CN107369825B - Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 title claims 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 87
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 39
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- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 25
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 25
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
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- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 6
- 229960003638 dopamine Drugs 0.000 abstract description 6
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明公开了一种氮掺杂碳包覆氧化锰锂离子电池复合负极材料及其制备方法与应用，该复合材料由纳米级氧化锰和多巴胺复合而成，其中氧化锰呈球形。该方法是将制备的球形氧化锰纳米颗粒与盐酸多巴胺进行混合，过滤洗涤、干燥后得到氧化锰和聚多巴胺的复合物；然后通过高温碳化将聚合层转化为氮掺杂的碳层；本发明所制备的氮掺杂碳包覆氧化锰（MnO@NC）锂离子电池复合负极材料结构稳定，导电性能好，作为锂离子电池负极材料具有优异的倍率性能和循环稳定性能；多巴胺的聚合只需要在室温和弱碱性条件下完成，所以成本低廉，能耗较低、控制方便、环境友好，适合锂离子电池实际应用，能够实现工业化规模生产。
The invention discloses a nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material and a preparation method and application thereof. The composite material is composed of nano-scale manganese oxide and dopamine, wherein the manganese oxide is spherical. The method comprises the following steps: mixing the prepared spherical manganese oxide nanoparticles with dopamine hydrochloride, filtering, washing and drying to obtain a composite of manganese oxide and polydopamine; then converting the polymerized layer into a nitrogen-doped carbon layer through high-temperature carbonization; The prepared nitrogen-doped carbon-coated manganese oxide (MnO@NC) composite anode material for lithium-ion batteries has stable structure and good electrical conductivity, and has excellent rate performance and cycle stability as anode materials for lithium-ion batteries; the polymerization of dopamine only requires It is completed under room temperature and weak alkaline conditions, so the cost is low, the energy consumption is low, the control is convenient, and the environment is friendly. It is suitable for practical application of lithium-ion batteries and can realize industrial scale production.
Description
技术领域technical field
本发明属于电化学领域，具体涉及一种氮掺杂碳包覆氧化锰锂离子电池复合负极材料及其制备方法与应用。The invention belongs to the field of electrochemistry, and in particular relates to a nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material and a preparation method and application thereof.
背景技术Background technique
二十一世纪科学技术发展的三大主题是能源、环境和信息，其中能源的匮乏以及严重的环境污染问题已经成为亟待解决的两大难题。为了应对以上两大难题，人们致力于发展太阳能、风能以及潮汐能等新型的绿色清洁能源，从而逐渐取代不可再生的且引起环境污染的化石类燃料。但是，现已经利用的大部分清洁能源都是非可控，以及间歇性的，这增加了能源储存与管理的成本，从而促使人们对储能材料进行大量的研究。The three major themes of science and technology development in the 21st century are energy, environment and information, among which the lack of energy and serious environmental pollution have become two major problems to be solved urgently. In order to cope with the above two major problems, people are committed to developing new green and clean energy such as solar energy, wind energy and tidal energy, so as to gradually replace non-renewable fossil fuels that cause environmental pollution. However, most of the clean energy that has been utilized is uncontrollable and intermittent, which increases the cost of energy storage and management, thus prompting a lot of research on energy storage materials.
传统的储能设备有铅酸电池、铬镍电池，其中，铅酸电池和铬镍电池的能量密度较低，还会引起环境污染，已经不能满足人们的需求。锂离子电池具有电压高、使用时间长、容量大、体积小、无记忆效应和安全性能好等优点，正逐渐取代铅酸电池和铬镍电池，已成为人们关注的焦点。随着便携式电子设备的迅速普及和电动汽车的迅猛发展，商用的天然石墨负极材料以及不能满足电动设备对能量密度和功率密度的要求，因此迫切需要高性能的锂离子负极材料。因此，开发新一代锂离子电池负极材料迫在眉睫。Traditional energy storage devices include lead-acid batteries and chrome-nickel batteries. Among them, lead-acid batteries and chrome-nickel batteries have low energy density and cause environmental pollution, which can no longer meet people's needs. Lithium-ion batteries have the advantages of high voltage, long service time, large capacity, small size, no memory effect and good safety performance. They are gradually replacing lead-acid batteries and chromium-nickel batteries and have become the focus of attention. With the rapid popularization of portable electronic devices and the rapid development of electric vehicles, commercial natural graphite anode materials cannot meet the energy density and power density requirements of electric devices, so high-performance lithium-ion anode materials are urgently needed. Therefore, the development of a new generation of lithium-ion battery anode materials is imminent.
