g, capacity can reach 254mAh/g, although obtained certain progress about manganese monoxide electrode material study on the modification at present, but, comprise that most of document of above-mentioned document and patent system are all comparatively complicated for the method for manganese monoxide composite material, cost is large at present, simultaneously, under high current density (being greater than 500mA/g), cycle life is still difficult to more than 500 circles or higher, and specific capacity is still lower.
Summary of the invention
Technical problem to be solved by this invention is to provide the coated manganese monoxide composite material of a kind of one dimension porous nucleocapsid structure nitrogen-doped carbon, this composite structure is novel, in conjunction with porous, one dimension, N doping, characteristic that specific area is large, greatly inhibit in charge and discharge process because material volume expands the problem that the efflorescence brought, the capacity that causes of reuniting decay rapidly, simultaneously, nitrogen-doped carbon also can store lithium ion, improve the reversible specific capacity of this composite material, there is good structural stability, excellent cycle performance; Further, this preparation method is comparatively simple novel, and cost is low, and prepared material has good structural stability, excellent cycle performance, is suitable for suitability for industrialized production, has huge application potential in energy storage material field.
For achieving the above object, the present invention adopts following technical scheme:
The coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon, doped with nitrogen in this composite material, for the coated manganese monoxide nucleocapsid structure of one dimension porous carbon, manganese monoxide is nano bar-shape structure, and the external sheath of manganese monoxide nanometer rods has amorphous carbon layer.The preparation method of the coated manganese monoxide composite material of a kind of one dimension porous nucleocapsid structure nitrogen-doped carbon is provided, comprises the steps:
1) add in oxidizing agent solution by manganese dioxide nano-rod, ultrasonic process makes it disperse, and under 0 ~ 10 DEG C of condition, magnetic agitation, makes manganese dioxide nano-rod be uniformly dispersed;
2) aniline monomer is added in acid solution, stir under 0 ~ 10 DEG C of condition, make aniline be dispersed in acid solution, obtain aniline suspension;
3) by step 1) solution adds step 2 rapidly) suspension, 0 ~ 10 DEG C leaves standstill reprocessing in 0.5 ~ 36 hour, obtains the compound of the coated manganese dioxide of polyaniline polymer;
4) by step 3) gained compound carries out high-temperature heat treatment under reproducibility or inert atmosphere, and naturally cool, obtain the coated manganese monoxide nano composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
By such scheme, described step 1) in sonication treatment time be 5 ~ 30 minutes, mixing time is 10 ~ 60 minutes.
By such scheme, described step 3) in reprocessing for water centrifuge washing 3 times, dry at 60 ~ 120 DEG C.
By such scheme, the ratio of the amount of substance of described manganese dioxide nano-rod and the volume of aniline is: 0.3 ~ 50mmol:30 ~ 250 μ L, and the amount of substance proportion of aniline and oxidant is 1:1 ~ 1:4.
By such scheme, described oxidant be iron chloride, hydrogen peroxide, Potassiumiodate, potassium bichromate, ammonium persulfate, cesium sulfate any one.
By such scheme, described acid be inorganic acid hydrochloric acid, sulfuric acid, perchloric acid and nitric acid, organic acid dodecyl sodium sulfonate, phytic acid, oxalic acid, citric acid, DBSA, camphorsulfonic acid and naphthalene sulfonic acids any one, the ratio of the volume of aniline and the amount of substance of acid is 30 ~ 250 μ L:1 ~ 5mmol.
By such scheme, described reducing atmosphere is that by volume percentages is the mist of nitrogen containing 5% hydrogen, surplus, and inert atmosphere is nitrogen, argon gas atmosphere.
By such scheme, described high-temperature heat treatment is with the heating rate of 1 ~ 10 DEG C/min, is raised to target temperature 500 ~ 800 DEG C insulation 2 ~ 10 hours.
The method is aided with calcining by in-situ polymerization thing cladding process, when the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon of preparation is applied to lithium ion battery negative material, there is the characteristic of higher theoretical specific capacity, lower charging potential platform, utilize nitrogen-doped carbon greatly can promote material conductivity simultaneously, the characteristic of memory capacity can be additionally provided; Layer of charcoal in addition in this one dimension porous nucleocapsid clad structure can overcome structural deterioration that manganese monoxide nanometer rods causes due to volumetric expansion in charge and discharge process, efflorescence, reunion and the problem causing capacity to be decayed rapidly, thus, the present invention can obtain a kind of preparation method with the coated manganese monoxide combination electrode material of one dimension porous nucleocapsid structure nitrogen-doped carbon that capacity is high, cyclical stability is excellent.
