WO2024087567A1 - 一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料及其制备方法 - Google Patents

一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料及其制备方法 Download PDF

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WO2024087567A1
WO2024087567A1 PCT/CN2023/091993 CN2023091993W WO2024087567A1 WO 2024087567 A1 WO2024087567 A1 WO 2024087567A1 CN 2023091993 W CN2023091993 W CN 2023091993W WO 2024087567 A1 WO2024087567 A1 WO 2024087567A1
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nanowire
wrapped
nitrogen
preparation
doped carbon
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French (fr)
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杨秋云
王娜
樊晓宇
谢珂
吕成云
陈圆
刘梓宁
张岚
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安徽科技学院
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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
    • 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

Definitions

  • 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 nanomaterials.
  • Manganese oxide nanomaterials including MnO 2 , MnO, Mn 2 O 3 , Mn 3 O 4
  • their derivatives have attracted wide attention in the fields of biomedicine, lithium batteries, supercapacitors, electrocatalytic hydrogen evolution, environmental treatment, zinc batteries, photocatalysis, etc. due to their adjustable structure and morphology, unique physical and chemical properties, abundant resources, environmental friendliness and good biosafety.
  • manganese oxides have high theoretical specific capacities (the theoretical specific capacities of MnO 2 , Mn 2 O 3 , MnO and Mn 3 O 4 in lithium-ion batteries are 1233, 1018, 756 and 937 mAhg -1 , respectively), and are very promising alternative negative electrode materials.
  • pure manganese oxides are not directly used as battery electrode materials. On the one hand, such materials have poor conductivity. On the other hand, such materials expand and fragment during the charge and discharge process, and stack together, resulting in significantly reduced performance and poor cycle stability. In addition, industrial production also limits the use of such materials.
  • the present invention provides a nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material with high chemical stability, good rate performance, excellent cycle stability and coulombic efficiency, and a preparation method thereof.
  • a method for preparing a nitrogen-doped carbon film-wrapped manganese monoxide nanowire lithium battery material comprises the following steps Steps: preparing a manganese dioxide nanowire precursor by hydrothermal synthesis; mixing the obtained manganese dioxide nanowire precursor and dopamine hydrochloride in a water and ethanol solution to which ammonia water is added, and continuously stirring with magnetic force to prepare a polydopamine film-wrapped manganese dioxide nanowire; annealing the obtained polydopamine film-wrapped manganese dioxide nanowire under an inert atmosphere to obtain the target product, nitrogen-doped carbon film-wrapped manganese monoxide nanowire, which is recorded as NC@MnO.
  • the preparation method comprises the following steps:
  • step (2) dispersing 0.12 g of the MnO2 nanowire precursor obtained in step (1) and 0.13-0.26 g of dopamine hydrochloride in 150 mL of a mixed solution of deionized water and ethanol, adding 0.1-0.5 mL of 25-28% ammonia water, and magnetically stirring for 5-12 h to allow the dopamine hydrochloride to polymerize into a polydopamine film with the MnO2 nanowire as a template and wrap around the MnO2 nanowire to obtain MnO2 nanowires wrapped with a polydopamine film, centrifuging with acetone, collecting, and drying;
  • step (3) In a CVD tube furnace, under an inert atmosphere (nitrogen or argon), annealing the polydopamine film-wrapped MnO2 nanowires obtained in step (2) at 600-700°C for 2-3h, then opening the lid of the tube furnace and rapidly cooling the temperature to obtain the target product, nitrogen-doped carbon film-wrapped manganese monoxide nanowires.
  • an inert atmosphere nitrogen or argon
  • the hydrothermal reaction kettle is a polytetrafluoroethylene substrate with a volume of 100 mL.
  • the centrifugal force of the centrifugation is 4000 ⁇ g to 6000 ⁇ g, the single centrifugation time is 5 min, and the centrifugation is performed no less than 3 times.
  • the heating rate of the CVD tube furnace is 10 to 20° C./min.
  • the method for preparing N-C@MnO nanowire material of the present invention is simple, mature and low-cost, and the obtained material has good chemical stability, high energy density, excellent cycle stability and coulombic efficiency.
