Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries

被引:245
作者
Tsai, Ping-Chun [1 ,2 ]
Wen, Bohua [1 ]
Wolfman, Mark [3 ]
Choe, Min-Ju [4 ]
Pan, Menghsuan Sam [1 ]
Su, Liang [1 ]
Thornton, Katsuyo [4 ]
Cabana, Jordi [3 ]
Chiang, Yet-Ming [1 ]
机构
[1] MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA
[2] Natl Cheng Kung Univ, Dept Mat Sci & Engn, Tainan, Taiwan
[3] Univ Illinois, Dept Chem, Chicago, IL USA
[4] Univ Michigan, Dept Mat Sci & Engn, Ann Arbor, MI 48109 USA
关键词
LIALYNI1-X-YCOXO2; CATHODE; ACCELERATED CALENDAR; SHOCK; ELECTRODES; DISCHARGE; CHARGE; IMPEDANCE; FRACTURE; LINI1/3CO1/3MN1/3O2; PERFORMANCE;
D O I
10.1039/c8ee00001h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The electrochemical kinetics of battery electrodes at the single-particle scale are measured as a function of state-of-charge, and interpreted with the aid of concurrent transmission X-ray microscopy (TXM) of the evolving particle microstructure. An electrochemical cell operating with near-picoampere current resolution is used to characterize single secondary particles of two widely-used cathode compounds, NMC333 and NCA. Interfacial charge transfer kinetics are found to vary by two orders of magnitude with state-of-charge (SOC) in both materials, but the origin of the SOC dependence differs greatly. NCA behavior is dominated by electrochemically-induced microfracture, although thin binder coatings significantly ameliorate mechanical degradation, while NMC333 demonstrates strongly increasing interfacial reaction rates with SOC for chemical reasons. Micro-PITT is used to separate interfacial and bulk transport rates, and show that for commercially relevant particle sizes, interfacial transport is rate-limiting at low SOC, while mixed-control dominates at higher SOC. These results provide mechanistic insight into the mesoscale kinetics of ion intercalation compounds, which can guide the development of high performance rechargeable batteries.
引用
收藏
页码:860 / 871
页数:12
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