Compared with prior art, beneficial effect of the present invention is:
1) porosity characteristic, one dimension manganese monoxide nanometer rods, conduction nitrogen-doped carbon effectively to combine the composite material provided by the present invention, conductivity and the specific area of composite material can be improved, electrolyte is effectively contacted with composite material, thus can effectively improve high rate performance and specific capacity; The loose structure simultaneously introduced and conduction nitrogen-doped carbon effectively can suppress the rapid attenuation problem of capacity because volume acute variation causes, and make prepared composite material have excellent structural stability and cycle life.The nitrogen-doped carbon introduced also has storage lithium ion function, makes composite material specific capacity higher than manganese monoxide theoretical capacity.
2) the present invention utilizes polyaniline in-situ polymerization cladding process, first in containing the solution of manganese dioxide, add oxidant, and then add aniline monomer, allow the acid solution containing aniline mix rapidly with the mixed liquor containing manganese dioxide nano-rod and to react under static conditions be polymerized, can in the process of the coated manganese dioxide nano-rod of synthesized polyaniline in position, manganese dioxide is suppressed to participate in reaction, ensure that polyaniline can evenly be coated on manganese dioxide nano-rod, and then also can be used as reducing agent and carbon source with obtained polyaniline, carry out high-temperature heat treatment and can obtain the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon, the method is simple, raw material is easy to regulate, with low cost, be easy to realize industrialization,
Accompanying drawing explanation
Fig. 1 is the XRD photo of embodiment 1 products obtained therefrom;
Fig. 2 is the TEM photo (upper left corner accompanying drawing is HRTEM figure) of embodiment 1 products obtained therefrom;
Fig. 3 is the XPS photo of embodiment 1 products obtained therefrom;
Fig. 4 is the cycle performance photo of simulated battery under 1000mA/g prepared by embodiment 1 products obtained therefrom;
Fig. 5 is the cycle performance photo of simulated battery under 4000mA/g prepared by embodiment 1 products obtained therefrom;
Fig. 6 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 protection scope of the present invention is not limited thereto.
Embodiment 1
1) manganese dioxide (MnO prepared by 0.52g hydro thermal method is taken respectively 2) nanometer rods, 0.46g ammonium persulfate ((NH 4) 2s 2o 8) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes; Manganese dioxide nano-rod can adopt following hydro thermal method to prepare: 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 clear water centrifuge washing 3 times, dry, stand-by.
2) by 90 μ L aniline monomers (aniline and ammonium persulfate mol ratio are 1:2), 0.15g oxalic acid (H 2c 2o 4) add in 24mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly in the solution of step (1), move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 12 hours, after clear water centrifuge washing 3 times, dry under 90 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline;
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of nitrogen, with the heating rate of 10 DEG C/min, at 650 DEG C, be incubated 10 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.Fig. 1 is X-ray diffraction (XRD) figure of this material, contrasts with standard card, and products therefrom is manganese monoxide, and 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 obvious one dimension porous nucleocapsid structure, nanorod length is about 1 μm, and diameter is 100 ~ 150nm, the upper left corner accompanying drawing of Fig. 2 can find out that carbon coated is amorphous carbon, and carbon layer is about 10nm; Fig. 3 is the x-ray photoelectron power spectrum (XPS) of compound, can find containing Mn, O, N, C, the nitrogen-doped carbon that N, C element obtain after should be polyaniline calcining, meets the composition of the coated manganese monoxide of compound nitrogen-doped carbon.
Electrode is made as follows with the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon of embodiment 1 gained:
The coated manganese monoxide composite material of one dimension porous nitrogen-doped carbon is taken respectively: acetylene black: polytetrafluoroethylene (PVDF) with the mass ratio of 7:2:1, after grinding, add the ultrasonic process of 1-METHYLPYRROLIDONE (NMP) 1 hour of designated volume, evenly be 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. 4 is the long-time cyclic curve of battery under the current density of 1000mA/g in 0.01 ~ 3.0V voltage range that this composite material is assembled into, can find that this combination electrode material has extraordinary cyclical stability, under the current density of 1000mA/g, first circle charging capacity is 641.9mAh/g, after circulation 50 circle, capacity tends towards stability, and reversible capacity is 536.2mAh/g; Fig. 5 is battery cycle performance figure under the current density of 4000mA/g that this composite material is assembled into, first circle charging capacity is 246.6mAh/g, after circulation 50 circle, capacity is increased to 301mAh/g gradually, and after circulation 2100 circle, capacity still has 266.7mAh/g, capacity relative is in a few circle above, almost undamped, even if compared with peak capacity in cyclic process, capability retention also has 88.6%; As can be seen from Figure 6, this combination electrode material has good high rate performance, capacity is under the current density of 50mA/g, and first circle charging capacity is about 895.6mAh/g, and capacity declines gradually subsequently, after circulation 5 circle, charging capacity is 819.2mAh/g, even if the discharge and recharge of experience high current density, when returning to low current density (50mA/g), its charge specific capacity can recover substantially, and capacity is about 795mAh/g.
