硅酸盐学报

调控钠位点占比设计高性能P2型钠电正极材料

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韩嘉俊 ¹ , 温敏 ¹ , 郑其林 ¹ , 袁伟伟 ¹ , 陈康 ¹ , 廖俊杰 ¹ , 姚胡蓉 ¹^,²

硅酸盐学报 | 研究论文 2024,52(6): 2016-2023

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硅酸盐学报 |研究论文 2024 , 52 (6) : 2016 -2023

调控钠位点占比设计高性能P2型钠电正极材料

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韩嘉俊¹, 温敏¹, 郑其林¹, 袁伟伟¹, 陈康¹, 廖俊杰¹, 姚胡蓉¹^,²

作者信息

^1．福建师范大学物理与能源学院，福州 350117

^2．福建省先进高场超导材料与工程协同创新中心，福州 350117

通讯作者:

姚胡蓉（1988—），女，博士，教授。

作者简介:

韩嘉俊（1997—），男，硕士研究生。

High Performance Na-Based P2-Type Cathodes Designed by Na Sites Modulation

Jiajun HAN¹, Min WEN¹, Qilin ZHENG¹, Weiwei YUAN¹, Kang CHEN¹, Junjie LIAO¹, Hurong YAO¹^,²

Affiliations

^1.School of Physics and Energy, Fujian Normal University, Fuzhou 350117, China

^2.Fujian Collaborative Innovation Center for Advanced High-Field Superconducting Materials and Engineering, Fuzhou 350117, China

Corresponding Author:

YAO Hurong (1988-), female, Ph.D., Professor. E-mail: hryao126@126.com

HAN Jiajun (1997-), male, Master candidate. E-mail: hanjia1667109755@163.com

出版时间: 2024-06-20 doi: 10.14062/j.issn.0454-5648.20230870

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摘要

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在众多Na离子电池正极材料中，P2型层状氧化物因其优异的动力学性能受到研究者们的广泛关注。在P2型层状氧化物材料中，Na离子有2种不同的位点，即Na_e和Na_f。由于配位环境的差异，Na离子在不同位点间的迁移行为不同。本工作提出通过调控材料中Na含量的策略实现了对同一过渡金属组分材料的Na_e/Na_f位点占位比的优化。研究发现，与Na_0.45Ni_0.1Mn_0.9O₂和Na_0.65Ni_0.1Mn_0.9O₂相比，具有更高Na_e/Na_f位点占比值的Na_0.55Ni_0.1Mn_0.9O₂材料表现出最为优异的电化学性能，其电化学曲线平滑，在0.2 C（1 C=173 mA·g^-1）的倍率下容量高达174.5 mA·h·g^-1，在3 C，循环200次容量保持率高达92.95%，10 C的高倍率下仍能发挥83.6 mA·h·g^-1的容量，该策略为设计高性能P2型钠电正极材料打开了新的思路。

关键词

Na离子电池 / P2型层状正极材料 / Na位点

Abstract

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Introduction

Na-ion batteries (NIBs) have a great potential as next-generation large-scale energy storage devices. Among various cathode materials for NIBs, P2-type layered transition metal oxides have attracted much attention because of their excellent kinetics and easy processability. In P2-type layered oxides, Na ion occupies two different sites, i.e., Na_e and Na_f. The triangular prism polyhedron of Na_f site shares faces with two TmO6 octahedrons, while Na_e shares edges with six TmO6. The migration behavior of Na ions at different positions is diverse due to the distinction of distance and electrostatic force between Na⁺-Tmⁿ⁺. The migration of Na ions at Na_e site has a lower migration energy barrier, compared to that of Na_f position. Namely, more Na ions at Na_e site and increasing the occupation ratio of Na_e/Na_f can effectively improve the electrochemical performance of P2 layered oxides. Previous research indicates that the ratio of Na ions at different sites can be modulated by introducing inactive ions to transition metal layers. However, the introduction inevitably results in the capacity sacrifice. The ration of Na_e/Na_f is mainly affected by two aspects, i.e., the interaction between Tmⁿ⁺ and Na⁺, and the interaction between Na⁺ and Na⁺. In the case with the same transition metal component, the design of Na content is expected to achieve the regulation of Na_e/Na_f ratio, mainly from the following three reasons: 1) Na content affects the valence state of transition metals, and thus modulates the interaction between Tmⁿ⁺ and Na⁺; 2) Na content changes the Na interlayer distance, and then affects the distance between Na⁺ and Tmⁿ⁺ and the corresponding interaction between Na⁺ and Tmⁿ⁺; and 3) Na content regulates the distance between Na⁺ and Na⁺. In this paper, we proposed a novel strategy to optimize the Na_e/Na_f occupancy ratio with the same transition metal composition via adjusting Na content in the material. This strategy could open up new opportunities to design high-performance cathode materials for NIBs.