过渡金属氧化物因其具有高的比容量，在锂离子电池领域得到广泛的研究。在众多的过渡金属氧化物中，氧化锰由于具有较高的初始比容量，以及环境友好和成本低等优点，使其成为有潜力的新一代锂离子电池负极材料。但是大多数的金属氧化物的电子导电率和离子导电率都比较差，从而导致其倍率性能较差。同时，在重复的充放电过程中，金属氧化物较大的体积变化会降低材料的循环稳定性。因此，如何提高金属氧化物的电子导电性和循环稳定性，是对研究人员的巨大挑战。目前，减小颗粒尺寸、包覆或者掺杂导电物质是提高材料电化学性能的主要手段。Transition metal oxides have been widely studied in the field of lithium-ion batteries due to their high specific capacity. Among many transition metal oxides, manganese oxide is a potential anode material for next-generation lithium-ion batteries due to its high initial specific capacity, environmental friendliness and low cost. However, most metal oxides have poor electronic and ionic conductivity, resulting in poor rate capability. At the same time, the large volume change of the metal oxide reduces the cycling stability of the material during repeated charge and discharge processes. Therefore, how to improve the electronic conductivity and cycling stability of metal oxides is a great challenge for researchers. At present, reducing particle size, coating or doping conductive substances are the main means to improve the electrochemical performance of materials.
本发明利用自然聚合法将氧化锰与盐酸多巴胺复合制备出氮掺杂碳包覆氧化锰（MnO@NC）复合材料，截止目前为止，还没有将球形氧化锰与聚多巴胺复合的相关报道。The present invention utilizes the natural polymerization method to compound manganese oxide and dopamine hydrochloride to prepare nitrogen-doped carbon-coated manganese oxide (MnO@NC) composite material. So far, there is no related report on compounding spherical manganese oxide and polydopamine.
发明内容SUMMARY OF THE INVENTION
针对目前传统的过渡金属氧化物锂离子电池负极材料导电性能和循环稳定性差等缺点，本发明提供一种氮掺杂碳包覆氧化锰（MnO@NC）锂离子电池负极材料及其制备方法与应用，该方法可改善材料的导电性和结构稳定性，从而提高负极材料的电化学性能。另外，本发明提供的氮掺杂碳包覆氧化锰（MnO@NC）的制备方法简单、成本较低、环境友好，能够促进规模锂离子电池负极材料的发展，有望大规模的工业化应用。In view of the shortcomings of the current traditional transition metal oxide lithium ion battery negative electrode materials such as poor electrical conductivity and cycle stability, the present invention provides a nitrogen-doped carbon-coated manganese oxide (MnO@NC) lithium ion battery negative electrode material, and a preparation method thereof and the like. Application, this method can improve the electrical conductivity and structural stability of the material, thereby improving the electrochemical performance of the negative electrode material. In addition, the preparation method of nitrogen-doped carbon-coated manganese oxide (MnO@NC) provided by the present invention is simple, low in cost, and environmentally friendly, which can promote the development of large-scale lithium-ion battery negative electrode materials, and is expected to be applied in large-scale industrialization.
本发明的目的通过以下技术方案实现。The object of the present invention is achieved through the following technical solutions.
