Citation: Zilin Hu, Yaoshen Niu, Xiaohui Rong, Yongsheng Hu. Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries[J]. Acta Physico-Chimica Sinica, ;2024, 40(6): 230600. doi: 10.3866/PKU.WHXB202306005 shu

Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries

Zilin Hu ^{1, 2} ,
Yaoshen Niu ¹ ,
Xiaohui Rong ^{1, 2, 3,,} ,
Yongsheng Hu ^{1, 2, 3, 4,,}

1.
Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
2.
College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China
3.
Yangtze River Delta Physics Research Center Co. Ltd., Liyang 213300, Jiangsu Province, China
4.
Huairou Division, Institute of Physics, Chinese Academy of Sciences, Beijing 101400, China

Corresponding author: Xiaohui Rong, rong@iphy.ac.cn Yongsheng Hu, yshu@iphy.ac.cn
Received Date: 1 June 2023
Revised Date: 29 June 2023
Accepted Date: 17 July 2023
Available Online: 17 August 2023
Fund Project: the National Key R&D Program of China 2022YFB2402500the National Natural Science Foundation of China 51725206the National Natural Science Foundation of China 52122214the National Natural Science Foundation of China 52072403the National Natural Science Foundation of China 52002394the Youth Innovation Promotion Association of the Chinese Academy of Sciences 2020006the Beijing Municipal Natural Science Foundation 2212022the Young Elite Scientists Sponsorship Program by CAST 2022QNRC001

The storage of intermittent wind and solar electricity requires grid-level energy storage devices, and due to the abundance and wide distribution of Na resources, Na-ion batteries (NIBs) are much more cost-effective and have shown greater potential for large-scale energy storage than Li-ion batteries (LIBs). However, the lack of suitable cathode hinders the practical use of NIBs, so exploring suitable cathode materials that can maintain a balance between high energy density and cost-effectiveness is essential for NIBs. Ni-Mn based layered oxides are important cathode materials for NIBs, offering relatively high potential through the multi-electron redox reaction of Ni⁴⁺/Ni³⁺/Ni²⁺ as well as the low-cost and non-toxic nature of Mn⁴⁺. P2-Na_0.67[Ni_0.33Mn_0.67]O₂ was the first reported Ni-Mn based Na-ion battery cathode with a high capacity of ~160 mAh∙g⁻¹ in the voltage range of 2.0–4.5 V, while irreversible P2-O2 phase transition above 4.1 V makes poor capacity retention and limits their applications. Moreover, a dilemma has emerged in that a costly element (Ni) is used for sodium-ion batteries, which is supposed to be low-cost. With the intensive research in recent years, introducing an appropriate amount of anionic redox can effectively improve energy density while simultaneously reducing the amount of high-cost transition metals, such as V, Co, and Ni. However, because of irreversible oxygen loss and Mn⁴⁺/Mn³⁺ redox activation, voltage decay is difficult to avoid for most of these anion-redox materials. In this research, we report a Li-substituted Na_x[Ni, Mn]O₂ cathode, the designed formula being Na_0.85[Li_0.2Ni_0.15Mn_0.65]O₂. This material shows a unique combination of both cationic redox (Ni⁴⁺/Ni³⁺/Ni²⁺) and anionic redox (O²⁻/O₂ⁿ⁻) during charge and discharge, showing a high capacity of ~150 mAh∙g⁻¹ (10 mA∙g⁻¹, 1.5–4.5 V) with only 0.15 Ni. With an optimized voltage range, the material shows a capacity of ~100 mAh∙g⁻¹ and stable cycling performance (80% of initial capacity after 100 cycles at 10 mA∙g⁻¹ within 2.5–4.25 V) and high-rate capability (the capacity of 500 mA∙g⁻¹ is 80% of 10 mA∙g⁻¹, 2.5–4.25 V). Moreover, we demonstrate an effective way to suppress the voltage decay and Mn reduction through Ni³⁺ as a redox barrier. Specifically, during the discharge process, the Mn⁴⁺/Mn³⁺ reduction process was replaced by the Ni³⁺/Ni²⁺ reduction process with higher redox potential in the layered oxides. In addition, the full Ni²⁺/Ni⁴⁺ redox can compensate for the partial oxygen redox loss in the subsequent cycles. We believe that introducing the anion redox through Li substitution and the use of Ni³⁺ as a redox barrier to suppress the voltage decay will provide a new way in the design of NIBs’ cathode materials, with potential benefits such as higher energy density, lower cost, and longer cycle life.
- Na-ion battery,
- Anion-redox,
- Voltage decay,
- Single-phase solid solution reaction
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沈阳化工大学材料科学与工程学院沈阳 110142

Suppression of Voltage Decay through Ni3+ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries

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通讯作者: 陈斌, bchen63@163.com

Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries