Thermodynamics of Lithium Intercalation into Graphites and Disordered Carbons

The temperature dependence of the open-circuit potential of lithium half-cells was measured for electrodes of carbon materials having different amounts of structural disorder. The entropy of lithium intercalation, DeltaS, and enthalpy of intercalation, DeltaH, were determined over a broad range of lithium concentrations. For the disordered carbons, DeltaS is small. For graphite, an initially large DeltaS decreases with lithium concentration, becomes negative, and then shows two plateaus associated with the formation of intercalation compounds. For all carbons DeltaH is negative, and decreases in magnitude with increased lithium concentration. For lithium concentrations less than x = 0.5 in LixC6, for the disordered carbons the magnitude of DeltaH is significantly more negative than for graphite (i.e., intercalation is more exothermic). The measurements of DeltaH provide an energy spectrum of chemical environments for lithium. This spectrum can be used to understand some of the concentration dependence of configurational entropy, but the negative values of DeltaS require another contribution to entropy, perhaps vibrational in origin

An XRD Study of Chemical Self-Discharge in Delithiated Cobalt Oxide

Changes in samples of Li1–xCoO2 were measured by X-ray diffractometry (XRD) after thermal aging treatments that cause capacity losses in electrochemical cells. Changes in lattice parameters were used to identify lithium re-intercalation into Li1–xCoO2 when it was aged in the presence of LiClO4, LiPF6, and LiAsF6 in propylene carbonate (PC). Li+ re-intercalation could account for the reversible capacity loss. Thermal aging at 75°C in pure PC or pure argon gas resulted in other changes that are attributed to the formation of spinel phase. The rate of the lithium re-intercalation increases in the following sequence: LiPF6<LiClO4<LiAsF6

Strongly Tunable Anisotropic Thermal Transport in MoS2 by Strain and Lithium Intercalation: First--Principles Calculations

The possibility of tuning the vibrational properties and the thermal conductivity of layered van der Waals materials either chemically or mechanically paves the way to significant advances in nanoscale heat management. Using first-principles calculations we investigate the modulation of heat transport in MoS2 by lithium intercalation and cross-plane strain. We find that both the in-plane and cross-plane thermal conductivity (kr, kz) of MoS2 are extremely sensitive to both strain and electrochemical intercalation. Combining lithium intercalation and strain, the in-plane and cross-plane thermal conductivity can be tuned over one and two orders of magnitude, respectively. Furthermore, since kr and kz respond in different ways to intercalation and strain, the thermal conductivity anisotropy can be modulated by two orders of magnitude. The underlying mechanisms for such large tunability of the anisotropic thermal conductivity of \Mos are explored by computing and analyzing the dispersion relations, group velocities, relaxation times and mean free paths of phonons. Since both intercalation and strain can be applied reversibly, their stark effect on thermal conductivity can be exploited to design novel phononic devices, as well as for thermal management in MoS2-based electronic and optoelectronic systems

The Joint Center for Energy Storage Research: A New Paradigm for Battery Research and Development

The Joint Center for Energy Storage Research (JCESR) seeks transformational change in transportation and the electricity grid driven by next generation high performance, low cost electricity storage. To pursue this transformative vision JCESR introduces a new paradigm for battery research: integrating discovery science, battery design, research prototyping and manufacturing collaboration in a single highly interactive organization. This new paradigm will accelerate the pace of discovery and innovation and reduce the time from conceptualization to commercialization. JCESR applies its new paradigm exclusively to beyond-lithium-ion batteries, a vast, rich and largely unexplored frontier. This review presents JCESR's motivation, vision, mission, intended outcomes or legacies and first year accomplishments.Comment: 17 pages, 14 figures, 96 reference

On the Balance of Intercalation and Conversion Reactions in Battery Cathodes

We present a thermodynamic analysis of the driving forces for intercalation and conversion reactions in battery cathodes across a range of possible working ion, transition metal, and anion chemistries. Using this body of results, we analyze the importance of polymorph selection as well as chemical composition on the ability of a host cathode to support intercalation reactions. We find that the accessibility of high energy charged polymorphs in oxides generally leads to larger intercalation voltages favoring intercalation reactions, whereas sulfides and selenides tend to favor conversion reactions. Furthermore, we observe that Cr-containing cathodes favor intercalation more strongly than those with other transition metals. Finally, we conclude that two-electron reduction of transition metals (as is possible with the intercalation of a $2+$ ion) will favor conversion reactions in the compositions we studied

Nanoscale Voltage Enhancement at Cathode Interfaces in Li-ion Batteries

Interfaces are ubiquitous in Li-ion battery electrodes, occurring across compositional gradients, regions of multiphase intergrowths, and between electrodes and solid electrolyte interphases or protective coatings. However, the impact of these interfaces on Li energetics remains largely unknown. In this work, we calculated Li intercalation-site energetics across cathode interfaces and demonstrated the physics governing these energetics on both sides of the interface. We studied the olivine/olivine-structured LixFePO4/LixMPO4 (x=0 and 1, M=Co, Ti, Mn) and layered/layered-structured LiNiO2/TiO2 interfaces to explore different material structures and transition metal elements. We found that across an interface from a high- to low-voltage material the Li voltage remains constant in the high-voltage material and decays approximately linearly in the low-voltage region, approaching the Li voltage of the low-voltage material. This effect ranges from 0.5-9nm depending on the interfacial dipole screening. This effect provides a mechanism for a high-voltage material at an interface to significantly enhance the Li intercalation voltage in a low-voltage material over nanometer scale. We showed that this voltage enhancement is governed by a combination of electron transfer (from low- to high-voltage regions), strain and interfacial dipole screening. We explored the implications of this voltage enhancement for a novel heterostructured-cathode design and redox pseudocapacitors