一种氮掺杂碳包覆氧化锰锂离子电池复合负极材料的制备方法，包括以下步骤：A method for preparing a nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material, comprising the following steps:
1）将锰源与碳酸氢铵溶解在溶剂中，随后转入聚四氟乙烯内衬高压釜后进行水热处理，再离心洗涤，干燥，得到碳酸锰纳米球；1) Dissolve the manganese source and ammonium bicarbonate in a solvent, then transfer to a polytetrafluoroethylene-lined autoclave, perform hydrothermal treatment, and then centrifugally wash and dry to obtain manganese carbonate nanospheres;
2）将碳酸锰纳米球与盐酸多巴胺溶解在缓冲溶液中反应，再将反应产物固液分离，洗涤固体，干燥，得到碳酸锰/聚多巴胺复合材料；2) Dissolving the manganese carbonate nanospheres and dopamine hydrochloride in a buffer solution to react, then separating the reaction product from solid and liquid, washing the solid, and drying to obtain a manganese carbonate/polydopamine composite material;
3）将步骤2）所得碳酸锰/聚多巴胺复合材料在氮气气氛下进行煅烧处理，得到氮掺杂碳包覆氧化锰锂离子电池复合负极材料。3) calcining the manganese carbonate/polydopamine composite material obtained in step 2) in a nitrogen atmosphere to obtain a nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material.
作为优选，步骤1）所述锰源为乙酸锰、硝酸锰、硫酸锰和氯化锰中的一种或几种。Preferably, the manganese source in step 1) is one or more of manganese acetate, manganese nitrate, manganese sulfate and manganese chloride.
作为优选，步骤1）所述溶剂为乙二醇、水和无水乙醇中的一种或几种。Preferably, the solvent in step 1) is one or more of ethylene glycol, water and absolute ethanol.
作为优选，步骤1）所述水热处理是在鼓风干燥箱中进行。Preferably, the hydrothermal treatment in step 1) is carried out in a blast drying oven.
作为优选，步骤1）所述水热处理的温度为150-200℃，时间为10-15h。Preferably, the temperature of the hydrothermal treatment in step 1) is 150-200°C, and the time is 10-15h.
作为优选，步骤1）所述洗涤是用水和无水乙醇分别洗涤3-5次。Preferably, the washing in step 1) is to wash with water and absolute ethanol for 3-5 times respectively.
作为优选，步骤1）所述干燥是在真空干燥箱中80℃下干燥。Preferably, the drying in step 1) is in a vacuum drying oven at 80°C.
作为优选，步骤2）所述碳酸锰/聚多巴胺复合材料中的碳酸锰/聚多巴胺纳米球的粒径为400~600 nm。Preferably, the manganese carbonate/polydopamine nanospheres in the manganese carbonate/polydopamine composite material in step 2) have a particle size of 400-600 nm.
作为优选，步骤2）所述氧化锰纳米球与盐酸多巴胺加入质量比控制在1:（1~1.5）。Preferably, the mass ratio of the manganese oxide nanospheres and dopamine hydrochloride added in step 2) is controlled at 1:(1~1.5).
作为优选，步骤2）所述反应是在室温下进行。Preferably, the reaction in step 2) is carried out at room temperature.
作为优选，步骤2）所述反应的时间为10-48h。Preferably, the reaction time of step 2) is 10-48h.
作为优选，步骤3）所述洗涤是用水和无水乙醇分别洗涤3-5次。Preferably, the washing in step 3) is to wash with water and absolute ethanol for 3-5 times respectively.
作为优选，步骤3）所述干燥是在真空干燥箱中80℃下干燥。Preferably, the drying in step 3) is in a vacuum drying oven at 80°C.
作为优选，步骤4）所述煅烧处理是先在600~800℃下煅烧3-8h，然后降温至300-500℃煅烧1-3h。Preferably, the calcination treatment in step 4) is firstly calcined at 600-800°C for 3-8 hours, and then cooled to 300-500°C and calcined for 1-3 hours.
由以上所述的方法制得的一种氮掺杂碳包覆氧化锰锂离子电池复合负极材料，该氮掺杂碳包覆氧化锰锂离子电池复合负极材料由层状碳层均匀包裹纳米氧化锰颗粒构成；所述的碳包覆氧化锰的粒径为400~600 nm；所述的碳包覆氧化锰是盐酸多巴胺聚合在氧化锰表面而成。A nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material prepared by the method described above, the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material is uniformly wrapped by a layered carbon layer with nano-oxide Manganese particles; the particle size of the carbon-coated manganese oxide is 400-600 nm; the carbon-coated manganese oxide is formed by polymerizing dopamine hydrochloride on the surface of the manganese oxide.