  • the NC@MnO nanowire lithium battery material synthesized by the present invention improves the service life and cycle stability of the MnO material.
  • the carbon film protects and supports manganese monoxide and promotes the transmission of charge.
  • Li ions The transport of lithium ions is outside the carbon film, between the nanowires, and not in contact with manganese oxide. The movement of lithium ions has no effect on the structure of manganese oxide.
  • the volume expansion and fragmentation of MnO occur inside the carbon film, and it does not collapse into a pile like pure MnO.
  • the doping of nitrogen in the carbon film improves the conductivity of the material.
  • a three-dimensional porous structure is formed between the nanowires, providing a transmission path for lithium ions and improving the conductivity.
  • the advantages of the nanowires obtained by the present invention are that the MnO nanowire material wrapped by the nitrogen-doped carbon film has a stable structure and good conductivity. As a lithium battery material, it has excellent cycle stability, rate performance and coulombic efficiency, and can be mass-produced (with a yield of up to 79%), which is suitable for industrial production.
  • FIG1 is a SEM image of MnO2 nanowires and polydopamine membrane-wrapped MnO2 nanowires obtained in Example 1, wherein: (a) is a SEM image of MnO2 nanowires; (b) is a SEM image of polydopamine membrane-wrapped MnO2 nanowires;
  • FIG2 is a TEM image of N-doped carbon film-wrapped MnO nanowires obtained in Example 1, wherein (a) and (b) are images of N-doped carbon film-wrapped MnO nanowires, and (b) is a partial enlarged image of (a);
  • FIG3 is an XRD pattern of polydopamine film-wrapped MnO 2 nanowires and N-doped carbon film-wrapped MnO nanowires obtained in Example 1, wherein: (a) is an XRD pattern of polydopamine film-wrapped MnO 2 nanowires; (b) is an XRD pattern of N-doped carbon film-wrapped MnO nanowires;
  • FIG4 is a TEM and element mapping image of N-doped carbon film wrapped MnO nanowires obtained in Example 1, wherein: (a) and (b) are TEM and mapping images of N-doped carbon film wrapped MnO nanowires, respectively; (c)-(f) are element analysis images of Mn, O, C, and N, respectively;
  • FIG5 is an XPS spectrum of the N-doped carbon film wrapped MnO nanowires obtained in Example 1, wherein: (a) corresponds to the Mn2p peak of the nanowire; (b) corresponds to the C1s peak of the nanowire; (c) corresponds to the O1s peak of the nanowire; (d) corresponds to the N1s peak of the nanowire;
  • FIG6 is a performance test of a lithium battery of N-doped carbon film wrapped MnO nanowires obtained in Example 1, wherein: (a) is a cyclic voltammetry (CV) curve; (b) is a rate performance graph; (c) is a constant current charge and discharge (GCD) graph; (d) is a cycle stability test graph, specifically a graph of charge and discharge capacitance and coulomb efficiency during 1000 charge and discharge cycles;
  • CV cyclic voltammetry
  • GCD constant current charge and discharge
  • FIG. 7 is an electrochemical impedance spectroscopy (EIS) of the N-doped carbon film wrapped MnO nanowires obtained in Example 1.
  • N-C@MnO nanowires were prepared according to the following steps:
  • 0.39g KMnO 4 solid and 0.5mL hydrochloric acid with a mass concentration of 36-38% were added to 45mL deionized water, stirred with a glass rod to form a homogeneous solution, poured into a hydrothermal reactor and sealed. Then transferred to a constant temperature blower, heated to 160°C at a heating rate of 5°C/min, kept warm for 10h, and naturally cooled to room temperature. The reaction product adhered to the wall and bottom of the reactor, the aqueous solution was removed, and the product was shoveled off with a medicine spoon while deionized water was added dropwise to form a suspension.
  • deionized water and acetone were centrifuged and collected (centrifugal force 4000xg, centrifugal time 5min, centrifuged 3 times, first centrifuged once with deionized water, and then centrifuged twice with acetone), and then dried at 60°C in a constant temperature drying oven for 5h to obtain a MnO 2 nanowire precursor.
  • 0.12 g of the MnO2 nanowire precursor obtained in step (1) and 0.26 g of dopamine hydrochloride are dispersed in a mixed solution of 150 mL of deionized water and ethanol (water:ethanol volume ratio is 2:1), 0.2 mL of ammonia water with a mass concentration of 25-28% is added, and magnetic stirring is performed for 12 hours to allow dopamine hydrochloride to polymerize into a polydopamine film using the MnO2 nanowire as a template, and wrap the MnO2 nanowire to obtain MnO2 nanowires wrapped with a polydopamine film, which is extracted with acetone (centrifugal force 4000xg, centrifugal time 5min, centrifugation 3 times), collected by centrifugation, and then dried at 60°C in a constant temperature drying oven for 5 hours.
  • acetone centrifugal force 4000xg, centrifugal time 5min, centrifugation 3 times
  • Anneal the polydopamine film-wrapped MnO2 nanowires obtained in step (2) using a CVD tube furnace First, place the polydopamine film-wrapped MnO2 nanowires in a quartz boat and place it in the center of the quartz tube. First, pass 300sccm of nitrogen and purge for 10 minutes. Then, under 150sccm of nitrogen, heat up to 700°C at a rate of 15°C/min, maintain at 700°C for 2.5 hours, then open the lid of the tube furnace and cool it down quickly. The target product NC@MnO nanowires is obtained.
  • Figure 1 shows the MnO 2 nanowires (Figure 1(a)) and the MnO 2 nanowires wrapped with polydopamine membranes obtained in this example. SEM image of the nanowires ( Figure 1(b)), in which it can be seen that the final product has a distinct nanowire morphology, relatively uniform size, and a rough surface, which is conducive to the adsorption of reactants.
  • FIG2 is a TEM image of the NC@MnO nanowires obtained in this embodiment. It can be clearly seen that the manganese oxide nanowires are wrapped with a layer of carbon film. Due to the removal of some O elements in MnO2 (or the removal of carbon oxides formed with C) during the annealing process, the surface of the nanowires is uneven. In FIG2(a), there are also some spherical nanoparticles at the edge, which are carbon spheres, which are formed by annealing of polydopamine spheres formed by excess dopamine hydrochloride in an alkaline environment and magnetic stirring. These carbon spheres can improve the conductivity of NC@MnO nanowires.
  • Figure 3 is the XRD spectrum of the polydopamine film wrapped MnO2 nanowire and the N-doped carbon film wrapped MnO nanowire obtained in this embodiment, wherein: (a) is the MnO2 XRD comparison spectrum of the polydopamine film wrapped MnO2 nanowire and the standard PDF card 44-0141; (b) is the MnOXRD comparison spectrum of the N-doped carbon film wrapped MnO nanowire and the standard PDF card 71-1177. It can be clearly seen that the XRD characteristic peaks of the MnO2 nanowire are consistent with the standard spectrum, and the XRD characteristic peaks of the MnO nanowire are consistent with the standard spectrum, which can be proved to be MnO2 and MnO materials respectively.
  • Figure 4 is a TEM element mapping diagram of the N-C@MnO nanowire obtained in this embodiment, where: (a) is the TEM of the N-C@MnO nanowire; (b) is the surface scan mapping diagram of all elements; (c)-(f) are the Mn, O, C, and N element mapping diagrams of the N-C@MnO nanowire, respectively. From the element mapping diagram in Figure 4, it can be clearly seen that the Mn, O, C, and N elements in the N-C@MnO nanowire are evenly distributed.
  • Figure 5 is the XPS spectrum of NC@MnO nanowires obtained in this example.
  • (a) is the Mn2p orbital characteristic peak of the Mn element, where 653.8eV and 642.3eV are the Mn2p 1/2 and Mn2p 3/2 peaks respectively; 646.4eV is the vibration peak of MnO, which is consistent with the data in the literature. Combined with the characterization of XRD, it is also shown that the final product is MnO nanowires.
  • (c) is the peak spectrum of the O element, where 531.1eV and 533.3eV correspond to metal oxide and carbon nitrogen oxide peaks respectively, indicating that the oxygen element exists in the form of manganese oxide and carbon nitrogen oxide.
