CN105552336A - Hydrothermal method synthesized MnO2/NCNTs nanocomposite and preparation method thereof - Google Patents

Hydrothermal method synthesized MnO2/NCNTs nanocomposite and preparation method thereof Download PDF

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CN105552336A
CN105552336A CN201610026952.XA CN201610026952A CN105552336A CN 105552336 A CN105552336 A CN 105552336A CN 201610026952 A CN201610026952 A CN 201610026952A CN 105552336 A CN105552336 A CN 105552336A
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ncnts
composite material
mno
nitrogen
doped carbon
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吕金钊
李延锋
程浩然
李进潘
刘宁宁
赵成龙
王瑛
王胜伟
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Shandong Yuhuang New Energy Technology Co Ltd
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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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

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Abstract

The invention belongs to the new energy material and electrochemistry field, relates to a lithium battery anode material, and especially relates to a hydrothermal method synthesized MnO2/NCNTs nanocomposite and a preparation method thereof. According to the hydrothermal method synthesized MnO2/NCNTs nanocomposite, nitrogen-doped carbon nano tubes NCNTs and manganese dioxide MnO2 are intertwined to form the nanocomposite; the MnO2 accounts for 10-90 % of the total quality of the nanocomposite. The particle powder of the MnO2/NCNTs composite anode material prepared by the invention is small and is evenly distributed; the conductivity is good; through adding the nitrogen-doped carbon nano tubes, the problems that the volume of iron oxide is changed fiercely in the charge/discharge process, the capacity fading is rapid and the circulation performance is relatively poor are effectively avoided; the rate capability and the primary charge/discharge efficiency of the nanocomposite are remarkably improved; and the nanocomposite and the method are featured by simple preparation technology, low cost, environmental protection, high safety and good test repeatability.

Description

A kind of water heat transfer MnO 2/ NCNTs nano composite material and preparation method thereof
(1) technical field
The invention belongs to new energy materials and electrochemical field, relate to a kind of lithium battery negative material, particularly a kind of water heat transfer MnO 2/ NCNTs nano composite material and preparation method thereof.
(2) background technology
Lithium ion battery has high-energy-density, voltage is steady, self-discharge rate is little, the lasting advantage such as cycle performance and environmental protection compared to traditional plumbic acid, Ni-MH battery.Along with lithium ion battery is in the development in the high-power electric appliance fields such as electric automobile, people have higher requirement to business-like lithium ion battery.At present, the negative material mainly carbon/graphite-based material of the lithium ion battery marketization, its lower theoretical specific capacity is difficult to the requirement (Nature2000,28:407) of satisfied high-power electric appliance of new generation to lithium ion battery.Therefore, Jian sends out that specific capacity is high a kind of, the lithium ion battery negative material of good cycle, high rate performance excellence has important practical significance for the overall performance improving lithium ion battery.
Some transition metal oxides, as the aboundresources, cheap and be easy to the features such as preparation of iron and manganese oxides, have important practical significance to its potential application.But some intrinsic features that transition metal oxide has constrain its further practical application (ElectrochemistryCommun.2008,10; Adv.Mater.2007,19:2087).At present, although take nanometer (Chem.Mater.2008,20:667), porous (Electrochim.Acta.2012,75:123), the coated (Chem.Mater.2010 of carbon, 22:5306), special appearance (Adv.Funct.Mater.2008,18:3941) etc. measure improves the cycle performance of transition metal oxide, but still is difficult to fundamentally to overcome the deficiency that its aspect of performance exists.Grind the discovery that makes internal disorder or usurp, transition metal oxide and other materials compound effectively can alleviate above shortcoming (Adv.Funct.Mater.2013,23:4049).Be used for that the material of compound can be that carbon pipe, graphite are rare, conducting polymer etc.Auxiliary material usually play in the composite and improve the electronic conductivity of electrode material, the effect of stabilized nanoscale material structure.These composite means all improve significantly to the coulombic efficiency first of electrode, the aspect such as high rate performance and cyclical stability.