以上所述的一种氮掺杂碳包覆氧化锰锂离子电池复合负极材料在制备锂离子电池中的应用。Application of the above-mentioned nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material in the preparation of lithium-ion batteries.
与现有技术相比，本发明具有如下优点：Compared with the prior art, the present invention has the following advantages:
1）由于包覆的碳层具有良好的导电性，可以增加材料的导电率，使得本发明氮掺杂碳包覆氧化锰锂离子电池复合负极材料在充放电过程具有较好的倍率性能；同时，碳层还可以作为缓冲层，能有效地缓解充放电过程中材料的体积变化，从而使得材料具有较好的稳定性。1) Since the coated carbon layer has good electrical conductivity, the conductivity of the material can be increased, so that the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material of the present invention has better rate performance during the charging and discharging process; at the same time; , the carbon layer can also be used as a buffer layer, which can effectively alleviate the volume change of the material during the charging and discharging process, so that the material has better stability.
2）在复合材料中有氮元素的掺杂，氮掺杂的碳材料也能够提高材料的循环性能和倍率性能。2) There is nitrogen doping in the composite material, and the nitrogen-doped carbon material can also improve the cycle performance and rate performance of the material.
3）本发明多巴胺的聚合方法非常简单，只需要在室温和弱碱性条件下进行，因此合成成本低廉，能耗较低、环境友好，适合锂离子电池实际应用，能够实现工业化规模生产。3) The polymerization method of dopamine in the present invention is very simple, and only needs to be carried out at room temperature and under weak alkaline conditions, so the synthesis cost is low, the energy consumption is low, and the environment is friendly, which is suitable for practical application of lithium ion batteries, and can realize industrial scale production.
附图说明Description of drawings
图1为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料的XRD图。1 is an XRD pattern of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention.
图2为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料的拉曼光谱图。2 is a Raman spectrum diagram of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention.
图3为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料的SEM图。3 is a SEM image of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention.
图4为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料的TEM图。4 is a TEM image of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention.
图5为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料作为锂离子电池负极材料的恒流充放电性能图。5 is a graph showing the constant current charge-discharge performance of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention as a lithium-ion battery negative electrode material.
图6为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料作为锂离子电池负极材料循环50周后的恒流充放电性能图。6 is a graph showing the constant current charge-discharge performance of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention as a lithium-ion battery negative electrode material after 50 cycles of cycles.
图7为本发明实施例1中所得氮掺杂碳包覆氧化锰锂离子电池复合负极材料作为锂离子电池负极材料的倍率性能图。7 is a rate performance diagram of the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in Example 1 of the present invention as a lithium-ion battery negative electrode material.
