Advanced Nanomaterials for Lithium-Ion Batteries

A novel method for surface modification of LiNi_0.5Mn_1.5O₄ (LNMO) was proposed, in which a hybrid layer combined by Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) and carbon (C) composite on LNMO material were connected by lithium iodide. Structure and morphology analyses illustrated that a higher contact area of active substances was achieved by the LATP/C composite layer without changing the original crystal structure of LNMO. XPS analysis proved that I⁻ promoted the reduction of trace Mn⁴⁺, resulting in a higher ion conductivity. Galvanostatic charge–discharge tests exhibited the capacity of the LNMO with 5% LATP/C improved with 35.83% at 25 °C and 95.77% at 50 °C, respectively, compared with the bare after 100 cycles, implying the modification of high-temperature deterioration. EIS results demonstrated that one order of magnitude of improvement of the lithium-ion diffusion coefficient of LATP/C-LNMO was achieved (3.04 × 10⁻¹¹ S cm⁻¹). In conclusion, the effective low-temperature modification strategy improved the ionic and electronic conductivities of the cathode and suppressed the side reactions of high-temperature treatment. Full article

Spinel ZnMn₂O₄ is considered a promising anode material for high-capacity Li-ion batteries due to their higher theoretical capacity than commercial graphite anode. However, the insufficient cycling and rate properties seriously limit its practical application. In this work, porous ZnMn₂O₄ hollow micro-rods (ZMO HMRs) are synthesized by a facile co-precipitation method coupled with annealing treatment. On the basis of electrochemical analyses, the as-obtained samples are first characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy techniques. The influences of different polyethylene glycol 400 (PEG 400) additions on the formation of the hollow rod structure are also discussed. The abundant multi-level pore structure and hollow feature of ZMO HMRs effectively alleviate the volume expansion issue, rendering abundant electroactive sites and thereby guaranteeing convenient Li⁺ diffusion. Thanks to these striking merits, the ZMO HMRs anode exhibits excellent electrochemical lithium storage performance with a reversible specific capacity of 761 mAh g⁻¹ at a current density of 0.1 A g⁻¹, and a long-cycle specific capacity of 529 mAh g⁻¹ after 1000 cycles at 2.0 A g⁻¹ and keep a remarkable rate capability. In addition, the assembled ZMO HMRs-based full cells deliver an excellent rate capacity, and when the current density returns to 0.05 A g⁻¹, the specific capacity can still reach 105 mAh g⁻¹ and remains at 101 mAh g⁻¹ after 70 cycles, maintaining a material-level energy density of approximately 273 Wh kg⁻¹. More significantly, such striking electrochemical performance highlights that porous ZMO HMRs could be a promising anode candidate material for LIBs. Full article

Silicon is a promising anode material that can increase the theoretical capacity of lithium-ion batteries (LIBs). However, the volume expansion of silicon remains a challenge. In this study, we employed a novel combination of conductive additives to effectively suppress the volume expansion of Si during charging/discharging cycles. Rather than carbon black (CB), which is commonly used in SiO anodes, we introduced single-walled carbon nanotubes (SWCNTs) as a conductive additive. Owing to their high aspect ratio, CNTs enable effective connection of SiO particles, leading to stable electrochemical operation to prevent volume expansion. In addition, we explored a combination of CB and SWCNTs, with results showing a synergetic effect compared to a single-component of SWCNTs, as small-sized CB particles can enhance the interface contact between the conductive additive and SiO particles, whereas SWCNTs have limited contact points. With this hybrid conductive additive, we achieved a stable operation of full-cell LIBs for more than 200 cycles, with a retention rate of 91.1%, whereas conventional CB showed a 74.0% specific capacity retention rate. Full article

This article shows the results of experiments to grow Nitrogen incorporated ultrananocrystalline diamond (N-UNCD) films on commercial natural graphite (NG)/Cu anodes by hot chemical vapor deposition (HFCVD) using a gas mixture of Ar/CH₄/N₂/H₂. The experiments focused on studying the effect of the pressure in the HFCVD chamber, filament-substrate distance, and temperature of the substrate. It was found that a substrate distance of 3.0 cm and a substrate temperature of 575 C were optimal to grow N-UNCD film on the graphite surface as determined by Raman spectroscopy, SEM, and TEM imaging. XPS analysis shows N incorporation through the film. Subsequently, the substrate surface temperature was increased using a heater, while keeping the substrate-filament distance constant at 3.0 cm. In this case, Raman spectra and SEM images of the substrate surface showed a major composition of graphite in the film as the substrate-surface temperature increased. Finally, the process pressure was increased to 10 Torr where it was seen that the growth of N-UNCD film occurred at 2.0 cm at a substrate temperature of 675 C. These results suggest that as the process pressure increases a smaller substrate-filament distance and consequently a higher substrate surface temperature can still enable the N-UNCD film growth by HFCVD. This effect is explained by a mean free path analysis of the main precursors H₂ and CH₃ molecules traveling from the filament to the surface of the substrate The potential impact of the process developed to grow electrically conductive N-UNCD films using the relatively low-cost HFCVD process is that this process can be used to grow N-UNCD films on commercial NG/Cu anodes for Li-ion batteries (LIBs), to enable longer stable capacity energy vs. charge/discharge cycles. Full article

Silicon is a worthy substitute anode material for lithium-ion batteries because it offers high theoretical capacity and low working potentials vs. Li⁺/Li. However, immense volume changes and the low intrinsic conductivity of Si hampers its practical applications. In this study, nano/micro silicon particles are achieved by ball milling silicon mesh powder as a scalable process. Subsequent metal (Cu/Fe/Mn) doping into nano/micro silicon by low-temperature annealing, followed by high-temperature annealing with graphite, gives a metal-doped silicon/graphite composite. The obtained composites were studied as anodes for Li-ion batteries, and they delivered high reversible capacities of more than 1000 mAh g⁻¹ with improved Li⁺ diffusion properties. The full cells from these composite anodes vs. LiCoO₂ cathodes delivered suitable energy densities for Li⁺ storage applications. The enhanced electrochemical properties are accredited to the synergistic effect of metal doping and graphite addition to silicon and exhibit potential for suitable Li⁺ energy storage applications. Full article