CN115663138A - Nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material and preparation method thereof - Google Patents
Nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material and preparation method thereof Download PDFInfo
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- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002070 nanowire Substances 0.000 title claims abstract description 106
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000002243 precursor Substances 0.000 claims abstract description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 13
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- H01M4/36—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material and a preparation method thereof, and the preparation method comprises the following steps: firstly, preparing a manganese dioxide nanowire precursor by using a hydrothermal synthesis mode; then mixing the manganese dioxide nanowire precursor with dopamine hydrochloride in a water and ethanol solution dropwise added with ammonia water, and continuously magnetically stirring to prepare the manganese dioxide nanowire wrapped by the polydopamine film; and finally, annealing the manganese dioxide nanowire wrapped by the polydopamine film in an inert atmosphere to obtain the target product manganese monoxide nanowire (N-C @ MnO) wrapped by the N-doped C film. The preparation method is simple and mature, has low cost, can realize mass production, and the obtained material has good chemical stability, high speed performance, excellent cycle stability and excellent coulombic efficiency.
Description
Technical Field
The invention relates to a manganese monoxide nanowire lithium battery material wrapped by a nitrogen-doped carbon film and a preparation method thereof, belonging to the technical field of nano materials.
Background
Manganese oxide nanomaterials (MnOx, including MnO) 2 、MnO、Mn 2 O 3 、Mn 3 O 4 ) And the derivatives thereof have attracted wide attention in the fields of biomedicine, lithium batteries, supercapacitors, electro-catalytic hydrogen evolution, environmental treatment, zinc batteries, photocatalysis and the like due to adjustable structure and morphology, unique physical and chemical properties, abundant resources, environmental friendliness and good biological safety. Particularly in the field of lithium batteries, manganese oxides have a high theoretical specific capacity (MnO in lithium ion batteries) 2 、Mn 2 O 3 MnO and Mn 3 O 4 Has theoretical specific capacities of 1233, 1018, 756 and 937mAh g respectively -1 ) The material is a promising alternative anode material. However, in general, pure manganese oxide is not directly used as a battery electrode material, and on one hand, the material has poor conductivity, and on the other hand, the material expands in volume and fragments during charging and discharging and is stacked together, so that the performance is remarkably reduced, and the cycle stability is poor; in addition, the use of such materials is limited by the industrial production. To address the first two problems, some work has been done to improve the conductivity, cycling stability and service life of such materials by improving the structure of oxides of manganese, e.g., layered porous MnO/carbon microsphere materials, delta-MnO 2 Porous composite material and porous Mn coated in carbon shell 2 O 3 A nano-cubic material.
Disclosure of Invention
Based on the problems in the prior art, the invention provides the nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material with high chemical stability, good rate performance, excellent cycle stability and excellent coulombic efficiency and the preparation method thereof.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a manganese monoxide nanowire lithium battery material wrapped by a nitrogen-doped carbon film is characterized by comprising the following steps: firstly, preparing a manganese dioxide nanowire precursor by using a hydro-thermal synthesis mode; then mixing the manganese dioxide nanowire precursor with dopamine hydrochloride in a water and ethanol solution dropwise added with ammonia water, and continuously magnetically stirring to prepare the manganese dioxide nanowire wrapped by the polydopamine film; and finally, annealing the manganese dioxide nanowire wrapped by the polydopamine film in an inert atmosphere to obtain the target product manganese monoxide nanowire wrapped by the N-doped C film, and marking the target product manganese monoxide nanowire as N-C @ MnO. The method specifically comprises the following steps:
(1) 0.39-0.50 g of KMnO 4 Adding 0.5mL of hydrochloric acid with the mass concentration of 36-38% into 45-60 mL of deionized water, stirring by a glass rod to form a homogeneous solution, pouring the homogeneous solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, transferring the hydrothermal reaction kettle into a constant-temperature air blowing box, heating to 160 ℃, preserving heat for 10 hours, and naturally cooling to room temperature; the reaction product is sequentially centrifuged, collected and dried by deionized water and acetone to obtain MnO 2 A nanowire precursor;
(2) MnO obtained in the step (1) 2 Dispersing 0.12g of nanowire precursor and 0.13-0.26g of dopamine hydrochloride into 150mL of deionized water and ethanol mixed solution, adding 0.1-0.5mL of ammonia water with the mass concentration of 25-28%, and magnetically stirring for 5-12h to ensure that the dopamine hydrochloride is in MnO 2 The nano wire is taken as a template, polymerized into a polydopamine film and wrapped in MnO 2 MnO wrapped by polydopamine film is obtained outside the nanowire 2 Centrifuging the nanowires with acetone, collecting, and drying;
(3) MnO wrapping the polydopamine film obtained in the step (2) in a CVD tube furnace under inert atmosphere (nitrogen or argon) 2 And (3) annealing the nanowires for 2-3 h at 600-700 ℃, then opening the cover of the tube furnace, and rapidly cooling to obtain the target product of the manganese monoxide nanowires wrapped by the N-doped carbon film.
