Development Of High-energy Silicon-based Anode Materials For Lithium-ion Storage

Open Access
Yi, Ran
Graduate Program:
Mechanical Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
January 29, 2015
Committee Members:
  • Donghai Wang, Dissertation Advisor
  • Christopher Rahn, Committee Member
  • Michael Anthony Hickner, Committee Member
  • Sulin Zhang, Committee Member
  • Lithium-ion batteries
  • anodes
  • silicon
  • composite
  • hybrid capacitors
The emerging markets of electric vehicles (EV) and hybrid electric vehicles (HEV) generate a tremendous demand for low-cost lithium-ion batteries (LIBs) with high energy and power densities, and long cycling life. The development of such LIBs requires development of low cost, high-energy-density cathode and anode materials. Conventional anode materials in commercial LIBs are primarily synthetic graphite-based materials with a capacity of ~370 mAh/g. Improvements in anode performance, particularly in anode capacity, are essential to achieving high energy densities in LIBs for EV and HEV applications. This dissertation focuses on development of micro-sized silicon-carbon (Si-C) composites as anode materials for high energy and power densities LIBs. First, a new, low-cost, large-scale approach was developed to prepare a micro-sized Si-C composite with excellent performance as an anode material for LIBs. The composite shows a reversible capacity of 1459 mAh/g after 200 cycles at 1 A/g (97.8% capacity retention) and excellent high rate performance of 700 mAh/g at 12.8 A/g, and also has a high tap density of 0.78 g/cm3. The structure of the composite, micro-sized as a whole, features the interconnected nanoscale size of the Si building blocks and the uniform carbon filling, which enables the maximum utilization of silicon even when the micro-sized particles break into small pieces upon cycling. To understand the effects of key parameters in designing the micro-sized Si-C composites on their electrochemical performance and explore how to optimize them, the influence of Si nanoscale building block size and carbon coating on the electrochemical performance of the micro-sized Si-C composites were investigated. It has been found that the critical Si building block size is 15 nm, which enables a high capacity without compromising the cycling stability, and that carbon coating at higher temperature improves the 1st cycle coulombic efficiency (CE) and the rate capability. Corresponding reasons underneath electrochemical performance have been revealed by various characterizations. Combining both optimized Si building block size and carbon coating temperature, the resultant composite can sustain 600 cycles at 1.2 A/g with a fixed lithiation capacity of 1200 mAh/g, the best cycling performance with such a high capacity for micro-sized Si-based anodes. To further improve the the rate capability of Si-based anode materials, an effecitive method of facile boron doping was demonstrated. Boron-doped Si-C composite can deliver a high capacity of 575 mAh/g at 6.4 A/g without addition of any conductive additives, 80% higher than that of undoped composite. Compared to the obvious capacity fading of undoped Si-C composite, boron-doped Si-C composite maintains its capacity well upon long cycling at a high current density. Electrochemical impedance spectroscopy (EIS) measurement shows boron-doped Si-C composite has lower charge transfer resistance, which helps improve its rate capability. A novel micro-sized graphene/Si-C composite (G/Si-C) was then developed to translate the performance of such micro-sized Si-C composites from the material level to the electrode level aiming to achieve high areal capacities (mAh/cm2) besides gravimetric capacities (mAh/g). Owing to dual conductive networks both within single particles formed by carbon and between different particles formed by graphene, low electrical resistance can be maintained at high mass loading, which enables a high degree of material utilization. Areal capacity thus increases almost linearly with mass loading. As a result, G/Si-C exhibits a high areal capacity of 3.2 mAh/cm2 after 100 cycles with high coulombic efficiency (average 99.51% from 2nd to 100th cycle), comparable to that of commercial anodes. Finally, a micro-sized Si-based material (B-Si/SiO2/C) featuring high rate performance was developed via a facile route without use of toxic hydrofluoric acid. A Li-ion hybrid battery constructed of such a Si-based anode and a porous carbon cathode was demonstrated with both high power and energy densities. Boron-doping is employed to improve the rate capability of B-Si/SiO2/C. At a high current density of 6.4 A/g, B-Si/SiO2/C delivers a capacity of 685 mAh/g, 2.4 times that of the undoped Si/SiO2/C. Benefiting from the high rate performance along with low working voltage, high capacity and good cycling stability of B-Si/SiO2/C, the hybrid battery exhibits a high energy density of 128 Wh/kg at 1229 W/kg. Even when power density increases to the level of a conventional supercapacitor (9704 W/kg), 89 Wh/kg can be obtained, the highest values of any hybrid battery to date. Long cycling life (capacity retention of 70% after 6000 cycles) and low self-discharge rate (voltage retention of 82% after 50 hours) are also achieved.