Nearest research finds, utilizes the grappling effect of (NCNTs) nitrogen in nitrogen-doped carbon nanometer pipe and by the content of nitrogen in modulation nitrogen-doped carbon nanometer pipe and distribution and then the intermetallic interaction coming modulation and its grappling, can stablize Fe 3o 4nano particle, the catalyst built with this presents excellent heterogeneous catalysis performance (ACSCatal.2014,4:613 in fischer-tropsch reaction; CN103406137A).But up to now, there is not yet NCNTs and MnO 2compound builds composite construction and for the application of lithium ion battery.In invention, we are intended to utilize simple method to construct high performance lithium ion cell nano combination electrode material, to MnO to be solved 2in charge and discharge process, change in volume is violent, and cause the problem that its cycle performance is poor, the development for lithium ion battery negative material provides useful exploration.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides a kind of water heat transfer MnO 2/ NCNTs nano composite material and preparation method thereof, this material for carrier, utilizes hydro thermal method and manganese dioxide (MnO with nitrogen-doped carbon nanometer pipe (NCNTs) 2) compound, build MnO 2the method of/NCNTs composite material, to MnO to be solved 2negative material change in volume in charge and discharge process is violent, causes the problem that capacity attenuation is fast, cycle performance is poor.Nitrogen-doped carbon nanometer pipe prepared by the present invention and MnO 2negative material granular powder is tiny and be evenly distributed, and has good conductivity.Material presents high, the good high rate performance of higher recycle ratio capacity, first charge-discharge efficiency and cyclical stability in electro-chemical test.
The present invention is achieved through the following technical solutions:
A kind of water heat transfer MnO 2/ NCNTs nano composite material, its special character is: nitrogen-doped carbon nanometer pipe NCNTs and manganese dioxide MnO 2be intertwined, form nano composite material, wherein, MnO 2account for the 10-90% of nano composite material gross mass.
In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for the 0.5-7% of nitrogen-doped carbon nanometer pipe gross mass.
In nano composite material, MnO 2for irregular polygon.Described NCNTs and MnO 2closely be intertwined, form the nano composite material that pattern is homogeneous.
Described MnO 2/ NCNTs composite material is made up of micro-nano structure, and this micro-nano structure both can prevent the efflorescence of composite material in charge and discharge process from keeping the stability of material, also contributed to embedding and the transmission of lithium ion.
Need to add nitrogen-doped carbon nanometer pipe in described composite material, its effect mainly contains: the intermetallic electron interaction that 1) can be come modulation and its grappling by the content of nitrogen in modulation nitrogen-doped carbon nanometer pipe and distribution; 2) realize micro-nano structure compound, this micro-nano structure both can prevent the efflorescence of composite material in charge and discharge process from keeping the stability of material, also contributed to embedding and the transmission of lithium ion; 3) nitrogen-doped carbon nanometer pipe itself has basic character (ACSCatal.2014,4:613) can increase active material to the wettability of electrolyte and pick up; 4) conductivity of nitrogen-doped carbon nanometer pipe is at ~ 100s/cm, can increase the conductivity of active material; 5) nitrogen-doped carbon nanometer pipe has good heat conduction and mechanical performance, can evacuate the energy of lithium ion charge and discharge process release in time.More than consider, the scope that in nitrogen-doped carbon nanometer pipe, the comparision contents of nitrogen is good is 0.5-7%.
Described water heat transfer MnO 2the preparation method of/NCNTs nano composite material, comprise the following steps: the pH regulating reaction medium, nitrogen-doped carbon nanometer pipe is added in reaction medium, heating-up temperature, to 80-200 DEG C, then adds manganese salt, obtains sample after reaction a period of time, this sample first carries out drying, then through roasting, then cool, namely obtain MnO 2/ NCNTs nano composite material, sintering temperature is 200 ~ 700 DEG C, and wherein, when in manganese salt, manganese valence is+6 valency, the pH of reaction medium is 1-6, in manganese salt manganese valence be+6 ,+divalent time, the pH of reaction medium is 7-8.5.