  • (d) is the N element peak spectrum, where 398.4 eV, 400.7 eV, and 403.5 eV correspond to the characteristic peaks of nitrides. Since the N element comes from dopamine hydrochloride, in dopamine hydrochloride, the nitrogen element forms a bond with the carbon element and the hydrogen element. Therefore, some nitrides still exist after annealing.
  • FIG6 is a lithium battery performance test of NC@MnO nanowires obtained in this embodiment.
  • the battery preparation process is as follows: NC@MnO sample is mixed with conductive agent (acetylene black) and binder (polyvinylidene fluoride) in a certain ratio (7:2:1wt%), and dispersed in n-methylpyrrolidone (NMP) to make a slurry. The above slurry is evenly coated on copper foil, dried in a vacuum oven for 10 hours, and cut into small discs (area 1.13cm2 ) to prepare working electrode sheets.
  • a coin-type (LIR2032) battery based on this material is prepared in an argon-filled glove box as a half-cell.
  • Celgard2400 and lithium metal disk are used as diaphragms and reference/counter electrodes, and the electrolyte is LiPF6 with a concentration of 1M.
  • the rate performance and cycle 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 a CHI760E electrochemical workstation.
  • (a) is a CV graph, in which oxidation peaks and reduction peaks can be seen, corresponding to the oxidation and reduction processes of MnO, respectively.
  • (b) is a rate performance graph, showing the charge and discharge performance at different currents (0.1-5.0Ag -1 ).
  • the specific capacitance gradually decreases with the increase of current; but at the same current, the specific capacitance has a good stability effect; and after returning to the current of 0.1A ⁇ g -1 again, the specific capacitance is relatively improved, indicating that the rate performance of NC@MnO nanowires as lithium battery negative electrode materials is good.
  • GCD constant current charge and discharge
