Titanium-based potassium-ion battery positive electrode with extraordinarily high redox potential

被引:107
作者
Fedotov, Stanislav S. [1 ]
Luchinin, Nikita D. [2 ]
Aksyonov, Dmitry A. [1 ]
Morozov, Anatoly V. [1 ]
Ryazantsev, Sergey V. [1 ,2 ]
Gaboardi, Mattia [3 ]
Plaisier, Jasper R. [3 ]
Stevenson, Keith J. [1 ]
Abakumov, Artem M. [1 ]
Antipov, Evgeny V. [1 ,2 ]
机构
[1] Skolkovo Inst Sci & Technol, Skoltech Ctr Energy Sci & Technol, Moscow 121205, Russia
[2] Lomonosov Moscow State Univ, Dept Chem, Moscow 119991, Russia
[3] Elettra Sincrotrone Trieste SCpA, Area Sci Pk, I-34012 Basovizza, Italy
基金
俄罗斯科学基金会;
关键词
ENERGY-LOSS SPECTRA; CATHODE MATERIALS; THERMAL-DECOMPOSITION; K-ION; LI; INTERCALATION; CHALLENGES; PHOSPHATES; STABILITY; TRANSPORT;
D O I
10.1038/s41467-020-15244-6
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
The rapid progress in mass-market applications of metal-ion batteries intensifies the development of economically feasible electrode materials based on earth-abundant elements. Here, we report on a record-breaking titanium-based positive electrode material, KTiPO4F, exhibiting a superior electrode potential of 3.6V in a potassium-ion cell, which is extraordinarily high for titanium redox transitions. We hypothesize that such an unexpectedly major boost of the electrode potential benefits from the synergy of the cumulative inductive effect of two anions and charge/vacancy ordering. Carbon-coated electrode materials display no capacity fading when cycled at 5C rate for 100 cycles, which coupled with extremely low energy barriers for potassium-ion migration of 0.2eV anticipates high-power applications. Our contribution shows that the titanium redox activity traditionally considered as "reducing" can be upshifted to near-4V electrode potentials thus providing a playground to design sustainable and cost-effective titanium-containing positive electrode materials with promising electrochemical characteristics. The Ti4+/Ti3+ redox couple is usually a good choice for anodes due to its low potential. Here, the authors show that the potential can be increased to nearly 4.0V in KTiPO4F, which serves as a high-performance cathode for K-ion batteries.
引用
收藏
页数:11
相关论文
共 69 条
[11]   Cathode properties of Na3M2(PO4)2F3 [M = Ti, Fe, V] for sodium-ion batteries [J].
Chihara, Kuniko ;
Kitajou, Ayuko ;
Gocheva, Irina D. ;
Okada, Shigeto ;
Yamaki, Jun-ichi .
JOURNAL OF POWER SOURCES, 2013, 227 :80-85
[12]   THE NASICON-TYPE TITANIUM PHOSPHATES LITI2(PO4)3, NATI2(PO4)3 AS ELECTRODE MATERIALS [J].
DELMAS, C ;
NADIRI, A ;
SOUBEYROUX, JL .
SOLID STATE IONICS, 1988, 28 :419-423
[13]   A NASICON-TYPE PHASE AS INTERCALATION ELECTRODE - NATI2(PO4)3 [J].
DELMAS, C ;
CHERKAOUI, F ;
NADIRI, A ;
HAGENMULLER, P .
MATERIALS RESEARCH BULLETIN, 1987, 22 (05) :631-639
[14]   Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study [J].
Dudarev, SL ;
Botton, GA ;
Savrasov, SY ;
Humphreys, CJ ;
Sutton, AP .
PHYSICAL REVIEW B, 1998, 57 (03) :1505-1509
[15]   A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries [J].
Ellis, B. L. ;
Makahnouk, W. R. M. ;
Makimura, Y. ;
Toghill, K. ;
Nazar, L. F. .
NATURE MATERIALS, 2007, 6 (10) :749-753
[16]   Reversible facile Rb+ and K+ ions de/insertion in a KTiOPO4-type RbVPO4F cathode material [J].
Fedotov, Stanislav S. ;
Samarin, Aleksandr Sh. ;
Nikitina, Victoria A. ;
Aksyonov, Dmitry A. ;
Sokolov, Sergey A. ;
Zhugayevych, Andriy ;
Stevenson, Keith J. ;
Khasanova, Nellie R. ;
Abakumov, Artem M. ;
Antipov, Evgeny V. .
JOURNAL OF MATERIALS CHEMISTRY A, 2018, 6 (29) :14420-14430
[17]   Crystallochemical tools in the search for cathode materials of rechargeable Na-ion batteries and analysis of their transport properties [J].
Fedotov, Stanislav S. ;
Kabanova, Natalya A. ;
Kabanov, Artem A. ;
Blatov, Vladislav A. ;
Khasanova, Nellie R. ;
Antipov, Evgeny V. .
SOLID STATE IONICS, 2018, 314 :129-140
[18]   Crystal Structure and Li-Ion Transport in Li2CoPO4F High-Voltage Cathode Material for Li-Ion Batteries [J].
Fedotov, Stanislav S. ;
Kabanov, Artem A. ;
Kabanova, Natalia A. ;
Blatov, Vladislav A. ;
Zhugayevych, Andriy ;
Abakumov, Artem M. ;
Khasanova, Nellie R. ;
Antipov, Evgeny V. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2017, 121 (06) :3194-3202
[19]   AVPO4F (A = Li, K): A 4 V Cathode Material for High-Power Rechargeable Batteries [J].
Fedotov, Stanislav S. ;
Khasanova, Nellie R. ;
Samarin, Aleksandr Sh. ;
Drozhzhin, Oleg A. ;
Batuk, Dmitry ;
Karakulina, Olesia M. ;
Hadermann, Joke ;
Abakumov, Artem M. ;
Antipov, Evgeny V. .
CHEMISTRY OF MATERIALS, 2016, 28 (02) :411-415
[20]   Challenges for Rechargeable Li Batteries [J].
Goodenough, John B. ;
Kim, Youngsik .
CHEMISTRY OF MATERIALS, 2010, 22 (03) :587-603