Engineering topics
Karki, Khim
Publications and source records attributed to Karki, Khim.
Ultra-low liquid helium temperature in-situ TEM sample holder
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Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF 2
Intercalation-type electrodes have now been commonly employed in today’s batteries as such materials are capable of storing and releasing lithium reversibly via topotactic transformation, conducive to small structural change, but they have limited interstitial sites to hold Li. In contrast, conversion electrodes feature high Li-storage capacity, but often undergo large structural change during (de)lithiation, resulting in cycling instability. One exception is iron fluoride (FeF 2 ), a conversion-type cathode that exhibits both high capacity and high cycling stability. Herein, we report a lithiation-driven topotactic transformation in a single crystal of FeF2, unveiled by in situ visualization of the spatial and crystallographic correlation between the parent and converted phases. Specifically, conversion in FeF 2 resembles the intercalation process but involves transport of both Li + and Fe 2+ ions within the F-anion array, leading to formation of Fe preferentially along specific crystallographic orientations of FeF 2 . Throughout the process, the F-anion framework is retained, creating a checkerboard-like structure, within which the volume change is largely compensated, thereby enabling the high cyclability in FeF 2 . Lastly, findings from this study, with unique insights into conversion reaction mechanisms, may help to pave the way for designing conversion-type electrodes for the next-generation high energy lithium batteries.
Structural Changes in a High-Energy Density VO 2 F Cathode upon Heating and Li Cycling
Structural changes in VO 2 F, which allow two-electron transfer during electrochemical Li cycling, were investigated in this work. This compound adopts a rhombohedral structure, space group $R\overline{3}c$, with O and F sharing one site, and was synthesized by high-energy ball-milling. The thermal stability of VO 2 F, which is related to the battery safety, is studied by in situ XRD upon heating and by thermal gravimetric analysis. VO 2 F is found to be stable up to 160 °C under inert atmosphere; above this temperature, it converts into vanadium oxide with fluorine loss. The structure evolution upon lithium cycling was studied by ex situ X-ray diffraction and absorption techniques. The results show that lithiation of VO 2 F goes through a solid-solution reaction, and the rhombohedral structure is preserved if no more than one lithium ion is intercalated. Upon a second Li insertion, an irreversible transition to a rock-salt structure occurs. We show using first-principles calculations that this irreversible transformation can be explained by an asymmetric energetic preference between the rhombohedral and rock-salt forms of Li x VO 2 F, which result in large thermodynamic driving forces to convert to the rock-salt structure at x > 1 and relatively small thermodynamic driving forces to convert back to the rhombohedral structure when delithiating to x < 1.
Intergranular Cracking as a Major Cause of Long-Term Capacity Fading of Layered Cathodes
Capacity fading has limited commercial layered Li-ion battery electrodes to <70% of their theoretical capacity. Higher capacities can be achieved initially by charging to higher voltages, however, these gains are quickly eroded by a faster fade in capacity. In-creasing lifetimes and reversible capacity is contingent on identifying the origin of this capacity fade to inform electrode design and synthesis. We must understand how the battery reactions change following capacity loss after long-term cycling. Using operando X-ray diffraction, we followed the reaction of a LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) electrode after months of charge-discharge cycles. Furthermore, the heterogeneous reaction kinetics observed during extended cycles quantitatively explain the capacity loss, which is ultimately attributed to inter-granular fracturing that degrades the connectivity of sub-surface grains within the polycrystalline NCA aggregate.
Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2 VO 2 F
Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2 VO 2 F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2 VO 2 F are optimized. The thermal stability of Li 2 VO 2 F, which is related to the safety of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2 VO 2 F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.
Atomic Insight into the Layered/Spinel Phase Transformation in Charged LiNi 0.80 Co 0.15 Al 0.05 O 2 Cathode Particles
Layered LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA) holds great promise as a potential cathode material for high energy density lithium ion batteries. However, its high capacity is heavily dependent on the stability of its layered structure, which suffers from a severe structure degradation resulting from a not fully understood layered → spinel phase transformation. Using high-resolution transmission electron microscopy and electron diffraction, we probe the atomic structure evolution induced by the layered → spinel phase transformation in the NCA cathode. We show that the phase transformation results in the development of a particle structure with the formation of complete spinel, spinel domains, and intermediate spinel from the surface to the subsurface region. The lattice planes of the complete and intermediate spinel phases are highly interwoven in the subsurface region. The layered → spinel transformation occurs via the migration of transition metal (TM) atoms from the TM layer into the lithium layer. Incomplete migration leads to the formation of the intermediate spinel phase, which is featured by tetrahedral occupancy of TM cations in the lithium layer. Finally, the crystallographic structure of the intermediate spinel is discussed and verified by the simulation of electron diffraction patterns.