  • (d) is a cyclic stability test graph, specifically the charge and discharge capacitance and coulomb efficiency graphs during 1000 charge and discharge cycles.
  • the current was 2A ⁇ g -1
  • the specific capacitance fluctuated around 350mA ⁇ g -1 , indicating good cycle stability and reversibility.
  • the coulomb efficiency was greater than or close to 100%
  • the specific capacitance after 1000 cycles was 300mA ⁇ g -1 , which was 80% of the initial maximum value of 375mA ⁇ g -1 during the relative cycle process, indicating that the material has good reversibility and a long cycle life.
  • the present invention analyzes the electrochemical impedance spectroscopy (EIS) of the N-C@MnO nanowire material, as shown in FIG7 . It is obvious that the material has a smaller impedance after the cycle performance test, which is beneficial to the transport of carriers and improves the conductivity.
  • EIS electrochemical impedance spectroscopy

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Abstract

一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料的制备方法，包括以下步骤：利用水热合成方式制备二氧化锰纳米线前驱体；将所得到的二氧化锰纳米线前驱体与盐酸多巴胺在滴加氨水的水与乙醇溶液中混合，并持续磁力搅拌，制备得到聚多巴胺膜包裹的二氧化锰纳米线；将所得到的聚多巴胺膜包裹的二氧化锰纳米线在惰性气氛下退火，获得氮掺杂碳膜包裹的一氧化锰纳米线(N-C@MnO)。

Description

一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料及其制备方法
本申请要求于2022年10月28日提交中国专利局、申请号为CN202211340300.5、发明名称为“一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料及其制备方法，属于纳米材料技术领域。
背景技术
氧化锰纳米材料(MnOx，包括MnO2、MnO、Mn2O3、Mn3O4)及其衍生物，由于其可调的结构和形貌、独特的物理和化学性质、丰富的资源、环境友好性和良好的生物安全性，在生物医学、锂电池、超级电容器、电催化析氢、环境处理、锌电池、光催化等领域的应用受到了广泛关注。特别是在锂电池领域，锰氧化物具有较高的理论比容量(锂离子电池中MnO2、Mn2O3、MnO和Mn3O4的理论比容量分别为1233、1018、756和937mAhg-1)，是极有前途的替代负极材料。然而，通常情况下，纯锰氧化物不会直接用作电池电极材料，一方面该类材料导电性差，另一方面该类材料在充放电过程中体积膨胀和碎片化，并堆叠在一起，导致性能显著降低，循环稳定性差；此外，产业化生产也限制了该类材料的使用。为了解决前两类问题，已经提出通过改善锰氧化物的结构，来提高此类材料的导电性、循环稳定性和使用寿命，例如分层多孔MnO/碳微球材料、δ-MnO2多孔复合材料和包覆在碳壳中的多孔Mn2O3纳米立方材料。
发明内容
基于上述现有技术所存在的问题，本发明提供了一种化学稳定性高、速率性能好、循环稳定性和库伦效率优异的氮掺杂碳膜包裹的一氧化锰纳米线锂电材料及其制备方法。
本发明为实现目的，采用如下技术方案：