Wherein, reaction medium is the mixed solution of water or water and acid.Acid is at least one of sulfuric acid, hydrochloric acid, nitric acid.
Reaction time is 0.5-10h, and after reaction, suction filtration is dried.
Under inert gas, final drying is obtained the rear roasting of sample intensification, its gas flow rate 20-1000sccm, roasting time is 0.1-10h.Nitrogen-doped carbon nanometer pipe is first dispersed in the aqueous solution of alcohol or 10-50% alcohol, and then added in reaction medium.Inert atmosphere is N 2or Ar atmosphere, alcohol be methyl alcohol, ethanol, propyl alcohol one or more.
The preparation method of above-mentioned material, is preferably:
(1) NCNTs ultrasonic disperse is in alcoholic solution;
(2) a certain amount of concentrated sulfuric acid is added in (1);
(3), under stirring, oil bath heating (2) is to temperature required;
(4) treat that in (3), temperature rises to temperature required, adds a certain amount of manganese salt;
(5) continue reaction a period of time, suction filtration is dried;
(6) under inert gas, final drying is obtained the rear roasting of sample intensification, then cool, namely obtain MnO 2/ NCNTs nano composite material.
Electrochemical property test carries out in following condition: mixed by the weight ratio of 8:1:1 with Kynoar (PVDF) and conductive agent by obtained active material, with 1-METHYLPYRROLIDONE (NMP) for solvent, stir and be applied to equably on Copper Foil after 6 hours, 110 DEG C of vacuum drying compressing tablets, obtain work electrode sheet.Electrolyte is the LiPF of 1mol/L 6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (volume ratio 1:1).Barrier film is polypropylene, polyethylene microporous barrier (Celgard2500).All batteries (2032 type button cell) are all assembled in the glove box of anhydrous and oxygen-free, and lithium sheet is as to electrode.After battery assembling, activation was measured after 12 hours, infiltrated fully on electrode to make electrolyte.The electric battery performance testing system of indigo plant carries out charge-discharge test, and voltage range is 0.5-3.0V.
Compared to existing technology, the present invention has the following advantages:
1), the MnO for preparing of the present invention 2/ NCNTs composite negative pole material granular powder is tiny and be evenly distributed (0.1-1um), has good conductivity (10 -2~ 10s/cm);
2), adding nitrogen-doped carbon nanometer pipe can effectively suppress manganese oxide change in volume in charge and discharge process acutely, to cause the problem (MnO that capacity attenuation is fast, cycle performance is poor 2blank sample 1C circulation 100 circle capability retention is ~ 30%, MnO 2can up to 99% under/NCNTs composite material the same terms, capacity has no obvious decay);
3) high rate performance (MnO that nitrogen-doped carbon nanometer pipe can significantly improve composite material, is added 2specific capacity can up to 300mAh/g under 5C multiplying power for/NCNTs) and first charge-discharge efficiency (MnO 2/ NCNTs head effect can up to 77%);
4), preparation technology of the present invention is simple, and cost is low, environmental friendliness, and fail safe is high, and experimental repeatability is good.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 MnO 2the XRD of/NCNTs composite material;
Fig. 2 MnO 2the SEM of/NCNTs composite material;
The MnO that this experiment of Fig. 3 is obtained 2the SEM of blank sample;
Fig. 4 MnO 2/ NCNTs and MnO 2high rate performance contrasts;
Fig. 5 is that MnO is prepared in manganese source with potassium permanganate 2the cyclical stability of/NCNTs under 1C multiplying power;
Fig. 6 MnO 2the cyclical stability of blank sample under 1C multiplying power.
(5) embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not limited to protection scope of the present invention.
Embodiment 1 is with 80 DEG C of preparation 90%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 0.54gNCNTs and be first scattered in (it is 40% that methyl alcohol accounts for its volume ratio) in methanol aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 4% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 80 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 90%MnO 2/ NCNTs composite material.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 882mAh/g, first efficiency 62%; Under 5C multiplying power, specific discharge capacity is the capability retention under 200mAh/g, 1C multiplying power after circulation 100 circle is 90%.