Furthermore, the hydrothermal reaction kettle used in the step (1) is a polytetrafluoroethylene substrate, and the volume is 100mL.
Further, in the step (1) and the step (2), the centrifugal force of the centrifugation is 4000 Xg-6000 Xg, the single centrifugation time is 5min, and the centrifugation is not less than 3 times.
Further, in the step (3), the temperature rise rate of the CVD tube furnace is 10-20 ℃/min.
The invention has the beneficial effects that:
1. the method for preparing the N-C @ MnO nanowire material is simple and mature, has low cost, and the obtained material has good chemical stability, higher energy density, excellent cycle stability and excellent coulombic efficiency.
2. The N-C @ MnO nanowire lithium battery material synthesized by the method disclosed by the invention has the advantages that the service life of the MnO material is prolonged, and the cycle stability of the MnO material is improved. The carbon film has protection and support effects on the manganese monoxide, and promotes charge transmission. During the charge and discharge processes of the lithium battery prepared by the cathode material, li ions are transported outside the carbon film and between the nanowires without contacting with manganese oxide. The movement of lithium ions has no influence on the structure of manganese oxide. The volume expansion and fragmentation of MnO occurs inside the carbon film without collapsing into a pile like pure MnO. The doping of nitrogen in the carbon film increases the conductivity of the material. A three-dimensional porous structure is formed among the nanowires, so that a transmission path is provided for lithium ions, and the conductivity is improved.
3. The advantages of the nanowire obtained by the invention are as follows: the MnO nanowire material wrapped by the nitrogen-doped carbon film has a stable structure and good conductivity, has excellent cycle stability, rate capability and coulombic efficiency when being used as a lithium battery material, can be produced in a large scale (the yield is up to 79%), and is suitable for industrial production.
Drawings
FIG. 1 shows MnO obtained in example 1 2 MnO wrapped by nanowire and polydopamine film 2 SEM picture of nanowires, wherein: (a) Is MnO 2 SEM image of the nanowire; (b) Coating MnO on polydopamine film 2 SEM image of nanowires.
Fig. 2 is a TEM picture of MnO nanowires wrapped in an N-doped carbon film obtained in example 1, wherein (a) and (b) are both pictures of MnO nanowires wrapped in an N-doped carbon film, and (b) is a partially enlarged view of (a).
FIG. 3 is a graph of MnO wrapped in polydopamine film obtained in example 1 2 Nanowire and N-doped carbon film wrappingXRD spectra of MnO nanowires, wherein: (a) Coating MnO with polydopamine film 2 A nanowire XRD spectrum; and (b) an XRD spectrum of the MnO nanowire wrapped by the N-doped carbon film.
Fig. 4 is a TEM and elemental mapping diagram of MnO nanowires coated with an N-doped carbon film obtained in example 1, wherein: (a) And (b) are TEM and mapping images of MnO nanowires wrapped by the N-doped carbon film respectively; and (C) to (f) are respectively Mn, O, C and N element analysis diagrams.
Fig. 5 is an XPS spectrum of the MnO nanowires encapsulated by an N-doped carbon film obtained in example 1, wherein: (a) a Mn2p spectral peak corresponding to the nanowire; (b) a spectral peak corresponding to nanowire C1 s; (c) an O1s peak corresponding to the nanowire; and (d) the N1s spectrum peak of the corresponding nanowire.
Fig. 6 is a lithium battery performance test of the MnO nanowire wrapped by the N-doped carbon film obtained in example 1, wherein: (a) is a Cyclic Voltammogram (CV) graph; (b) is a rate performance graph; (c) is a constant current charging and discharging (GCD) diagram; (d) The test chart of the cycling stability is specifically a chart of the charge and discharge capacitance and the coulomb efficiency in the process of 1000 times of charge and discharge.