一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料的制备方法，包括以下 步骤：利用水热合成方式制备二氧化锰纳米线前驱体；将所得到的二氧化锰纳米线前驱体与盐酸多巴胺混合在滴加氨水的水与乙醇溶液中，并持续磁力搅拌，制备得到聚多巴胺膜包裹的二氧化锰纳米线；将所得到的聚多巴胺膜包裹的二氧化锰纳米线在惰性气氛下退火，即获得目标产物氮掺杂碳膜包裹的一氧化锰纳米线，记为N-C@MnO。
优选的，所述制备方法包括以下步骤：
(1)将0.39～0.50gKMnO4和0.5mL质量浓度为36～38％的盐酸加入到45～60mL去离子水中，玻璃棒搅拌形成均质溶液，倒入水热反应釜内并封盖，然后转移到恒温鼓风箱中，升温至160℃，保温10h，自然冷却到室温；反应产物用去离子水和丙酮依次离心、收集，干燥，得到MnO2纳米线前驱体；
(2)将步骤(1)所得MnO2纳米线前驱体0.12g与0.13-0.26g盐酸多巴胺分散于150mL去离子水和乙醇混合溶液中，加入0.1-0.5mL质量浓度为25～28％的氨水，磁力搅拌5-12h，使盐酸多巴胺以MnO2纳米线为模板，聚合成聚多巴胺膜并包裹在MnO2纳米线外，得到聚多巴胺膜包裹的MnO2纳米线，用丙酮离心、收集，干燥；
(3)在CVD管式炉中，惰性气氛(氮气或氩气)下，将步骤(2)所得聚多巴胺膜包裹的MnO2纳米线600～700℃退火2～3h，之后打开管式炉的盖子，迅速降温，即获得目标产物氮掺杂碳膜包裹的一氧化锰纳米线。
优选的，步骤(1)中，所述水热反应釜为聚四氟乙烯衬底，容积为100mL。
优选的，步骤(1)与步骤(2)中，所述离心的离心力为4000×g～6000×g、单次离心时间为5min，离心不少于3次。
优选的，步骤(3)中，CVD管式炉的升温速度为10～20℃/min。
本发明的有益效果在于：
1、本发明制备N-C@MnO纳米线材料的方法简单成熟、成本低，获得材料化学稳定性好、能量密度较高、循环稳定性和库伦效率优异。
2、本发明合成出的N-C@MnO纳米线锂电材料，提高了MnO材料的使用寿命和循环稳定性。碳膜对一氧化锰具有保护和支撑作用，促进了电荷的传输。利用本发明所得的负极材料制备的锂电池在充放电过程中，Li离 子的输运是在碳膜外，在纳米线之间，不与锰氧化物接触。锂离子的移动对氧化锰的结构没有影响。MnO的体积膨胀和碎裂发生在碳膜内部，没有像纯MnO那样坍缩成一堆。碳膜中氮的掺杂提高了材料的导电性。纳米线之间形成了三维多孔结构，为锂离子提供了传输路径，同时提高了导电性能。
3、本发明所获得的纳米线的优点在于：氮掺杂碳膜包裹的MnO纳米线材料结构稳定、导电性好，作为锂电材料具有优异的循环稳定性、倍率性能和库伦效率，且可量产(产率高达79％)，适用于工业化生产。
附图说明
图1为实施例1所得MnO2纳米线、聚多巴胺膜包裹MnO2纳米线的SEM图片，其中：(a)为MnO2纳米线SEM图；(b)为聚多巴胺膜包裹MnO2纳米线SEM图；
图2为实施例1所得N掺杂碳膜包裹MnO纳米线的TEM图片，其中(a)、(b)均为N掺杂碳膜包裹MnO纳米线图片，(b)是(a)的局部放大图；
图3为实施例1所得聚多巴胺膜包裹MnO2纳米线及N掺杂碳膜包裹MnO纳米线的XRD图谱，其中：(a)为聚多巴胺膜包裹MnO2纳米线XRD图谱；(b)为N掺杂碳膜包裹MnO纳米线XRD图谱；
图4为实施例1所得N掺杂碳膜包裹MnO纳米线的TEM和元素mapping图，其中：(a)、(b)分别为N掺杂碳膜包裹MnO纳米线的TEM和mapping图；(c)-(f)分别为Mn、O、C、N元素分析图；
图5为实施例1所得N掺杂碳膜包裹MnO纳米线的XPS图谱，其中：(a)对应纳米线的Mn2p谱峰；(b)对应纳米线C1s的谱峰；(c)对应纳米线的O1s谱峰；(d)对应纳米线的N1s谱峰；
图6为实施例1所得N掺杂碳膜包裹MnO纳米线的锂电池性能测试，其中：(a)为循环伏安曲线(CV)图；(b)为倍率性能图；(c)为恒稳电流充放电(GCD)图；(d)为循环稳定性测试图，具体为1000次充放电过程中充、放电电容及库伦效率图；
图7为实施例1所得N掺杂碳膜包裹MnO纳米线的交流阻抗(EIS)。
具体实施方式
下面结合具体实施例和附图，对本发明的上述目的、特征和优点进行说明。本实施例是在上述发明技术方案为前提下进行的，具体包括详细的实施方式和操作过程。本发明的技术内涵包括但不限于本实施例，本发明能够以多种不同于本发明的材料来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
实施例1
本实施例按如下步骤制备N-C@MnO纳米线：
(1)制备MnO2纳米线