Embodiment 2 is with 80 DEG C of preparation 80%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 0.85gNCNTs and be first scattered in (it is 50% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 2% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 80 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 80%MnO 2/ NCNTs composite material.Gas flow rate 80sccm.
Lithium battery performance test, first discharge specific capacity is 962mAh/g, first efficiency 75%; Under 5C multiplying power, specific discharge capacity is the capability retention under 230mAh/g, 1C multiplying power after circulation 100 circle is 99%.
Embodiment 3 is with 80 DEG C of preparation 70%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 1.24gNCNTs and be first scattered in (it is 45% that propyl alcohol accounts for its volume ratio) in aqueous propanol solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 3.5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 80 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 10h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 70%MnO 2/ NCNTs composite material.Gas flow rate 100sccm.
Lithium battery performance test, first discharge specific capacity is 1020mAh/g, first efficiency 77%; Under 5C multiplying power, specific discharge capacity is that 300mAh/g(high rate performance is shown in accompanying drawing 4), the capability retention after 100 circles that circulate under 1C multiplying power is 95%.
Embodiment 4 is with 80 DEG C of preparation 60%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 1.77gNCNTs and be first scattered in (it is 20% that methyl alcohol accounts for its volume ratio, and ethanol accounts for 30% of its volume ratio) in methyl alcohol, the alcohol mixture aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 80 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 8h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 6h, obtains 60%MnO 2/ NCNTs composite material.Gas flow rate 700sccm.
Lithium battery performance test, first discharge specific capacity is 860mAh/g, first efficiency 67%; Under 5C multiplying power, specific discharge capacity is the capability retention under 280mAh/g, 1C multiplying power after circulation 100 circle is 93%.
Embodiment 5 is with 80 DEG C of preparation 50%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 2.50gNCNTs and be first scattered in (it is 55% that methyl alcohol accounts for its volume ratio) in methanol aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 2% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 80 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 50%MnO 2/ NCNTs composite material.Gas flow rate 600sccm.
Lithium battery performance test, first discharge specific capacity is 750mAh/g, first efficiency 70%; Under 5C multiplying power, specific discharge capacity is the capability retention under 265mAh/g, 1C multiplying power after circulation 100 circle is 93%.
Embodiment 6 is with 80 DEG C of preparation 10%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 21.10gNCNTs and be first scattered in (it is 50% that propyl alcohol accounts for its volume ratio) in aqueous propanol solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 0.5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 80 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 6h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 8h, obtains 10%MnO 2/ NCNTs composite material.Gas flow rate 500sccm.
Lithium battery performance test, first discharge specific capacity is 150mAh/g, first efficiency 70%; Under 5C multiplying power, specific discharge capacity is the capability retention under 65mAh/g, 1C multiplying power after circulation 100 circle is 23%.
Embodiment 7 is with 100 DEG C of preparation 90%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 0.54gNCNTs and be first scattered in (it is 40% that methyl alcohol accounts for its volume ratio) in methanol aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 1.5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 100 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 90%MnO 2/ NCNTs composite material.Gas flow rate 100sccm.
Lithium battery performance test, first discharge specific capacity is 901mAh/g, first efficiency 70%; Under 5C multiplying power, specific discharge capacity is the capability retention under 250mAh/g, 1C multiplying power after circulation 100 circle is 82%.
Embodiment 8 is with 100 DEG C of preparation 60%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 1.77gNCNTs and be first scattered in (it is 45% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 2.5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 100 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 60%MnO 2/ NCNTs composite material.Gas flow rate 50sccm.
Lithium battery performance test, first discharge specific capacity is 960mAh/g, first efficiency 70%; Under 5C multiplying power, specific discharge capacity is the capability retention under 300mAh/g, 1C multiplying power after circulation 100 circle is 90%.