具体实施方式Detailed ways
下面结合实施例和附图对本发明作进一步的说明，但本发明的实施方式不限于此。The present invention will be further described below with reference to the examples and drawings, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
（1）称取1mmol的乙酸锰与10mmol的碳酸氢铵溶解到30mL的乙二醇中，室温下搅拌30min后，得到混合均匀的溶液；将上述得到的溶液转移到50mL的反应釜中，在180℃下进行水热反应12h；将水热反应产物进行离心分离，用水和无水乙醇洗涤4次后，在80℃的真空干燥箱中进行烘干，得到前驱体纳米球碳酸锰颗粒；随后，进行多巴胺的包覆，过程如下：分别称取100mg的纳米球碳酸锰和100mg盐酸多巴胺，溶解在50 mL的Tris缓冲溶液（pH=8.5）中，室温下搅拌24h，用无水乙醇离心洗涤4次，干燥，得到碳酸锰@聚多巴胺复合物。最后将得到的碳酸锰@聚多巴胺复合物放入瓷舟中置于管式炉中，在氮气气氛保护下，700℃反应5h，随后降温到500℃，再持续反应2h，最后冷却至室温，得到氮掺杂碳包覆氧化锰颗粒，即氮掺杂碳包覆氧化锰锂离子电池复合负极材料。X射线粉末衍射（XRD）分析表明所得的产物为纯氧化锰，没有发现杂相，说明纯度较高（如图1所示）。从Raman光谱图中可以看到，G峰出现在1350cm-1 左右，D峰出现在1600cm-1左右，说明本发明所得到的产品中具有的碳以无定形碳为主（如图2所示）。从扫描电子显微镜（SEM）和透射电镜（TEM）图中可以看出碳层均匀的包裹球形氧化锰颗粒表面，粒径为 400-600nm（如图3、4所示）。(1) Weigh 1 mmol of manganese acetate and 10 mmol of ammonium bicarbonate and dissolve them in 30 mL of ethylene glycol. After stirring for 30 min at room temperature, a well-mixed solution is obtained; The hydrothermal reaction was carried out at 180 °C for 12 h; the hydrothermal reaction product was centrifuged, washed with water and anhydrous ethanol for 4 times, and dried in a vacuum drying oven at 80 °C to obtain the precursor nanospheres of manganese carbonate particles; then , carry out dopamine coating, the process is as follows: Weigh 100 mg of nanospheres of manganese carbonate and 100 mg of dopamine hydrochloride respectively, dissolve them in 50 mL of Tris buffer solution (pH=8.5), stir at room temperature for 24 hours, and wash with absolute ethanol by centrifugation. 4 times and dried to obtain manganese carbonate@polydopamine complex. Finally, the obtained manganese carbonate@polydopamine complex was placed in a porcelain boat and placed in a tube furnace, under the protection of nitrogen atmosphere, reacted at 700 °C for 5 h, then cooled to 500 °C, continued to react for 2 h, and finally cooled to room temperature, The nitrogen-doped carbon-coated manganese oxide particles are obtained, that is, the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material. X-ray powder diffraction (XRD) analysis showed that the obtained product was pure manganese oxide, and no impurity phase was found, indicating high purity (as shown in Figure 1). It can be seen from the Raman spectrum that the G peak appears at about 1350 cm -1 and the D peak appears at about 1600 cm -1 , indicating that the carbon in the product obtained by the present invention is mainly amorphous carbon (as shown in Figure 2 ). ). From the scanning electron microscope (SEM) and transmission electron microscope (TEM) images, it can be seen that the carbon layer evenly wraps the surface of spherical manganese oxide particles with a particle size of 400-600 nm (as shown in Figures 3 and 4).
（2）将步骤（1）得到的氮掺杂碳包覆氧化锰锂离子电池复合负极材料作为活性材料，乙炔黑为导电剂，聚偏氟乙烯为粘结剂，并按照活性材料：导电剂：粘结剂=7：2：1的质量比置入5 mL的西林瓶中，然后滴加0.5 mL的氮甲基吡咯烷酮搅拌4 h后成浆状，将浆体均匀涂于铜箔上，而后放入80 ℃的恒温干燥箱干燥12 h，烘干至恒重后使用冲片机冲出为12mm的小圆片即为工作电极，在保证无水的情况下将小圆片放入充满氩气的手套箱，购买的锂片作为对电极和参比电极，使用的Celgard 2400型隔膜，电解液为1 mol L-1的LiPF6与碳酸乙烯酯（EC）、碳酸二甲酯（DMC）（EC：DMC=1：2，ν/ν）的混合液，最后在手套箱内组装成型号CR2025的扣式电池，整个过程中的手套箱必须保持氧气和水蒸气含量均小于1 ppm。25℃温度下，以100 mA/g的电流密度下进行恒流充放电测试时，其首次放电容量为2312 mAh/g，首次充电容量达到1444 mAh/g（如图5所示）。25℃温度下，在100 mA/g的电流密度下进行恒流充放电测试时，循环50周后，其可逆容量为1126 mAh/g（如图6所示）。25℃温度下，不同电流密度下的倍率性能如图6所示，在5000mA/g的大电流密度下，仍然具有大约330 mAh/g的可逆容量，具有较好的倍率性能（如图7所示）。