Embodiment 2
1) manganese dioxide (MnO prepared by 0.26g hydro thermal method is taken respectively 2) nanometer rods, 0.46g ammonium persulfate ((NH 4) 2s 2o 8) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 5 minutes, ice bath stirs 10 minutes;
2) by 180 μ L aniline monomers (aniline and ammonium persulfate mol ratio are 1:1), 1.2g phytic acid (C 6h 18o 24p 6) add in 24mL deionized water, ice bath stirs 10 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 0.5 hour, after clear water centrifuge washing 3 times, dry under 60 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline;
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of argon gas, with the heating rate of 1 DEG C/min, at 500 DEG C, be incubated 2 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 3
1) manganese dioxide (MnO prepared by 0.52g hydro thermal method is taken respectively 2) nanometer rods, 80 μ L hydrogen peroxide ((H 2o 2) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 60 μ L aniline monomers (aniline and hydrogen peroxide mol ratio are 1:4), 0.15g oxalic acid (H 2c 2o 4) add in 24mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 6 hours, after clear water centrifuge washing 3 times, dry under 90 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline;
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of nitrogen, with the heating rate of 5 DEG C/min, at 800 DEG C, be incubated 2 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 4
1) manganese dioxide (MnO prepared by 4.30g hydro thermal method is taken respectively 2) nanometer rods, 0.33g iron chloride (FeCl 3) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 60 minutes;
2) by 180 μ L aniline monomers (aniline and iron chloride mol ratio are 1:1), 0.3g oxalic acid (H 2c 2o 4) add in 24mL deionized water, ice bath stirs 60 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 36 hours, after clear water centrifuge washing 3 times, dry under 120 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of reducibility gas (nitrogen: hydrogen volume is than being 95:5), with the heating rate of 10 DEG C/min, 10 hours are incubated at 800 DEG C, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 5
1) manganese dioxide (MnO prepared by 0.26g hydro thermal method is taken respectively 2) nanometer rods, 0.86g Potassiumiodate (KIO 3) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 90 μ L aniline monomers (aniline and Potassiumiodate mol ratio are 1:2), 0.96g citric acid (C 6h 8o 7) add in 24mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 30 hours, after clear water centrifuge washing 3 times, dry under 90 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of reducibility gas (nitrogen: hydrogen volume is than being 95:5), with the heating rate of 1 DEG C/min, 10 hours are incubated at 500 DEG C, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 6
1) manganese dioxide (MnO prepared by 1.04g hydro thermal method is taken respectively 2) nanometer rods, 1.76g potassium bichromate (K 2gr 2o 7) add in 60mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 180 μ L aniline monomers (aniline and potassium bichromate mol ratio are 1:2), 1.2g oxalic acid (H 2c 2o 4) add in 48mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 24 hours, after clear water centrifuge washing 3 times, dry under 120 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of nitrogen, with the heating rate of 10 DEG C/min, at 650 DEG C, be incubated 5 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 7
1) manganese dioxide (MnO prepared by 1.04g hydro thermal method is taken respectively 2) nanometer rods, 1.09g cesium sulfate (Cs 2sO4) add in 60mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 180 μ L aniline monomers (aniline and cesium sulfate mol ratio are 1:1.5), 1mL hydrochloric acid (HCl; 38% mass fraction concentrated acid) add in 48mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 36 hours, after clear water centrifuge washing 3 times, dry under 100 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of nitrogen, with the heating rate of 5 DEG C/min, at 700 DEG C, be incubated 5 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 8
1) manganese dioxide (MnO prepared by 0.44g hydro thermal method is taken respectively 2) nanometer rods, 1.81g cesium sulfate (Cs2SO4) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 180 μ L aniline monomers (aniline and cesium sulfate mol ratio are 1:2.5), 1.2g phytic acid (C 6h 18o 24p 6) add in 24mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 12 hours, after clear water centrifuge washing 3 times, dry under 90 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of argon gas, with the heating rate of 10 DEG C/min, at 650 DEG C, be incubated 5 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 9
1) 4.30g manganese dioxide (MnO is taken respectively 2) nanometer rods, 6.38g ammonium persulfate ((NH 4) 2s 2o 8) add in 300mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 250 μ L aniline monomers (aniline and ammonium persulfate mol ratio are 1:1), 1.5g oxalic acid (C 6h 18o 24p 6) add in 240mL deionized water, ice bath stirs 15 minutes;
