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Utilizing Co2+/Co3+ Redox Couple in P2‐Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium‐Ion Batteries
Advanced Science ( IF 14.3 ) Pub Date : 2017-07-06 , DOI: 10.1002/advs.201700219 Qin-Chao Wang 1 , Enyuan Hu 2 , Yang Pan 1 , Na Xiao 1 , Fan Hong 1 , Zheng-Wen Fu 3 , Xiao-Jing Wu 1 , Seong-Min Bak 2 , Xiao-Qing Yang 2 , Yong-Ning Zhou 1
Advanced Science ( IF 14.3 ) Pub Date : 2017-07-06 , DOI: 10.1002/advs.201700219 Qin-Chao Wang 1 , Enyuan Hu 2 , Yang Pan 1 , Na Xiao 1 , Fan Hong 1 , Zheng-Wen Fu 3 , Xiao-Jing Wu 1 , Seong-Min Bak 2 , Xiao-Qing Yang 2 , Yong-Ning Zhou 1
Affiliation
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Developing sodium‐ion batteries for large‐scale energy storage applications is facing big challenges of the lack of high‐performance cathode materials. Here, a series of new cathode materials Na0.66CoxMn0.66–xTi0.34O2 for sodium‐ion batteries are designed and synthesized aiming to reduce transition metal‐ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66CoxMn0.66–xTi0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2‐type layered structure delivers a reversible capacity of 120 mAh g−1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g−1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+‐induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X‐ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2‐layered cathodes for sodium‐ion batteries. This finding may open new approaches to design advanced intercalation‐type cathode materials.
中文翻译：
在 P2 层状 Na0.66Co0.22Mn0.44Ti0.34O2 钠离子电池正极中使用 Co2+/Co3+ 氧化还原对
开发用于大规模储能应用的钠离子电池面临着缺乏高性能正极材料的巨大挑战。本文设计并合成了一系列用于钠离子电池的新型正极材料Na 0.66 Co x Mn 0.66– x Ti 0.34 O 2，旨在减少过渡金属离子有序性、电荷有序性以及Na +和空位有序性。当Co含量从x = 0增加到0.33时，Na 0.66 Co x Mn 0.66– x Ti 0.34 O 2从斜方晶系到六方晶系的有趣结构变化被揭示。特别是，具有P2型层状结构的Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2在0.1 C下可逆容量为120 mAh g -1。当电流密度增加到10 C时，可逆容量为63.2 mAh g -1 。仍然可以获得-1 ，表明有希望的倍率能力。低价Co 2+取代导致Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2中形成平均Mn 3.7+价态，有效抑制Mn 3+引起的Jahn-Teller畸变，从而稳定层状结构。 。X射线吸收光谱结果表明，Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2在充放电过程中的电荷补偿是由Co 2.2+ /Co 3+和Mn 3.3+ /Mn 4+氧化还原电对贡献的。这是首次在钠离子电池的P2层状正极中观察到高度可逆的Co 2+ /Co 3+氧化还原电对。这一发现可能开辟设计先进插层型正极材料的新方法。
更新日期：2017-07-06
中文翻译：
在 P2 层状 Na0.66Co0.22Mn0.44Ti0.34O2 钠离子电池正极中使用 Co2+/Co3+ 氧化还原对
开发用于大规模储能应用的钠离子电池面临着缺乏高性能正极材料的巨大挑战。本文设计并合成了一系列用于钠离子电池的新型正极材料Na 0.66 Co x Mn 0.66– x Ti 0.34 O 2，旨在减少过渡金属离子有序性、电荷有序性以及Na +和空位有序性。当Co含量从x = 0增加到0.33时，Na 0.66 Co x Mn 0.66– x Ti 0.34 O 2从斜方晶系到六方晶系的有趣结构变化被揭示。特别是，具有P2型层状结构的Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2在0.1 C下可逆容量为120 mAh g -1。当电流密度增加到10 C时，可逆容量为63.2 mAh g -1 。仍然可以获得-1 ，表明有希望的倍率能力。低价Co 2+取代导致Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2中形成平均Mn 3.7+价态，有效抑制Mn 3+引起的Jahn-Teller畸变，从而稳定层状结构。 。X射线吸收光谱结果表明，Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2在充放电过程中的电荷补偿是由Co 2.2+ /Co 3+和Mn 3.3+ /Mn 4+氧化还原电对贡献的。这是首次在钠离子电池的P2层状正极中观察到高度可逆的Co 2+ /Co 3+氧化还原电对。这一发现可能开辟设计先进插层型正极材料的新方法。
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