(2) Using the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material obtained in step (1) as an active material, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder, and according to active material: conductive agent : Binder=7:2:1 mass ratio into a 5 mL vial, then dropwise add 0.5 mL of nitrogen methyl pyrrolidone and stir for 4 h to form a slurry, apply the slurry evenly on the copper foil, Then put it into a constant temperature drying box at 80 °C to dry for 12 h, and then use a punching machine to punch out a small wafer of 12 mm, which is the working electrode. An argon glove box, a purchased lithium sheet as a counter electrode and a reference electrode, a
实施例2Example 2
（1）称取1mmol的硝酸锰与5 mmol的碳酸氢铵溶解到30mL的无水乙醇中，室温下搅拌30min后，得到混合均匀的溶液；将上述得到的溶液转移到50mL的反应釜中，在150℃下进行水热反应10h；将水热反应产物进行离心分离，用水和无水乙醇洗涤4次后，在80℃的真空干燥箱中进行烘干，得到前驱体纳米球碳酸锰颗粒；随后，进行多巴胺的包覆，过程如下：分别称取100mg的纳米球碳酸锰和150mg盐酸多巴胺，溶解在50 mL的Tris缓冲溶液（pH=8.5）中，室温下搅拌24h，用无水乙醇离心洗涤4次，干燥，得到产物碳酸锰@聚多巴胺复合物。最后将得到的碳酸锰@聚多巴胺复合物放入瓷舟中置于管式炉中，在氮气气氛保护下，800℃反应3h，随后降温到500℃，再持续反应2h，最后冷却至室温，得到氮掺杂碳包覆氧化锰颗粒，即氮掺杂碳包覆氧化锰锂离子电池复合负极材料。(1) Dissolve 1 mmol of manganese nitrate and 5 mmol of ammonium bicarbonate in 30 mL of absolute ethanol, and stir at room temperature for 30 min to obtain a well-mixed solution; transfer the obtained solution to a 50 mL reaction kettle, The hydrothermal reaction was carried out at 150 °C for 10 h; the hydrothermal reaction product was centrifuged, washed with water and anhydrous ethanol for 4 times, and dried in a vacuum drying oven at 80 °C to obtain the precursor nanospheres of manganese carbonate particles; Subsequently, the dopamine coating was carried out, and the process was as follows: 100 mg of nanospheres of manganese carbonate and 150 mg of dopamine hydrochloride were respectively weighed, dissolved in 50 mL of Tris buffer solution (pH=8.5), stirred at room temperature for 24 h, and centrifuged with absolute ethanol. Washed 4 times and dried to obtain the product manganese carbonate@polydopamine complex. Finally, the obtained manganese carbonate@polydopamine complex was placed in a porcelain boat and placed in a tube furnace. Under the protection of nitrogen atmosphere, the reaction was carried out at 800 °C for 3 h, then cooled to 500 °C, continued to react for 2 h, and finally cooled to room temperature. The nitrogen-doped carbon-coated manganese oxide particles are obtained, that is, the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material.
（2）采用本实施例制备的氮掺杂碳包覆氧化锰与锂片组装成扣式半电池，方法与实施例1中的一样。25℃温度下，以100 mA/g的电流密度下进行恒流充放电测试时，其首次放电容量为2002 mAh/g，首次充电容量达到1204 mAh/g。25℃温度下，在100 mA/g的电流密度下进行恒流充放电测试时，循环50周后，其可逆容量为1008 mAh/g。25℃温度下，在5000mA/g的大电流密度下，仍然具有大约300 mAh/g的可逆容量，具有较好的倍率性能。(2) A button-type half-cell was assembled by using the nitrogen-doped carbon-coated manganese oxide and lithium sheets prepared in this example, and the method was the same as that in Example 1. When the constant current charge and discharge test was performed at a current density of 100 mA/g at 25 °C, the first discharge capacity was 2002 mAh/g, and the first charge capacity reached 1204 mAh/g. The reversible capacity was 1008 mAh/g after 50 cycles of galvanostatic charge-discharge tests at a current density of 100 mA/g at 25 °C. At a temperature of 25 °C, under a large current density of 5000 mA/g, it still has a reversible capacity of about 300 mAh/g, and has good rate performance.