Fig. 7 shows the alternating current impedance (EIS) of the MnO nanowires wrapped with the N-doped carbon film obtained in example 1.
Detailed Description
The above objects, features and advantages of the present invention will be described in detail below with reference to the accompanying drawings. The embodiment is performed on the premise of the technical scheme of the invention, and specifically includes detailed implementation and operation processes. The technical spirit of the present invention includes but is not limited to the embodiment, the present invention can be implemented by various materials different from the present invention, and those skilled in the art can make similar modifications without departing from the spirit of the present invention, so that the present invention is not limited by the specific implementation disclosed below.
Example 1
In this example, N-C @ MnO nanowires were prepared as follows:
(1) Preparation of MnO 2 Nanowire and method of manufacturing the same
0.39g of KMnO 4 Adding solid and 0.5mL of hydrochloric acid with the mass concentration of 36-38% into 45mL of deionized water, stirring by a glass rod to form a homogeneous solution, and pouring the homogeneous solution into a hydrothermal reaction kettleAnd the inside is sealed. And then transferring the mixture into a constant-temperature blast box, raising the temperature to 160 ℃ at the temperature rise rate of 5 ℃/min, preserving the temperature for 10h, and naturally cooling the mixture to the room temperature. And attaching the reaction product to the wall and the bottom of the reaction kettle, sucking the aqueous solution, shoveling the product down by using a medicine spoon, and dripping deionized water to form a turbid liquid. Finally, centrifugally collecting the mixture by using deionized water and acetone (centrifugal force is 4000Xg, centrifugal time is 5min, centrifugation is carried out for 3 times, the mixture is firstly centrifuged by using deionized water once and then centrifuged by using acetone twice), and then drying the mixture for 5 hours at the temperature of 60 ℃ in a constant-temperature drying oven to obtain MnO 2 And (3) a nanowire precursor.
(2) MnO wrapped by polydopamine film 2 Nanowire and method of manufacturing the same
MnO obtained in the step (1) 2 0.12g and 0.26g of the nanowire precursor are dispersed in 150mL of a mixed solution of deionized water and ethanol (the volume ratio of water to ethanol is 2: 1), 0.2mL of ammonia water with the mass concentration of 25-28% is added, and the mixture is magnetically stirred for 12 hours, so that the dopamine hydrochloride is mixed with MnO for 12 hours 2 The nano-wire is taken as a template, polymerized into a polydopamine film and wrapped in MnO 2 MnO wrapped by polydopamine film is obtained outside the nanowire 2 The nano wires are extracted by acetone (centrifugal force 4000Xg, centrifugal time 5min, 3 times of centrifugation), collected by centrifugation and then dried for 5 hours in a constant temperature drying oven at 60 ℃.
(3) Preparation of N-C @ MnO nanowire
MnO wrapping the polydopamine film obtained in the step (2) 2 Annealing the nanowires by using a CVD tube furnace: mnO wrapping polydopamine film 2 The nano wire is arranged in the quartz boat and is arranged in the center of the quartz tube. Introducing nitrogen of 300sccm and washing for 10min. Then, under the condition of 150sccm nitrogen, the temperature is increased to 700 ℃ at the temperature increasing speed of 15 ℃/min, the temperature is kept at 700 ℃ for 2.5h, and then the cover of the tube furnace is opened and the temperature is rapidly reduced. Thus obtaining the target product N-C @ MnO nanowire.
FIG. 1 shows MnO obtained in this example 2 Nanowires (FIG. 1 (a)) and MnO wrapped with polydopamine film 2 The SEM image of the nanowire (FIG. 1 (b)) shows that the final product has a distinct nanowire shape, relatively uniform size and a non-smooth surface, which is beneficial to the adsorption of reactants.
FIG. 2 shows the present embodimentIn the TEM image of the obtained N-C @ MnO nanowire, a carbon film is clearly seen to wrap the manganese oxide nanowire. Due to MnO in the annealing process 2 Part of O element in the nanowire is removed (or is removed with C to form oxycarbide), so that the surface of the nanowire is uneven. In fig. 2 (a), the partial spherical nanoparticles at the edge position are carbon spheres, and are formed by annealing polydopamine spheres formed by excess dopamine hydrochloride under alkaline environment and magnetic stirring. These carbon spheres can improve the conductivity of N-C @ MnO nanowires.