Embodiment 9 is with 100 DEG C of preparation 10%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 21.10gNCNTs and be first scattered in (propyl alcohol accounts for 20% of its aqueous solution, and ethanol accounts for its aqueous solution 25%) in the mixture aqueous solution of ethanol, propyl alcohol, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 100 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 10%MnO 2/ NCNTs composite material.Gas flow rate 20sccm.
Lithium battery performance test, first discharge specific capacity is 190mAh/g, first efficiency 72%; Under 5C multiplying power, specific discharge capacity is the capability retention under 115mAh/g, 1C multiplying power after circulation 100 circle is 40%.
Embodiment 10 is with 120 DEG C of preparation 90%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 0.54gNCNTs and be first scattered in (it is 40% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 6% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 120 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 90%MnO 2/ NCNTs composite material.Gas flow rate 1000sccm.
Lithium battery performance test, first discharge specific capacity is 1000mAh/g, first efficiency 74%; Under 5C multiplying power, specific discharge capacity is the capability retention under 280mAh/g, 1C multiplying power after circulation 100 circle is 85%.
Embodiment 11 is with 120 DEG C of preparation 80%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 0.85gNCNTs and be first scattered in (it is 45% that methyl alcohol accounts for its volume ratio) in methanol aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 2.5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 120 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 80%MnO2/NCNTs composite material.Gas flow rate 100sccm.
Lithium battery performance test, first discharge specific capacity is 985mAh/g, first efficiency 77%; Under 5C multiplying power, specific discharge capacity is the capability retention under 300mAh/g, 1C multiplying power after circulation 100 circle is that 99%(cycle performance is shown in accompanying drawing 5).
Embodiment 12 is with 120 DEG C of preparation 10%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 2ml98% with graduated cylinder, slowly join in the beaker filling 350g deionized water under stirring.Then the sulfuric acid solution configured is joined in there-necked flask, take 21.10gNCNTs and be first scattered in (it is 45% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 7% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 120 DEG C, takes 4.00g potassium permanganate and adds in flask.Stop heating after reaction 5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Nitrogen atmosphere protects 220 DEG C to process 2h, obtains 10%MnO 2/ NCNTs composite material.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 205mAh/g, first efficiency 70%; Under 5C multiplying power, specific discharge capacity is the capability retention under 125mAh/g, 1C multiplying power after circulation 100 circle is 50%.
Embodiment 13 is with 140 DEG C of preparation 10%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 98% with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 1.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (it is 50% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 140 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 3h, be down to suction filtration after below 40 DEG C until oil bath temperature, 130 DEG C of oven dry.Argon gas atmosphere protects 200 DEG C to process 10h, obtains 10%MnO 2/ NCNTs composite material.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 205mAh/g, first efficiency 72%; Under 5C multiplying power, specific discharge capacity is the capability retention under 135mAh/g, 1C multiplying power after circulation 100 circle is 70%.
Embodiment 14 is with 150 DEG C of preparation 30%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 98% with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 3.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (it is 45% that methyl alcohol accounts for its volume ratio) in methanol aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 3% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 150 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 4h, be down to suction filtration after below 40 DEG C until oil bath temperature, 140 DEG C of oven dry.Argon gas atmosphere protects 300 DEG C to process 5h, obtains 30%MnO 2/ NCNTs composite material.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 650mAh/g, first efficiency 68%; Under 5C multiplying power, specific discharge capacity is the capability retention under 205mAh/g, 1C multiplying power after circulation 100 circle is 85%.
Embodiment 15 is with 160 DEG C of preparation 50%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 98% with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 5.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (it is 45% that propyl alcohol accounts for its volume ratio) in aqueous propanol solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 7% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 160 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 6h, be down to suction filtration after below 40 DEG C until oil bath temperature, 140 DEG C of oven dry.Argon gas atmosphere protects 500 DEG C to process 2h, obtains 50%MnO 2/ NCNTs composite material.Gas flow rate 500sccm.
