Silicon/graphite (Si/Gr) nanocomposites with controlled void spaces and encapsulated by a carbon shell (Si/Gr@void@C) are synthesized by utilizing high-energy ball milling to reduce micron-sized particles to nanoscale, followed by carbonization of polydopamine (PODA) to form a carbon shell, and finally partial etching of the nanostructured Si core by NaOH solution at elevated temperatures. In particular, the effects of ball milling time and NaOH etching temperature on the electrochemical properties of Si/Gr@void@C are investigated. Increasing the ball milling time results in the improved specific capacity of Si-based anodes. Carbon coating further enhances the specific capacity and capacity retention over charge/discharge cycles. The best cycle stability is achieved after partial etching of the Si core inside Si/Gr@void@C particles at either 70 or 80 C, leading to little or no capacity decay over 130 cycles. However, it is found that both carbon coating and NaOH etching processes cause some surface oxidation of the nanostructured Si particles derived from high-energy ball milling. The surface oxidation of the nanostructured Si results in decreases in specific capacity and should be minimized in future studies. The mechanistic understanding developed in this study paves the way to further improve the electrochemical performance of Si/Gr@void@C nanocomposites in future.
more »
« less
Synthesis and performance of nanostructured silicon/graphite composites with a thin carbon shell and engineered voids
Utilizing silicon as an anode material for Li-ion batteries has been the subject of many studies. However, due to the huge volume change of silicon during lithiation, the electrochemical performance of silicon is poor. Here, we have investigated a novel yet simple approach to synthesize nanostructured silicon/graphite composites with a carbon coating and engineered voids. High-energy ball mill is employed to convert micrometer-sized silicon and graphite to nanostructured silicon/graphite composite building blocks, while a thin carbon coating is applied to encapsulate these composite agglomerates, followed by partial etching of silicon to create engineered voids inside the composite agglomerates. The batteries made with this tailored nanostructure exhibit improved electrochemical performance over the counterparts made with silicon nanoparticles and exhibited a specific capacity of ~1800 mA h g-1 discharge capacity at the first cycle, 580 mA h g-1 after 40 cycles, and 350 mA h g-1 after 300 cycles. This study has established a novel method scalable at industry environment and capable of producing low cost Si anodes and clearly shown that the cycle stability of the tailored nanostructure improves with increasing engineered voids in the range we have investigated.
more »
« less
- Award ID(s):
- 1660572
- PAR ID:
- 10175288
- Date Published:
- Journal Name:
- Electrochimica acta
- Volume:
- 258
- ISSN:
- 0013-4686
- Page Range / eLocation ID:
- 274 - 283
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
A nanoporous Ni/NiO/C nanocomposite with a gyroid nanostructure was fabricated by using a nanoporous polymer with gyroid nanochannels as a template. The polymer template was obtained from the self-assembly of a degradable block copolymer, polystyrene- b -poly( l -lactide) (PS-PLLA), followed by the hydrolysis of PLLA blocks. Templated electroless plating followed by calcination was performed to create a precisely controlled Ni/NiO gyroid nanostructure. After carbon coating, a well-interconnected nanoporous gyroid Ni/NiO/C nanocomposite can be successfully fabricated. Benefiting from the well-interconnected nanoporous structure with ultrafine transition metal oxide and uniform carbon coating, the gyroid nanoporous Ni/NiO/C nanocomposite electrodes exhibited high specific capacities at various rates (1240 mA h g −1 at 0.2 A g −1 , 902 mA h g −1 at 2 A g −1 and 424 mA h g −1 at 10 A g −1 ) and excellent cyclability (809 mA h g −1 at 1 A g −1 after 1000 cycles, average coulombic efficiency 99.86%). This research demonstrates a universal approach for constructing a nanostructured electrode with explicitly controlled block copolymer phase separation.more » « less
-
Abstract Ni‐rich LiNi0.8Co0.1Mn0.1O2(NCM811) has been considered as a promising cathode material for high energy density lithium‐ion batteries. However, it experiences undesirable interfacial side‐reactions with the electrolyte, which lead to a rapid capacity decay. In this work, a homogeneous precipitation method is proposed for forming a uniform silicon dioxide (SiO2) coating on the NCM811 surface. The strong Si−O network provided a stable protective layer between the NCM811 active material and electrolyte to improve the electrochemical stability. As a result, the NCM811@SiO2cathode showed superior cycling stability (84.9 % after 100 cycles at 0.2 C) and rate capability (142.7 mA h g−1at 5 C) compared to the pristine NCM811 cathode (56.6 % after 100 cycles, 127.9 mA h g−1at 5 C). Moreover, the SiO2coating effectively suppressed voltage decay and pulverization of the NCM811 particles during long term cycling. This uniform coating technique offers a viable approach for stabilizing Ni‐rich cathode materials for high‐energy density lithium‐ion batteries.more » « less
-
In this study, two green organic solvents are reported in LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC111)-based slurry preparation and subsequent cathode fabrication for Li ion batteries. NMC111, conductive carbon and poly(vinylidene fluoride) binder composite slurries prepared with methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (PolarClean) and dimethyl isosorbide (DMI) exhibit mechanically stable, crack-free uniform coating structures. Both slurries showed similar shear-thinning viscosity behavior that suggests similar processibility during electrode casting and coating. When used as the cathode in Li/NMC111 half cells, the electrode slurries prepared with PolarClean show promising electrochemical performance metrics with an average specific charge capacity of 155 ± 1 mA h g −1 at C/10 over 100 cycles, comparable to the films (152 ± 3 mA h g −1 at C/10) prepared with traditional N -methyl pyrrolidone (NMP) solvent. The use of PolarClean points to a potential route to replace toxic NMP in cathode fabrication without altering the manufacturing process. However, electrodes prepared with DMI demonstrate inferior electrochemical performance with an average charge capacity of 120 mA h g −1 . Nonetheless, DMI may still offer some promising features and warrants further detailed investigation in terms of compatible electrolyte, tailoring the slurry preparation, and casting conditions.more » « less
-
Abstract Chloroaluminate ionic liquids are commonly used electrolytes in rechargeable aluminum batteries due to their ability to reversibly electrodeposit aluminum at room temperature. Progress in aluminum batteries is currently hindered by the limited electrochemical stability, corrosivity, and moisture sensitivity of these ionic liquids. Here, a solid polymer electrolyte based on 1‐ethyl‐3‐methylimidazolium chloride‐aluminum chloride, polyethylene oxide, and fumed silica is developed, exhibiting increased electrochemical stability over the ionic liquid while maintaining a high ionic conductivity of ≈13 mS cm−1. In aluminum–graphite cells, the solid polymer electrolytes enable charging to 2.8 V, achieving a maximum specific capacity of 194 mA h g−1at 66 mA g−1. Long‐term cycling at 2.7 V showed a reversible capacity of 123 mA h g−1at 360 mA g−1and 98.4% coulombic efficiency after 1000 cycles. Solid‐state nuclear magnetic resonance spectroscopy measurements reveal the formation of five‐coordinate aluminum species that crosslink the polymer network to enable a high ionic liquid loading in the solid electrolyte. This study provides new insights into the molecular‐level design and understanding of polymer electrolytes for high‐capacity aluminum batteries with extended potential limits.more » « less
An official website of the United States government