FIG. 3 shows MnO wrapped with the polydopamine film obtained in the present example 2 XRD (X-ray diffraction) spectrums of MnO nanowires wrapped by the nanowires and the N-doped carbon film, wherein: (a) Coating MnO on polydopamine film 2 MnO of nanowire and standard PDF card 44-0141 2 An XRD contrast map; (b) The MnO XRD comparison spectrum of the MnO nanowire wrapped by the N-doped carbon film and the standard PDF card 71-1177 is shown. MnO can be clearly seen 2 The XRD characteristic peaks 2 theta =18.107, 28.841, 37.522, 39.010, 49.864, 56.372 and the like of the nanowires are consistent with a standard map, and the XRD characteristic peaks 2 theta =34.840, 40.492, 58.618, 70.091 and 73.664 of the MnO nanowires are consistent with the standard map, which respectively can prove to be MnO 2 And MnO materials.
FIG. 4 is a TEM element mapping diagram of the N-C @ MnO nanowire obtained in the present example, wherein: (a) TEM of N-C @ MnO nanowires; (b) is a face-scan mapping graph of all elements; (c) - (f) respectively representing Mn, O, C and N element mapping graphs of the N-C @ MnO nanowires. The uniform distribution of Mn, O, C and N elements in the N-C @ MnO nanowire can be clearly seen from the element mapping graph in FIG. 4.
FIG. 5 is an XPS spectrum of N-C @ MnO nanowires obtained in this example. (a) Is a Mn2p orbital characteristic peak of Mn element, wherein Mn2p is respectively 653.8eV and 642.3eV 1/2 、Mn2p 3/2 A spectral peak; 646.4eV is the peak of oscillation for MnO, consistent with data in the literature. The characterization of XRD is combined, and the final product is MnO nanowire. (b) Is the peak spectrum of the C element, wherein 284.8eV, 286.9eV and 288.3eV correspond to the peaks of C-C, C-O-C/C-O and O-C = O respectively, and are consistent with the XPS characteristic peak of the carbon material in the literature. (c) Is the peak spectrum of O element, wherein, the 531.1eV and 533.3eV correspond to the metal oxide and the carbon nitrogen oxide respectivelyPeaks, indicating that elemental oxygen is present in the form of manganese oxide and carbon oxynitride. (d) The peak spectrum of the N element is shown, wherein 398.4eV, 400.7eV and 403.5eV correspond to characteristic peaks of nitrides, and the N element is derived from dopamine hydrochloride, and in the dopamine hydrochloride, nitrogen element, carbon element and hydrogen element form bonds, so that partial nitrides still exist after annealing.
FIG. 6 is a lithium battery performance test of the N-C @ MnO nanowire obtained in the present example. The battery was prepared by mixing a sample of N-c @ mno with a conductive agent (acetylene black) and a binder (polyvinylidene fluoride) in a certain ratio (7. Uniformly coating the slurry on copper foil, drying in a vacuum oven for 10h, and cutting into small wafers (area of 1.13 cm) 2 ) And preparing a working electrode plate. Coin-type (LIR 2032) cells based on this material were prepared as half-cells in a glove box filled with argon. Celgard 2400 and lithium metal disks were used as separator and reference/counter electrode, the electrolyte was LiPF at a concentration of 1M 6 . The rate capability and the cycling stability are carried out on a battery test system (CT-3008a, NEWARE, shenzhen), and the test range is 0.01-3.00V. Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) were tested on the CHI 760E electrochemical workstation. (a) In the CV diagram, the oxidation and reduction peaks are visible, corresponding to the oxidation and reduction processes of MnO, respectively. (b) Showing a graph of rate performance at different currents (0.1-5.0 Ag) -1 ) The following charge and discharge properties. It can be seen that the specific capacitance gradually decreases with increasing current; but under the same current, the specific capacitance stabilizing effect is better; and returned to 0.1A · g again -1 After the current is obtained, the specific capacitance is relatively improved, and the speed performance of the N-C @ MnO nanowire serving as the lithium battery negative electrode material is better. (c) In a constant-current charging and discharging (GCD) diagram, a longer platform is formed in the first discharging process, and the platforms of the charging and discharging curves of a plurality of times are almost constant, so that the stability and the reversibility of the material are better. (d) The test chart is a cyclic stability test chart, in particular to a charge and discharge capacitance and coulombic efficiency chart in a 1000-time charge and discharge process. The current was 2 A.g in 1000 cycles -1 Specific capacitance of 350mA g -1 Left and right float, which shows better circulation stabilityAnd reversibility. The coulombic efficiency in 1000 cycles is more than or close to 100 percent, and the specific capacitance after 1000 cycles is 300 mA-g -1 Relative to the initial maximum 375mA g in the circulation process -1 And 80% of specific capacitance is reserved, which indicates that the material has better reversibility and longer cycle life.
