Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 11, Issue 19, Pages 17313-17320Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.8b20436
Keywords
silicon nanowires; phosphorus dopant; lithiation/delithiation cycling; nanopore formation; phase-field simulation; lithium ion batteries
Funding
- National 1000 Talents Program of China tenable at the Huazhong University of Science and Technology (HUST), China
- National Natural Science Foundation of China [21802065]
- Shenzhen DRC project [[2018]1433]
- Pico Center at SUSTech - Presidential fund
- Development and Reform Commission of Shenzhen Municipality
- DOE's Office of Biological and Environmental Research
- DOE [DE-AC05-76RLO1830]
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Through in situ transmission electron microscopy (TEM) observation, we report the behaviors of phosphorus (P)-doped silicon nanowires (SiNWs) during electrochemical lithiation/delithiation cycling. Upon lithiation, lithium (Li) insertion causes volume expansion and formation of the crystalline Li15Si4 phase in the P-doped SiNWs. During delithiation, vacancies induced by Li extraction aggregate gradually, leading to the generation of nanopores. The as-formed nanopores can get annihilated with Li reinsertion during the following electrochemical cycle. As demonstrated by our phase-field simulations, such first-time-observed reversible nanopore formation can be attributed to the promoted lithiation/delithiation rate by the P dopant in the SiNWs. Our phase-field simulations further reveal that the delithiation-induced nanoporous structures can be controlled by tuning the electrochemical reaction rate in the SiNWs. The findings of this study shed light on the rational design of high-power performance Si-based anodes.
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