实施例3Example 3
（1）称取1mmol的硫酸锰与15mmol的碳酸氢铵溶解到30mL的去离子水中，室温下搅拌30min后，得到混合均匀的溶液；将上述得到的溶液转移到50mL的反应釜中，在200℃下进行水热反应15h；将水热反应产物进行离心分离，用去离子水和无水乙醇各洗涤4次后，在80℃的真空干燥箱中进行烘干，得到前驱体纳米球碳酸锰颗粒；随后，进行多巴胺的包覆，过程如下：分别称取100mg的纳米球碳酸锰和125mg盐酸多巴胺，溶解在50 mL的Tris缓冲溶液（pH=8.5）中，室温下搅拌24h，用无水乙醇离心洗涤4次，干燥，得到产物碳酸锰@聚多巴胺复合物。最后将得到的碳酸锰@聚多巴胺复合物放入瓷舟中置于管式炉中，在氮气气氛保护下，600℃反应8h，随后降温到500℃，再持续反应2h，最后冷却至室温，得到氮掺杂碳包覆氧化锰颗粒，即氮掺杂碳包覆氧化锰锂离子电池复合负极材料。(1) Weigh 1 mmol of manganese sulfate and 15 mmol of ammonium bicarbonate and dissolve them in 30 mL of deionized water. After stirring for 30 min at room temperature, a well-mixed solution was obtained; the solution obtained above was transferred to a 50 mL reaction kettle, and the solution was stirred at 200 The hydrothermal reaction was carried out at ℃ for 15h; the hydrothermal reaction product was centrifuged, washed 4 times with deionized water and anhydrous ethanol, and dried in a vacuum drying oven at 80 ℃ to obtain the precursor nanospheres of manganese carbonate. Then, dopamine coating is carried out. The process is as follows: Weigh 100 mg of nanospheres manganese carbonate and 125 mg of dopamine hydrochloride respectively, dissolve them in 50 mL of Tris buffer solution (pH=8.5), stir at room temperature for 24 h, and use anhydrous Ethanol was centrifuged and washed 4 times and dried to obtain the product manganese carbonate@polydopamine complex. Finally, the obtained manganese carbonate@polydopamine complex was placed in a porcelain boat and placed in a tube furnace, under the protection of nitrogen atmosphere, reacted at 600 °C for 8 h, then cooled to 500 °C, continued to react for 2 h, and finally cooled to room temperature, The nitrogen-doped carbon-coated manganese oxide particles are obtained, that is, the nitrogen-doped carbon-coated manganese oxide lithium-ion battery composite negative electrode material.
（2）采用本实施例制备的氮掺杂碳包覆氧化锰与锂片组装成扣式半电池，方法与实施例1中的一样。25℃温度下，以100 mA/g的电流密度下进行恒流充放电测试时，其首次放电容量为1908 mAh/g，首次充电容量达到1054 mAh/g。25℃温度下，在100 mA/g的电流密度下进行恒流充放电测试时，循环50周后，其可逆容量为1038 mAh/g。25℃温度下，在5000mA/g的大电流密度下，仍然具有大约310 mAh/g的可逆容量，具有较好的倍率性能。(2) A button-type half-cell was assembled by using the nitrogen-doped carbon-coated manganese oxide and lithium sheets prepared in this example, and the method was the same as that in Example 1. At a temperature of 25 °C and a constant current charge-discharge test at a current density of 100 mA/g, the first discharge capacity was 1908 mAh/g, and the first charge capacity reached 1054 mAh/g. The reversible capacity was 1038 mAh/g after 50 cycles of galvanostatic charge-discharge test at a current density of 100 mA/g at 25 °C. At a temperature of 25 °C, under a large current density of 5000 mA/g, it still has a reversible capacity of about 310 mAh/g, with good rate capability.
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