Lithium battery performance test, first discharge specific capacity is 770mAh/g, first efficiency 64%; Under 5C multiplying power, specific discharge capacity is the capability retention under 215mAh/g, 1C multiplying power after circulation 100 circle is 87%.
Embodiment 16 is with 170 DEG C of preparation 60%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 98% with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 6.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (propyl alcohol accounts for its aqueous solution 20%, and ethanol accounts for its aqueous solution 27%) in propyl alcohol, the alcohol mixture aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 0.5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 170 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 2h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Argon gas atmosphere protects 600 DEG C to process 2h, obtains 60%MnO 2/ NCNTs composite material.Gas flow rate 600sccm.
Lithium battery performance test, first discharge specific capacity is 820mAh/g, first efficiency 60%; Under 5C multiplying power, specific discharge capacity is the capability retention under 225mAh/g, 1C multiplying power after circulation 100 circle is 86%.
Embodiment 16 is with 190 DEG C of preparation 60%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 98% with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 2.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (propyl alcohol accounts for 20% of its aqueous solution, and methyl alcohol accounts for 30% of its aqueous solution) in propyl alcohol, the carbinol mixture aqueous solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 3% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 190 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 1h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Argon gas atmosphere protects 700 DEG C to process 1h, obtains 60%MnO 2/ NCNTs composite material.Gas flow rate 350sccm.
Lithium battery performance test, first discharge specific capacity is 720mAh/g, first efficiency 62%; Under 5C multiplying power, specific discharge capacity is the capability retention under 235mAh/g, 1C multiplying power after circulation 100 circle is 67%.
Embodiment 17 is with 200 DEG C of preparation 40%MnO 2/ NCNTs composite material is example.
First measure the concentrated sulfuric acid of 98% with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 2.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (it is 50% that propyl alcohol accounts for its volume ratio) in aqueous propanol solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 200 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 0.5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Argon gas atmosphere protects 700 DEG C to process 3h, obtains 40%MnO 2/ NCNTs composite material.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 550mAh/g, first efficiency 64%; Under 5C multiplying power, specific discharge capacity is the capability retention under 217mAh/g, 1C multiplying power after circulation 100 circle is 88%.
Embodiment 18 is with 200 DEG C of preparation 10%MnO 2/ NCNTs composite material is example.
First measure hydrochloric acid with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 4.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in (it is 40% that propyl alcohol accounts for its volume ratio) in aqueous propanol solution, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 200 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 0.5h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Argon gas atmosphere protects 600 DEG C to process 0.5h, obtains 10%MnO 2/ NCNTs composite material.Gas flow rate 350sccm.
Lithium battery performance test, first discharge specific capacity is 225mAh/g, first efficiency 68%; Under 5C multiplying power, specific discharge capacity is the capability retention under 102mAh/g, 1C multiplying power after circulation 100 circle is 81%.
Embodiment 19 is with 200 DEG C of preparation 15%MnO 2/ NCNTs composite material is example.
First measure nitric acid with graduated cylinder, slowly join and fill in the beaker of deionized water under stirring, surveying pH value is 4.Then the sulfuric acid solution configured is joined in there-necked flask, take NCNTs and be first scattered in propyl alcohol, and then add in flask.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 3% of nitrogen-doped carbon nanometer pipe gross mass.Be placed in by flask on heat collecting type constant-temperature heating magnetic stirring apparatus and stir, oil bath is heated, and when oil bath temperature rises to 200 DEG C, takes potassium permanganate and adds in flask.Stop heating after reaction 2h, be down to suction filtration after below 40 DEG C until oil bath temperature, 120 DEG C of oven dry.Argon gas atmosphere protects 700 DEG C to process 2h, obtains 15%MnO 2/ NCNTs composite material.Gas flow rate 20sccm.
Lithium battery performance test, first discharge specific capacity is 250mAh/g, first efficiency 66%; Under 5C multiplying power, specific discharge capacity is the capability retention under 185mAh/g, 1C multiplying power after circulation 100 circle is 92%.
Embodiment 20 prepares 90%MnO with potassium permanganate and manganese acetate 2/ NCNTs composite material is example.
