4.7 Article

Solution-Grown Phosphorus-Hyperdoped Silicon Nanowires/Carbon Nanotube Bilayer Fabric as a High-Performance Lithium-Ion Battery Anode

Journal

ACS APPLIED ENERGY MATERIALS
Volume 4, Issue 4, Pages 3160-3168

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsaem.0c02932

Keywords

silicon; nanowires; battery; lithium; energy storage

Funding

  1. Young Scholar Fellowship Program by the Ministry of Science and Technology in Taiwan [MOST 108-2636-E007-013, MOST 108-2622-8-007-016, MOST 109-2636E-007-011]
  2. National Tsing Hua University [107Q2708E1]

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Phosphorus-hyperdoped silicon nanowires (PH-SiNWs) are synthesized in large scale via the tin (Sn)-seeded supercritical fluid-liquid-solid (SFLS) method, with very low resistivity. These PH-SiNWs show improved cycling life and performance as an anode material in lithium-ion batteries.
The solution synthetic method can produce large quantities of silicon nanowires (SiNWs) for various applications, such as energy storage, texturing and composites materials, etc. However, solution-grown SiNWs exhibit very low conductivity compared to chemical vapor deposition (CVD)-grown SiNWs due to their poor crystallinity or reaction byproducts such as insulating polysiliane or polyphenylsilane. Here, we report the large-scale synthesis of phosphorus-hyperdoped Si nanowires (PH-SiNWs) with atomic ratios of the P content ranging from 1 to 2 atom % via the tin(Sn)-seeded supercritical fluid-liquid-solid (SFLS) through the use of red P nanoparticles as dopant precursors. The resistivity of PH-SiNWs is 4.3 X 10(-3) Omega.m, which is about 6 orders of magnitude lower than bulk silicon (Si) (1.86 X 10(3) Omega.m) and about 3 orders of magnitude lower than intrinsic SiNWs (1.19 Omega.m). PH-SiNWs can be assembled on fabrics used as active materials for lithium-ion batteries, and combined with carbon nanotube fabric as current collectors, the bilayer fabrics can be used as freestanding independent lithium-ion battery anodes without the need for binders and additive. The PH-SiNWs/carbon nanotube (CNT) bilayer fabric anode reaches 820 mAh g(-1) after 1000 cycles at a charge/discharge rate of 2 A g(-1), whereas the intrinsic SiNWs/CNT bilayer fabric only sustains its performance at the first 20 cycles. The PH-SiNWs/CNT bilayer fabric anode shows the first example of a solution-grown Si nanowire anode with a 1000-cycle life. The ex situ transmission electron microscopy (TEM) image shows that an evolved PH-SiNWs nanopore structure was formed after the cycle, whereas the intrinsic SiNWs anodes did not develop holes. This result can be attributed to the uniform doping of P in the Si nanowire, which enables the formation of nanopores for rapid lithium-ion transport tunnels.

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