3) treat step 1) institute join mixed liquor stop stir, by step 2) solution adds rapidly wherein, and move into refrigerator-freezer 0 ~ 10 DEG C and leave standstill 12 hours, after clear water centrifuge washing 3 times, dry under 120 DEG C of conditions, obtain the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of argon gas, with the heating rate of 10 DEG C/min, at 700 DEG C, be incubated 8 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
Embodiment 10
1) manganese dioxide (MnO prepared by 0.52g hydro thermal method is taken respectively 2) nanometer rods, 90 μ L hydrogen peroxide (H 2o 2) add in 30mL deionized water, with the ultrasonic process of ultrasonic cleaner after 30 minutes, ice bath stirs 15 minutes;
2) by 90 μ L aniline monomers (aniline and hydrogen peroxide mol ratio are 1:3), the 1mL concentrated sulfuric acid (H 2sO 4; 98% mass fraction concentrated acid) add in 24mL deionized water, ice bath stirs 15 minutes;
3) step 1 is treated) institute joins mixed liquor and stops stirring, by step 2) solution adds rapidly wherein, moves into refrigerator-freezer and leaves standstill 12 hours, after clear water centrifuge washing 3 times, dry under 90 DEG C of conditions, obtains the coated manganese dioxide nano-rod of core-shell structure polyaniline
4) polyaniline-coated manganese dioxide nano-rod is placed in the tube furnace being full of argon gas, with the heating rate of 2 DEG C/min, at 550 DEG C, be incubated 10 hours, treat that tube furnace cools naturally, obtain black powder, be the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
The method of the one dimension porous nucleocapsid structure nitrogen-doped carbon coated manganese monoxide composite material reference example 1 of embodiment 2-10 is prepared into electrode, carries out battery performance test, the results are shown in Table 1.
Table 1

Claims (10)

1. the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon, it is characterized in that: doped with nitrogen in this composite material, for the coated manganese monoxide nucleocapsid structure of one dimension porous carbon, manganese monoxide is nano bar-shape structure, and the external sheath of manganese monoxide nanometer rods has amorphous carbon layer.
2. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 1, is characterized in that: comprise the steps:
1) add in oxidizing agent solution by manganese dioxide nano-rod, ultrasonic process makes it disperse, and under 0 ~ 10 DEG C of condition, magnetic agitation, makes manganese dioxide nano-rod be uniformly dispersed;
2) aniline monomer is added in acid solution, stir under 0 ~ 10 DEG C of condition, make aniline be dispersed in acid solution, obtain aniline suspension;
3) by step 1) solution adds step 2 rapidly) suspension, 0 ~ 10 DEG C leaves standstill reprocessing in 0.5 ~ 36 hour, obtains the compound of the coated manganese dioxide of polyaniline polymer;
4) by step 3) gained compound carries out high-temperature heat treatment under reproducibility or inert atmosphere, and naturally cool, obtain the coated manganese monoxide nano composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon.
3. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, is characterized in that: described step 1) in sonication treatment time be 5 ~ 30 minutes, mixing time is 10 ~ 60 minutes.
4. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, is characterized in that: described step 3) in reprocessing for water centrifuge washing 3 times, dry at 60 ~ 120 DEG C.
5. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, it is characterized in that: the ratio of the amount of substance of manganese dioxide nano-rod and the volume of aniline is: 0.3 ~ 50mmol:30 ~ 250 μ L, the amount of substance proportion of aniline and oxidant is 1:1 ~ 1:4.
6. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, is characterized in that: described oxidant be iron chloride, hydrogen peroxide, Potassiumiodate, potassium bichromate, ammonium persulfate, cesium sulfate any one.
7. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, is characterized in that: described acid is any one in inorganic acid hydrochloric acid, sulfuric acid, perchloric acid and nitric acid, organic acid dodecyl sodium sulfonate, phytic acid, oxalic acid, citric acid, DBSA, camphorsulfonic acid and naphthalene sulfonic acids.
8. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, is characterized in that: the ratio of the volume of aniline and the amount of substance of acid is 30 ~ 250 μ L:1 ~ 5mmol.
9. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, it is characterized in that: reducing atmosphere is that by volume percentages is the mist of nitrogen containing 5% hydrogen, surplus, and inert atmosphere is nitrogen, argon gas atmosphere.
10. the preparation method of the coated manganese monoxide composite material of one dimension porous nucleocapsid structure nitrogen-doped carbon according to claim 2, it is characterized in that: high-temperature heat treatment is with the heating rate of 1 ~ 10 DEG C/min, be raised to target temperature 500 ~ 800 DEG C insulation 2 ~ 10 hours.
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