Methods

Na_xNi_0.1Mn_0.9O₂ (x = 0.45, 0.55, and 0.65, denoted as Na45, Na55, Na65) were prepared by a simple high-temperature solid-phase method. The precursors were Na₂CO₃, NiO and Mn₂O₃ and weighed according to a required stoichiometry ratio with a 5% excess of Na₂CO₃. After grinding, they were heatd in an alumina crucible in a muffle furnace at an elevated rate of 5 ℃/min up to 950 ℃. After heated at 950 ℃ for 15 h, the powdered materials were obtained by natural cooling and finally transferred to an argon-filled glove box. The working electrodes were prepared via spreading the slurry of active materials, acetylene black and polyvinylidene difluoride with a mass percent of 75∶15∶10 on Al foil. After drying in vacuum at 80 ℃ for 12 h, the electrodes were transferred to an argon-filled glove box and assembled into CR2032-type button cells. The counter electrode was metal sodium, the separator was a glass fiber, and the electrolyte was 1 M NaClO₄ in propylene carbonate (PC) solution with 5% fluoroethylene carbonate (FEC) additive.

Results and discussion

The effect of Na content on the occupancy ratio of Na_e/Na_f positions and the corresponding evolution of structure and electrochemical properties was investigated. All the Nax compounds have a hexagonal P2 structure with P6₃/mmc space group. According to the XRD refinement and eletrochemical results, Na55 material has the maximum Na_e/Na_f occupancy ratio and specific discharge capacity, mainly originating from the better mobility of Na ions at Na_e sites. Na55 exhibits a prominent capacity of 174.5 mAh·g^-1 at 0.2 C, which is much higher than that of Na45 and Na65. Benefited from the optimized Na_e/Na_f ration, Na55 displays 10^-10-10^-12 cm²·s^-1 of Na⁺ diffusion coefficient, which is much higher than 10^-12-10^-14 cm²·s^-1 of the usual transition metal layered oxides cathodes. Also, Na55 exhibits an excellent rate performance with a capacity of 83.6 mAh·g^-1 at 10 C rate, and a great cycling stability with a 92.95% capacity retention after 200 cycles.

Conclusions

Na_e/Na_f occupancy ratio of P2-type layered oxides was modulated by an extremely simple strategy for Na content optimization. The combined results of XRD refinement, electrochemical curve, transmission electron microscopy, cyclic voltammogram, ex-situ XRD and X-ray photoelectron spectroscopy showed that a higher Na_e/Na_f ratio in Na55 materials effectively enhanced the Na⁺ diffusion rate, consequently resulting in a high specific capacity (174.5 mAh·g^-1 at 0.2 C), an outstanding kinetic performance (87 mAh·g^-1 at 10 C) with an excellent cycling performance (92.95% capacity retention after 200 cycles). Compared to conventional P2 materials with common Na content, Na55 had a smaller volume change without any phase transition during electrochemical process. The simple and effective strategy could offer an insight into the rational design of high-performance layered cathode materials and also enhance the practical application of NIBs.

Key words

sodium ion battery / P2-type layer oxide / sodium site

引用本文

韩嘉俊, 温敏, 郑其林, 袁伟伟, 陈康, 廖俊杰, 姚胡蓉. 调控钠位点占比设计高性能P2型钠电正极材料. 硅酸盐学报, 2024 , 52 (6) : 2016 -2023 . DOI: 10.14062/j.issn.0454-5648.20230870

Jiajun HAN, Min WEN, Qilin ZHENG, Weiwei YUAN, Kang CHEN, Junjie LIAO, Hurong YAO. High Performance Na-Based P2-Type Cathodes Designed by Na Sites Modulation[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (6) : 2016 -2023 . DOI: 10.14062/j.issn.0454-5648.20230870

基金

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国家自然科学基金面上项目(22179021)
福建省杰出青年项目(2023J06028)

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2024年第52卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230870

接收时间：2023-11-14
首发时间：2026-10-22
出版时间：2024-06-20

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出版历史

收稿日期：2023-11-14
修回日期：2023-12-04

基金

国家自然科学基金面上项目(22179021)

福建省杰出青年项目(2023J06028)

作者信息

^1．福建师范大学物理与能源学院，福州 350117

^2．福建省先进高场超导材料与工程协同创新中心，福州 350117

通讯作者:

姚胡蓉（1988—），女，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230870

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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