将0.39gKMnO4固体、0.5mL质量浓度为36～38％的盐酸加入到45mL去离子水中，玻璃棒搅拌形成均质溶液，倒入水热反应釜内并封盖。随后转移到恒温鼓风箱中，以5℃/min的升温速率升温至160℃，保温10h，自然冷却到室温。反应产物附着在反应釜壁和底部，把水溶液吸除，一边用药勺将产物铲下，一边滴加去离子水形成悬浊液。最终用去离子水和丙酮离心收集(离心力4000xg，离心时间5min，离心3次，先用去离子水离心一次，再用丙酮离心两次)，随后在恒温干燥箱内60℃干燥5h，获得MnO2纳米线前驱体。
(2)聚多巴胺膜包裹的MnO2纳米线
将步骤(1)所得MnO2纳米线前驱体0.12g、0.26g盐酸多巴胺分散于150mL去离子水和乙醇(水：乙醇体积比为2:1)混合溶液中，加入0.2mL质量浓度为25～28％的氨水，磁力搅拌12h，使盐酸多巴胺以MnO2纳米线为模板，聚合成聚多巴胺膜，包裹在MnO2纳米线外，获得聚多巴胺膜包裹的MnO2纳米线，用丙酮提取(离心力4000xg，离心时间5min，离心3次)、离心收集，随后在恒温干燥箱内60℃干燥5h。
(3)制备N-C@MnO纳米线
将步骤(2)所得聚多巴胺膜包裹的MnO2纳米线用CVD管式炉退火：首先将聚多巴胺膜包裹的MnO2纳米线盛放在石英舟内，并置于石英管中心位置。先通300sccm的氮气，洗气10min。随后在150sccm的氮气条件下，以15℃/min的升温速度升温至700℃，在700℃保持2.5h，之后打开管式炉的盖子，迅速降温。即获得目标产物N-C@MnO纳米线。
图1为本实施例所得MnO2纳米线(图1(a))和聚多巴胺膜包裹的MnO2 纳米线(图1(b))的SEM图，图中可以看到最终产物具有明显的纳米线形态，尺寸相对均匀，表面不光滑，有利于反应物的吸附。
图2为本实施例所得N-C@MnO纳米线的TEM图，可以清楚的看见锰氧化物纳米线外有一层碳膜包裹。由于退火过程中MnO2中的部分O元素脱去(或与C形成碳氧化合物脱去)，导致纳米线表面凹凸不平。图2(a)中边缘位置还有部分球型纳米颗粒是碳球，是多余的盐酸多巴胺在碱性环境和磁力搅拌下形成的聚多巴胺球通过退火形成的。这些碳球可以提高N-C@MnO纳米线的导电性。
图3为本实施例所得聚多巴胺膜包裹MnO2纳米线及N掺杂碳膜包裹MnO纳米线的XRD图谱，其中：(a)为聚多巴胺膜包裹MnO2纳米线与标准PDF卡片44-0141的MnO2XRD对比图谱；(b)为N掺杂碳膜包裹MnO纳米线与标准PDF卡片71-1177的MnOXRD对比图谱。可以明显的看出MnO2纳米线的XRD特征峰2θ＝18.107、28.841、37.522、39.010、49.864、56.372等与标准图谱一致，MnO纳米线的XRD特征峰2θ＝34.840、40.492、58.618、70.091、73.664与标准图谱一致，可分别证明是MnO2和MnO材料。
图4为本实施例所得N-C@MnO纳米线的TEM元素mapping图，其中：(a)是N-C@MnO纳米线的TEM；(b)是全部元素的面扫mapping图；(c)-(f)分别为N-C@MnO纳米线的Mn、O、C、N元素mapping图。从图4元素mapping图中可以清晰地看出N-C@MnO纳米线中Mn、O、C、N元素分布均匀。
图5为本实施例所得N-C@MnO纳米线XPS图谱。(a)是Mn元素的Mn2p轨道特征峰，其中653.8eV和642.3eV分别Mn2p1/2、Mn2p3/2谱峰；646.4eV是MnO的振激峰，与文献中的数据相符。结合XRD的表征，同时说明最终产物是MnO纳米线。(b)是C元素的峰谱图，其中284.8eV、286.9eV、288.3eV分别对应于C-C、C-O-C/C-O、O-C＝O峰，与文献中碳材料的XPS特征峰相符。(c)是O元素峰谱图，其中531.1eV和533.3eV处分别对应金属氧化物和炭氮氧化物峰，表明氧元素以氧化锰和炭氮氧化物的形式存在。(d)是N元素峰谱图，其中398.4eV、400.7eV、403.5eV对应于氮化物特征峰，由于N元素来自于盐酸多巴胺，在盐酸多巴胺中，氮元素与碳元素、氢元素之间成键，因此退火后，依然存有部分氮化物。
图6为本实施例所得N-C@MnO纳米线的锂电池性能测试。电池制备过程如下，将N-C@MnO样品与导电剂(乙炔黑)和粘结剂(聚偏氟乙烯)按一定比例(7:2:1wt％)混合，分散在n-甲基吡咯烷酮(NMP)中制成浆液。将上述浆液均匀涂在铜箔上，在真空烘箱中干燥10h后切成小圆片(面积1.13cm2)，制备工作电极片。在一个充满氩气的手套箱中制备基于这种材料的硬币型(LIR2032)电池，为半电池。采用Celgard2400和锂金属盘作为隔膜和参比/对电极，电解质是浓度为1M的LiPF6。倍率性能和循环稳定性在电池测试系统(CT-3008a，NEWARE，深圳)上进行，测试范围是0.01～3.00V。循环伏安法(CV)和电化学阻抗谱(EIS)在CHI760E电化学工作站上进行测试。