The alternating current impedance (EIS) of the N-C @ MnO nanowire material is analyzed, as shown in FIG. 7, the fact that the material has smaller impedance after a cycle performance test is obviously shown, the transportation of current carriers is facilitated, and the conductivity is improved.
The present embodiment is performed under the condition of the claims of the present invention, and the technical content included in the present invention includes, but is not limited to, the above embodiments. Accordingly, the present embodiments are exemplary, and not limiting. Other oxide/non-oxide nanowire materials in the art, such as the oxide/non-oxide nanowire wrapped by the nitrogen-doped carbon film prepared according to the technical requirements of the present invention, should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material is characterized by comprising the following steps: firstly, preparing a manganese dioxide nanowire precursor by using a hydrothermal synthesis mode; then mixing the manganese dioxide nanowire precursor with dopamine hydrochloride in a water and ethanol solution dropwise added with ammonia water, and continuously magnetically stirring to prepare the manganese dioxide nanowire wrapped by the polydopamine film; and finally, annealing the manganese dioxide nanowire wrapped by the polydopamine film in an inert atmosphere to obtain the target product manganese monoxide nanowire wrapped by the N-doped C film, and marking the target product manganese monoxide nanowire as N-C @ MnO.
2. The preparation method of the nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material as claimed in claim 1, comprising the following steps:
(1) 0.39-0.50 g of KMnO 4 Adding 0.5mL of hydrochloric acid with the mass concentration of 36-38% into 45-60 mL of deionized water, stirring by a glass rod to form a homogeneous solution, pouring the homogeneous solution into a hydrothermal reaction kettle, sealing a cover, transferring the hydrothermal reaction kettle into a constant-temperature air blowing box, heating to 160 ℃, preserving heat for 10 hours,naturally cooling to room temperature; the reaction product is sequentially centrifuged, collected and dried by deionized water and acetone to obtain MnO 2 A nanowire precursor;
(2) MnO obtained in the step (1) 2 Dispersing 0.12g of nanowire precursor and 0.13-0.26g of dopamine hydrochloride into 150mL of deionized water and ethanol mixed solution, adding 0.1-0.5mL of ammonia water with the mass concentration of 25-28%, and magnetically stirring for 5-12h to ensure that the dopamine hydrochloride is in MnO form 2 The nano-wire is taken as a template, polymerized into a polydopamine film and wrapped in MnO 2 MnO wrapped by polydopamine film is obtained outside the nanowire 2 Centrifuging the nanowires with acetone, collecting, and drying;
(3) MnO wrapping the polydopamine film obtained in the step (2) in a CVD tube furnace under inert atmosphere 2 And (3) annealing the nanowires for 2-3 h at 600-700 ℃, then opening the cover of the tube furnace, and rapidly cooling to obtain the target product of the manganese monoxide nanowires wrapped by the N-doped carbon film.
3. The method for preparing the nitrogen-doped carbon film-coated manganese monoxide nanowire lithium battery material according to claim 2, wherein the method comprises the following steps: the hydrothermal reaction kettle used in the step (1) is a polytetrafluoroethylene substrate, and the volume is 100mL.
4. The preparation method of the nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material as claimed in claim 2, wherein the preparation method comprises the following steps: in the step (1) and the step (2), the centrifugal force of the centrifugation is 4000 Xg-6000 Xg, the single centrifugation time is 5min, and the centrifugation is not less than 3 times.
5. The preparation method of the nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material as claimed in claim 2, wherein the preparation method comprises the following steps: in the step (3), the temperature rise speed of the CVD tube furnace is 10-20 ℃/min.
6. The preparation method of the nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material as claimed in claim 2, wherein the preparation method comprises the following steps: in the step (3), the inert atmosphere is nitrogen or argon.
7. The nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material prepared by the preparation method of any one of claims 1 to 6.
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