B掺杂MnO2的制备及其电化学性能

doi:10.11901/1005.3093.2020.149

材料研究学报

2021, Vol. 35

Issue (1): 36-44 DOI: 10.11901/1005.3093.2020.149

研究论文

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B掺杂MnO₂的制备及其电化学性能

夏傲(

), 赵晨鹏, 曾啸雄, 韩曰鹏, 谈国强

陕西科技大学材料科学与工程学院无机材料绿色制备与功能化重点实验室西安 710021

Preparation and Electrochemical Properties of B-doped MnO₂

XIA Ao(

), ZHAO Chenpeng, ZENG Xiaoxiong, HAN Yuepeng, TAN Guoqiang

Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, Shaanxi University of Science & Technology, Xi'an 710021, China

引用本文:

夏傲, 赵晨鹏, 曾啸雄, 韩曰鹏, 谈国强. B掺杂MnO₂的制备及其电化学性能[J]. 材料研究学报, 2021, 35(1): 36-44.
Ao XIA, Chenpeng ZHAO, Xiaoxiong ZENG, Yuepeng HAN, Guoqiang TAN. Preparation and Electrochemical Properties of B-doped MnO₂[J]. Chinese Journal of Materials Research, 2021, 35(1): 36-44.

全文: PDF(2816 KB) HTML

摘要:

用一步水热法制备B³⁺掺杂Birnessite-MnO₂负极材料，使用XRD，Raman，SEM，TEM，XPS和恒电流充放电等手段表征了材料的结构和电化学性能。结果表明，B³⁺掺杂前后的MnO₂都是由二维纳米片组装而成的花球，B³⁺离子掺杂使纳米片的厚度减小，从而缩短了锂离子和电子在材料内部的传输路径；掺杂适量的B³⁺离子，使Birnessite-MnO₂的电荷转移电阻显著降低。B³⁺掺杂比例为9%的电极材料，具有最优的电化学性能。在电流密度为100 mA·g^-1和1000 mA·g^-1的条件下，首次充电比容量分别为855.1 mAh·g^-1和599 mAh·g^-1，循环100次后仍然保有805 mAh·g^-1和510.3 mAh·g^-1的可逆比容量，容量保持率分别为94.1%和85.2%。

关键词 ：材料合成与加工工艺, 锂离子电池, 水热法, MnO₂, 电化学性能

Abstract：

B³⁺ doped birnessite-MnO₂ anode materials were successfully prepared by one-step hydrothermal method, and then characterized by XRD, Raman, SEM, TEM, XPS and electrochemical performance tests. The pure- and doped-MnO₂ particles were globular nano-flowers composed of two-dimensional nano flakes . The thickness of nano flakes decreased after B³⁺ doping, thus the transmission path of Li-ions and electrons in the bulk material was shortened. The charge transfer resistance of birnessite-MnO₂ decreased obviously after a proper amount of B³⁺ ions doping. The B-MnO₂ doped with 9% B³⁺showed the optimal electrochemical performance. In conditions of the current density of 100 mA·g^-1 and 1000 mA·g^-1, the initial charging specific capacities were 855.1 mAh·g^-1 and 599 mAh·g^-1, respectively. After 100 cycles the corresponding reversible capacities still remained 805 mAh·g^-1 and 510.3 mAh·g^-1, and the respective retention rates were 94.1% and 85.2% respectively.

Key words： synthesizing and processing technics for materials lithium-ion battery hydrothermal method MnO₂ electrochemical performance

收稿日期: 2020-05-03

ZTFLH:

TM912.9

基金资助:中国博士后科学基金(2016M592746);陕西科技大学博士创业资助计划(BJ15-04)

作者简介: 夏傲，女，1981生，副教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2020.149 或 https://www.cjmr.org/CN/Y2021/V35/I1/36

图1 B掺杂MnO2样品的XRD图谱

表1 XRD图谱中得到的所有样品的晶格参数

图2 B掺杂MnO2样品的拉曼谱图

图3 B0M、B3M、 B9M以及B15M样品的SEM照片

图4 B9M的TEM图片

图5 B0M和B9M的XPS全谱、B9M的B1s窄谱、B0M的Mn2p窄谱、B9M的Mn2p窄谱、B0M的O1s窄谱以及B9M的O1s窄谱

表2 通过XPS拟合所得的元素状态分析

图6 纯相MnO2和B掺杂MnO2的晶体结构示意图

图7 样品的循环伏安曲线和首次充放电曲线

图8 电流密度为100 mA·g-1和1000 mA·g-1时样品的循环性能、样品的倍率性能以及电流密度为100 mA·g-1时样品三次循环后的阻抗谱图

表3 合成样品的EIS模型参数

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