Measuring 300ml deionized water joins in flask, stirs, and oil bath is heated, and oil bath temperature is initially set to 80 DEG C.Take 5.00gKMnO 4and 11.63gC 4h 6mnO 44H 2o puts into agate mortar, adds in flask after grinding 40min.React and add 0.76gNCNTs after 3 hours and be first scattered in (it is 50% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask, continue stirring reaction 2h, then cool, wash, suction filtration, 120 DEG C vacuumize dry 3h after obtain the 90%MnO of black 2/ NCNTs composite material.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5% of nitrogen-doped carbon nanometer pipe gross mass.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 950mAh/g, first efficiency 75%; Under 5C multiplying power, specific discharge capacity is the capability retention under 285mAh/g, 1C multiplying power after circulation 100 circle is 95%.
Embodiment 21 prepares 50%MnO with potassium permanganate and manganese acetate 2/ NCNTs composite material is example.
Measuring 300ml deionized water joins in flask, stirs, and oil bath is heated, and oil bath temperature is initially set to 80 DEG C.Take 5.00gKMnO 4and 11.63gC 4h 6mnO 44H 2o puts into agate mortar, adds in flask after grinding 40min.React and add 6.88NCNTs after 3 hours and be first scattered in (it is 50% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask, continue stirring reaction 2h, then cool, wash, suction filtration, 120 DEG C vacuumize dry 3h after obtain the 50%MnO of black 2/ NCNTs composite material.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 5.5% of nitrogen-doped carbon nanometer pipe gross mass.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 850mAh/g, first efficiency 72%; Under 5C multiplying power, specific discharge capacity is the capability retention under 262mAh/g, 1C multiplying power after circulation 100 circle is 93%.
Embodiment 22 prepares 10%MnO with potassium permanganate and manganese acetate 2/ NCNTs composite material is example.
Measuring 300ml deionized water joins in flask, stirs, and oil bath is heated, and oil bath temperature is initially set to 80 DEG C.Take 5.00gKMnO 4and 11.63gC 4h 6mnO 44H 2o puts into agate mortar, adds in flask after grinding 40min.React and add 61.92NCNTs after 3 hours and be first scattered in (it is 45% that methyl alcohol accounts for its volume ratio) in methanol aqueous solution, and then add in flask, continue stirring reaction 2h, then cool, wash, suction filtration, 120 DEG C vacuumize dry 3h after obtain the 50%MnO of black 2/ NCNTs composite material.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 4.5% of nitrogen-doped carbon nanometer pipe gross mass.Gas flow rate 400sccm.
Lithium battery performance test, first discharge specific capacity is 250mAh/g, first efficiency 64%; Under 5C multiplying power, specific discharge capacity is the capability retention under 135mAh/g, 1C multiplying power after circulation 100 circle is 85%.
Embodiment 23 prepares 30%MnO with potassium permanganate and manganese acetate 2/ NCNTs composite material is example.
Measuring 300ml deionized water joins in flask, stirs, and oil bath is heated, and oil bath temperature is initially set to 150 DEG C.Take 5.00gKMnO 4and 12.5gC 4h 6mnO 44H 2o puts into agate mortar, and add in flask after grinding 40min, pH value is 8.5.React and add NCNTs after 2 hours and be first scattered in (it is 40% that ethanol accounts for its volume ratio) in ethanol water, and then add in flask, continue stirring reaction 3h, then cool, wash, suction filtration, 120 DEG C vacuumize dry 2h after obtain the 30%MnO of black 2/ NCNTs composite material.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 3% of nitrogen-doped carbon nanometer pipe gross mass.Gas flow rate 500sccm.
Lithium battery performance test, first discharge specific capacity is 750mAh/g, first efficiency 68%; Under 5C multiplying power, specific discharge capacity is the capability retention under 245mAh/g, 1C multiplying power after circulation 100 circle is 90%.
Embodiment 24 prepares 40%MnO with potassium permanganate and manganese acetate 2/ NCNTs composite material is example.