(a)为CV图，图中可见氧化峰和还原峰，分别对应于MnO的氧化和还原过程。(b)为倍率性能图，在不同电流(0.1-5.0Ag-1)下的充放电性能。图中可见随着电流的增加，比电容逐渐下降；但在相同的电流下，比电容稳定效果较好；且再次回到0.1A·g-1的电流后，比电容相对有提升，说明作为锂电负极材料N-C@MnO纳米线的速率性能较好。(c)为恒稳电流充放电(GCD)图，第一次放电过程有一个较长的平台，随后几次充放电曲线的平台几乎一直，可见材料的稳定性和可逆性较好。(d)为循环稳定性测试图，具体为1000次充放电过程中充、放电电容及库伦效率图。在1000次的循环测试中，电流为2A·g-1，比电容在350mA·g-1左右浮动，说明具有较好的循环稳定性和可逆性。在1000次循环中库伦效率大于或接近100％，1000次循环后比电容为300mA·g-1，相对循环过程中初次最高值375mA·g-1，保留了80％的比电容，说明该材料的可逆性较好，具有较长的循环寿命。
本发明分析了N-C@MnO纳米线材料的交流阻抗(EIS)，如图7所示，明显看出循环性能测试后具有较小的阻抗，有利于载流子的输运，提升导电性能。
本实施例是在本发明权利要求条件下进行，本发明所包含的技术性内容包括但不限于上述实施例。因此，本实施例是示范性的，并非限制性的。本领域内其它氧化物/非氧化物纳米线材料，可依照本发明技术要求制备的氮掺杂碳膜包裹氧化物/非氧化物纳米线，应包含在本发明的保护范围之内。

Claims (11)

  1. 一种氮掺杂碳膜包裹的一氧化锰纳米线锂电材料的制备方法，其特征在于：利用水热合成方式制备二氧化锰纳米线前驱体；
    将所述二氧化锰纳米线前驱体与盐酸多巴胺混合在滴加氨水的水与乙醇溶液中，并持续磁力搅拌，制备得到聚多巴胺膜包裹的二氧化锰纳米线；
    将所述聚多巴胺膜包裹的二氧化锰纳米线在惰性气氛下退火，获得氮掺杂碳膜包裹的一氧化锰纳米线。
  2. 根据权利要求1所述的制备方法，其特征在于，包括以下步骤：
    (1)将0.39～0.50g KMnO4和0.5mL质量浓度为36～38％的盐酸加入到45～60mL去离子水中，玻璃棒搅拌形成均质溶液，倒入水热反应釜内并封盖，然后转移到恒温鼓风箱中，升温至160℃，保温10h，自然冷却到室温；反应产物用去离子水和丙酮依次离心、收集，干燥，得到MnO2纳米线前驱体；
    (2)将步骤(1)所得MnO2纳米线前驱体0.12g与0.13-0.26g盐酸多巴胺分散于150mL去离子水和乙醇混合溶液中，加入0.1-0.5mL质量浓度为25～28％的氨水，磁力搅拌5-12h，使盐酸多巴胺以MnO2纳米线为模板，聚合成聚多巴胺膜并包裹在MnO2纳米线外，得到聚多巴胺膜包裹的MnO2纳米线，用丙酮离心、收集，干燥；
    (3)在CVD管式炉中，惰性气氛下，将步骤(2)所得聚多巴胺膜包裹的MnO2纳米线600～700℃退火2～3h，之后打开管式炉的盖子，迅速降温，获得氮掺杂碳膜包裹的一氧化锰纳米线。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述水热反应釜为聚四氟乙烯衬底，容积为100mL。
  4. 根据权利要求2所述的制备方法，其特征在于，步骤(1)与步骤(2)中，所述离心的离心力为4000×g～6000×g、单次离心时间为5min，离心不少于3次。
  5. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中，所述CVD管式炉的升温速度为10～20℃/min。
  6. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中，所述惰性气氛为氮气或氩气。
  7. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，所述干燥的温度为60℃，所述干燥的时间为5h。
  8. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中，所述退火的升温速度为15℃/min。
  9. 一种权利要求1～8任意一项所述制备方法所制得的氮掺杂碳膜包裹的一氧化锰纳米线锂电材料。
  10. 根据权利要求9所述的氮掺杂碳膜包裹的一氧化锰纳米线锂电材料，其特征在于，所述氮掺杂碳膜包裹的一氧化锰纳米线锂电材料具有明显的纳米线形态，表面不光滑。
  11. 权利要求9～10任意一项所述氮掺杂碳膜包裹的一氧化锰纳米线锂电材料在锂电池中的应用。
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