This Review covers a sequence of key discoveries and technical achievements that eventually led to the birth of the lithium-ion battery. In doing so, it not only sheds light on the history with the advantage of contemporary hindsight but also provides insight and inspiration to aid in the ongoing quest for better batteries of the future. A detailed retrospective on ingenious designs, accidental discoveries, intentional breakthroughs, and deceiving misconceptions is given: from the discovery of the element lithium to its electrochemical synthesis; from intercalation host material development to the concept of dual-intercalation electrodes; and from the misunderstanding of intercalation behavior into graphite to the comprehension of interphases. The onerous demands of bringing all critical components (anode, cathode, electrolyte, solid-electrolyte interphases), each of which possess unique chemistries, into a sophisticated electrochemical device reveal that the challenge of interfacing these originally inco...

Before Li Ion Batteries

In the critical area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-density and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorganic solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochemical and mechanical properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of physical contact, the solutions to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials. Solid-state batteries are attractive due to their potential safety, energy-density and cycle-life benefits. Recent progress in understanding inorganic solid electrolytes considering multiscale ion transport, electrochemical and mechanical properties, and processing are discussed.

Fundamentals of inorganic solid-state electrolytes for batteries

Commercial lithium-ion (Li-ion) batteries suffer from low energy density and do not meet the growing demands of the energy storage market. Therefore, building next-generation rechargeable Li and Li-ion batteries with higher energy densities, better safety characteristics, lower cost and longer cycle life is of outmost importance. To achieve smaller and lighter next-generation rechargeable Li and Li-ion batteries that can outperform commercial Li-ion batteries, several new energy storage chemistries are being extensively studied. In this review, we summarize the current trends and provide guidelines towards achieving this goal, by addressing batteries using high-voltage cathodes, metal fluoride electrodes, chalcogen electrodes, Li metal anodes, high-capacity anodes as well as useful electrolyte solutions. We discuss the choice of active materials, practically achievable energy densities and challenges faced by the respective battery systems. Furthermore, strategies to overcome remaining challenges for achieving energy characteristics are addressed in the hope of providing a useful and balanced assessment of current status and perspectives of rechargeable Li and Li-ion batteries.

Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries.

Solid electrolytes (SEs) are widely considered as an ‘enabler’ of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li7La3Zr2O12 (LLZO) and Li2S–P2S5 is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li3PS4) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li3PS4. Our findings suggest the high electronic conductivity of LLZO and Li3PS4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries. Despite its importance in lithium batteries, the mechanism of Li dendrite growth is not well understood. Here the authors study three representative solid electrolytes with neutron depth profiling and identify high electronic conductivity as the root cause for the dendrite issue.

High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes

The propensity of metals to form irregular and nonplanar electrodeposits at liquid-solid interfaces has emerged as a fundamental barrier to high-energy, rechargeable batteries that use metal anodes. We report an epitaxial mechanism to regulate nucleation, growth, and reversibility of metal anodes. The crystallographic, surface texturing, and electrochemical criteria for reversible epitaxial electrodeposition of metals are defined and their effectiveness demonstrated by using zinc (Zn), a safe, low-cost, and energy-dense battery anode material. Graphene, with a low lattice mismatch for Zn, is shown to be effective in driving deposition of Zn with a locked crystallographic orientation relation. The resultant epitaxial Zn anodes achieve exceptional reversibility over thousands of cycles at moderate and high rates. Reversible electrochemical epitaxy of metals provides a general pathway toward energy-dense batteries with high reversibility.

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Reversible epitaxial electrodeposition of metals in battery anodes.

Enabling the reversible lithium metal electrode is essential for surpassing the energy content of today’s lithium-ion cells. Although lithium metal cells for niche applications have been developed already, efforts are underway to create rechargeable lithium metal batteries that can significantly advance vehicle electrification and grid energy storage. In this Perspective, we focus on three tasks to guide and further advance the reversible lithium metal electrode. First, we summarize the state of research and commercial efforts in terms of four key performance parameters, and identify additional performance parameters of interest. We then advocate for the use of limited lithium (≤30 μm) to ensure early identification of technical challenges associated with stable and dendrite-free cycling and a more rapid transition to commercially relevant designs. Finally, we provide a cost target and outline material costs and manufacturing methods that could allow lithium metal cells to reach 100 US$ kWh–1. Li metal batteries offer much hope for the future of high-energy storage systems. Albertus et al. survey the current status of research and commercial efforts, and discuss key metrics and measurements as well as cost issues in enabling high-performing lithium metal electrodes.

Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries

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A device useful for oral drug delivery device consisting of: (a) a capsule, tablet or pill designed to disperse in the gastrointestinal system; (b) an RFID tag positioned in the capsule, tablet or pill, the RFID tag comprising an antenna; (c) an object selected from the group consisting of a magnet, a ferromagnetic object, a ferrite object and an electromagnetic shielding object positioned within, over or adjacent the antenna of the RFID tag to alter the antenna characteristics of the RFID tag so that if the RFID tag is interrogated before the capsule, tablet or pill disperses in the gastrointestinal system, the response of the RFID tag is sufficiently altered or attenuated to determine that the capsule, tablet or pill has not dispersed in the gastrointestinal system and so that if the RFID tag is interrogated after the capsule, tablet or pill has dispersed in the gastrointestinal system, the object separates from the RFID tag so that the response of the RFID tag is sufficiently detectable to determine that the capsule, tablet or pill has dispersed in the gastrointestinal system. Alternatively, a switch can be used to signal ingestion of the device, and change the response of the device. In another embodiment, the instant invention is a device useful for oral drug delivery, consisting of: (a) a capsule, tablet or pill designed to disperse in the gastrointestinal system; (b) a first non-anti-collision RFID tag positioned in the capsule; (c) a second non-anti-collision RFID tag positioned in the capsule, so that if the RFID tags are interrogated by an RFID reader before the capsule, tablet or pill disperses in the gastrointestinal system, the response of the RFID tags collide and so that after the dispersible material of the capsule has dispersed in the gastrointestinal system thereby allowing the first and second non-anti-collision tags to separate from each other, then the response of the RFID tags is sufficiently different from each other to determine that the capsule has dispersed in the gastrointestinal system.

Oral drug compliance monitoring using radio frequency identification tags

The present invention relates to a composition and to a display device having the composition positioned between electrodes. The composition contains : (a) a compound that undergoes a reversible redox reaction to generate a pH gradient between the two electrodes, (b) an indicator dye, (c) a charge transport material, and optionally, (d) a matrix material and (e) an opacifier, and (f) secondary redox couple wherein components (a), (b), and (c) are different from one another and the standard reduction potential of component (a) is less than the standard reduction potential for the other components. Depending on the electric field present between the electrodes, a display image may be generated.

Electrochromic display device and compositions useful in making such devices

An electrode/separator assembly for use in an electrochemical cell includes a current collector; a porous composite electrode layer adhered to the current collector, said electrode layer comprising at least electroactive particles and a binder; and a porous composite separator layer comprising inorganic particles substantially uniformly distributed in a polymer matrix to form nanopores and having a pore volume fraction of at least 25%, wherein the separator layer is secured to the electrode layer by a solvent weld at the interface between the two layers, said weld comprising a mixture of the binder and the polymer. Methods of making and using the assembly are also described.

Susan J. Babinec

Papers

Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries

Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries

Oral drug compliance monitoring using radio frequency identification tags

Electrochromic display device and compositions useful in making such devices

Separator for electrochemical cell and method for its manufacture