Measuring 300ml deionized water joins in flask, stirs, and oil bath is heated, and oil bath temperature is initially set to 180 DEG C.Take 5.00gKMnO 4and 11.7gC 4h 6mnO 44H 2o puts into agate mortar, and add in flask after grinding 40min, pH value is 7.5.React and add CNTs after 2 hours and be first scattered in ethanol, and then add in flask, continue stirring reaction 3h, then cool, wash, suction filtration, 120 DEG C vacuumize dry 2h after obtain the 40%MnO of black 2/ NCNTs composite material.In described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for 3% of nitrogen-doped carbon nanometer pipe gross mass.Gas flow rate 600sccm.
Lithium battery performance test, first discharge specific capacity is 790mAh/g, first efficiency 71%; Under 5C multiplying power, specific discharge capacity is the capability retention under 265mAh/g, 1C multiplying power after circulation 100 circle is 94%.
Comparative example
Comparative example 1: the MnO not adding NCNTs 2blank sample (embodiment the results are shown in Figure 3 and Fig. 6).

Claims (10)

1. a water heat transfer MnO 2/ NCNTs nano composite material, is characterized in that: nitrogen-doped carbon nanometer pipe and manganese dioxide are intertwined, and forms nano composite material, wherein, and MnO 2account for the 10-90% of nano composite material gross mass.
2. water heat transfer MnO according to claim 1 2/ NCNTs nano composite material, is characterized in that: in described nitrogen-doped carbon nanometer pipe, nitrogen content accounts for the 0.5-7% of nitrogen-doped carbon nanometer pipe gross mass.
3. water heat transfer MnO according to claim 1 and 2 2/ NCNTs nano composite material, is characterized in that: in nano composite material, MnO 2for irregular polygon.
4. a water heat transfer MnO according to claim 1 2the preparation method of/NCNTs nano composite material, it is characterized in that: comprise the following steps: the pH regulating reaction medium, nitrogen-doped carbon nanometer pipe is added in reaction medium, heating-up temperature, to 80-200 DEG C, then adds manganese salt, obtains sample after reaction a period of time, this sample first carries out drying, then through roasting, then cool, namely obtain MnO 2/ NCNTs nano composite material, sintering temperature is 200 ~ 700 DEG C, and wherein, when in manganese salt, manganese valence is+6 valency, the pH of reaction medium is 1-6, in manganese salt manganese valence be+6 ,+divalent time, the pH of reaction medium is 7-8.5.
5. water heat transfer MnO according to claim 4 2the preparation method of/NCNTs nano composite material, is characterized in that: reaction medium is the mixed solution of water or water and acid.
6. water heat transfer MnO according to claim 5 2the preparation method of/NCNTs nano composite material, is characterized in that: acid is at least one of sulfuric acid, hydrochloric acid, nitric acid.
7. according to the arbitrary described water heat transfer MnO of claim 4-6 2the preparation method of/NCNTs nano composite material, is characterized in that: the reaction time is 0.5-10h, and after reaction, suction filtration is dried.
8. water heat transfer MnO according to claim 7 2the preparation method of/NCNTs nano composite material, is characterized in that: under inert gas, and final drying is obtained the rear roasting of sample intensification, its gas flow rate 20-1000sccm, roasting time is 0.1-10h.
9. water heat transfer MnO according to claim 8 2the preparation method of/NCNTs nano composite material, is characterized in that: nitrogen-doped carbon nanometer pipe is first dispersed in the aqueous solution of alcohol or 10-50% alcohol, and then added in reaction medium.
10. water heat transfer MnO according to claim 8 2the preparation method of/NCNTs nano composite material, is characterized in that: inert atmosphere is N 2or Ar atmosphere, alcohol be methyl alcohol, ethanol, propyl alcohol one or more.
CN201610026952.XA 2016-01-16 2016-01-16 Hydrothermal method synthesized MnO2/NCNTs nanocomposite and preparation method thereof Pending CN105552336A (en)

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