稀土离子掺杂硅藻负极材料的制备及其电化学性能

doi:10.11901/1005.3093.2024.426

材料研究学报

2025, Vol. 39

Issue (7): 499-509 DOI: 10.11901/1005.3093.2024.426

研究论文

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稀土离子掺杂硅藻负极材料的制备及其电化学性能

孙世贸¹, 刘红昌¹^,²(

), 刘宏伟¹^,², 王军¹^,², 商晨楷¹

^1.中南大学资源加工与生物工程学院长沙 410083
^2.中南大学生物冶金教育部重点实验室长沙 410083

Preparation and Electrochemical Properties of Rare Earth Ion Doped Diatom Anode Materials

SUN Shimao¹, LIU Hongchang¹^,²(

), LIU Hongwei¹^,², WANG Jun¹^,², SHANG Chenkai¹

^1.School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
^2.Key Lab of Biometallurgy of Ministry of Education, Central South University, Changsha 410083, China

引用本文:

孙世贸, 刘红昌, 刘宏伟, 王军, 商晨楷. 稀土离子掺杂硅藻负极材料的制备及其电化学性能[J]. 材料研究学报, 2025, 39(7): 499-509.
Shimao SUN, Hongchang LIU, Hongwei LIU, Jun WANG, Chenkai SHANG. Preparation and Electrochemical Properties of Rare Earth Ion Doped Diatom Anode Materials[J]. Chinese Journal of Materials Research, 2025, 39(7): 499-509.

全文: PDF(20538 KB) HTML

摘要:

将用离子型稀土矿制备的提取液添加到硅藻培养基中制备了硅藻。结果表明，浓度过高的稀土提取液抑制硅藻的生长。添加适量的稀土提取液培养硅藻，制备出由稀土离子修饰的硅藻壳体，即可用于制作锂离子电池的稀土离子掺杂硅藻负极材料。硅藻壳体的天然中空多孔结构能为SiO₂的体积应变提供足够的缓冲空间，稀土离子的掺杂降低了硅藻壳体负极的电化学阻抗，使硅藻壳体负极的长循环性能和倍率性能显著提高。稀土提取液添加量为10 mL/L制备的硅藻壳体负极(DBS@C-REE-10)循环150圈后的放电比容量为879 mAh·g^-1，远高于未经稀土离子修饰的硅藻负极的性能。

关键词 ：复合材料, 锂离子电池, 负极材料, 稀土离子, 硅藻

Abstract：

Diatoms were prepared by adding extraction solution prepared from ionic rare earth ores to diatom culture media. The results indicate that high concentrations of rare earth extraction solution inhibited the growth of diatoms. An appropriate amount of rare earth extraction solution was added to cultivate diatoms, and diatom frustules modified with rare earth ions were used as rare earth ion doped diatom anode materials for lithium-ion batteries. The natural hollow porous structure of diatom frustules provided enough buffering space for the volumetric strain of SiO₂. The doping of rare earth ions reduced the electrochemical impedance of the anode electrode of diatom frustules, significantly improving its long cycle and rate performance. The specific discharge capacity of the diatom frustule anode (DBS@C-REE-10) prepared with 10 mL/L rare earth extract after 150 cycles was 879 mAh·g^-1, which was much greater than that of the diatom anode without rare earth ion modification.

Key words： composite lithium-ion battery anode material rare earth ions diatoms

收稿日期: 2024-10-16

ZTFLH:

TQ152

基金资助:国家重点研发计划(2022YFC2105300)

通讯作者: 刘红昌，副教授，hchliu2050@csu.edu.cn，研究方向为资源、环境和能源生物技术

Corresponding author: LIU Hongchang, Tel: 15874293360, E-mail: hchliu2050@csu.edu.cn

作者简介: 孙世贸，男，2000年生，硕士

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https://www.cjmr.org/CN/10.11901/1005.3093.2024.426 或 https://www.cjmr.org/CN/Y2025/V39/I7/499

图1 稀土提取液添加量不同的硅藻生长和溶液理化参数

图2 稀土含量不同的稀土离子掺杂的硅藻负极材料的XRD谱和TG曲线

表1 不同稀土含量的稀土离子掺杂的硅藻负极材料的成分

图3 稀土含量不同的稀土离子掺杂的硅藻负极材料的透射电镜和高分辨透射电镜图像

图4 稀土含量不同的稀土离子掺杂的硅藻负极材料的扫描电镜照片和EDS映射谱

图5 稀土含量不同的稀土离子掺杂的硅藻负极材料的Raman光谱

图6 稀土提取液添加量不同的硅藻壳体负极的电化学性能

表2 稀土提取液添加量不同的硅藻壳体负极的倍率

图7 稀土含量不同稀土离子掺杂的硅藻负极材料的交流阻抗和赝电容

Sample	$σ$	D_Li+ / cm²·s^-1
DBS@C	466.2	2.17 $×$ 10^-15
DBS@C-REE-2.5	377.8	3.30 $×$ 10^-15
DBS@C-REE-5	349.1	3.86 $×$ 10^-15
DBS@C-REE-10	331.6	4.28 $×$ 10^-15

表3 DBS@C-REE电极材料的Warburg因子和Li+扩散系数

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