Tuning the Activity of Oxygen in LiNi 0.8 Co 0.15 Al 0.05 O 2 Battery Electrodes
Layered transition metal oxides such as LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) are highly desirable battery electrodes. However, these materials suffer from thermal runaway caused by deleterious oxygen loss and surface phase transitions at highly overcharged and overheated conditions, prompting serious safety concerns. Using in situ environmental transmission electron microscopy techniques, we demonstrate surface oxygen loss and structural changes in the highly overcharged NCA particles are suppressed by exposing them to an oxygen-rich environment. The onset temperature for the loss of oxygen from the electrode particle is delayed to 350 °C at oxygen gas overpressure of 400 mTorr. Similar heating of the particles in a reducing hydrogen gas demonstrated a quick onset of oxygen loss at 150 °C and rapid surface degradation of the particles. Lastly, the results reported here illustrate the fundamental materials science governing the failure processes of electrode particles and highlight possible strategies to circumvent such issues.
Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO 4 over Multiple Lithium Intercalation
ε -Li x VOPO 4 is a promising multi-electron cathode for rechargeable lithium-ion bat- teries that has an extremely high theoretical capacity of 318 mAh/g. In this w ork, we demonstrate the stable cycling of more than one Li in solid-state-syn thesized ε - LiVOPO 4 over more than 20 cycles for the first time. Using a combination of densit y functional theory (DFT) calculations, X-ray pair distribution funct ion (PDF) analy- sis and X-ray Absorption Near Edge Structure (XANES) measurements, we pre sent a comprehensive analysis of the thermodynamics, kinetics and stru ctural evolution of ε -Li x VOPO 4 over the entire lithiation range. We identify two intermediate ph ases at x = 1 . 5 and 1.75 in the low-voltage regime using DFT calculations, and the comput ed and electrochemically measured voltage profiles are in excellent agree ment. Operando PDF techniques show a reversible hysteretic change in the short ( < 2° A) V-O bond lengths coupled with an irreversible extension of the long V-O bond ( > 2.4 °A) dur- ing low-voltage cycling. These observations are confirmed with EXAFS spe ctra. We identify hydrogen intercalation from the electrolyte decomposition as a likely explana- tion for the ~ 2 . 4°A V-O bond and its irreversible extension. In terms of electronic conductivity, we find Li x VOPO 4 to be a large band gap insulator across the entire lithiation range, and calculated small polaron migration barriers are similar to those of the olivine LiMPO 4 cathodes. Finally, we demonstrate that ε -LiVOPO 4 is likely to be a one-dimensional diffuser using climbing-image nudged elastic ban d calculations. These results highlight the importance of nano-sizing and carbon coating in achieving good electrochemical performance in this material.
The Anode Challenge for Lithium‐Ion Batteries: A Mechanochemically Synthesized Sn–Fe–C Composite Anode Surpasses Graphitic Carbon
Carbon‐based anodes are the key limiting factor in increasing the volumetric capacity of lithium‐ion batteries. Tin‐based composites are one alternative approach. Nanosized Sn–Fe–C anode materials are mechanochemically synthesized by reducing SnO with Ti in the presence of carbon. The optimum synthesis conditions are found to be 1:0.25:10 for initial ratio of SnO, Ti, and graphite with a total grinding time of 8 h. This optimized composite shows excellent extended cycling at the C/10 rate, delivering a first charge capacity as high as 740 mAh g −1 and 60% of which still remained after 170 cycles. The calculated volumetric capacity significantly exceeds that of carbon. It also exhibits excellent rate capability, delivering volumetric capacity higher than 1.6 Ah cc −1 over 140 cycles at the 1 C rate.
Hoop-Strong Nanotubes for Battery Electrodes
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A Beaded-String Silicon Anode
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