The challenges and opportunities of battery-powered flight.

Aircraft, and the aviation ecosystem in which they operate, are shaped by complex trades among technical requirements, economics and environmental concerns, all built on a foundation of safety. This Perspective explores the requirements of battery-powered aircraft and the chemistries that hold promise to enable them. The difference between flight and terrestrial needs and chemistries are highlighted. Safe, usable specific energy rather than cost is the major constraint for aviation. We conclude that battery packs suitable for flight with specific energy approaching 600 kilowatt hours per kilogram may be achievable in the next decade given sufficient investment targeted at aeronautical applications.

Revisiting the cold case of cold fusion.

The 1989 claim of 'cold fusion' was publicly heralded as the future of clean energy generation. However, subsequent failures to reproduce the effect heightened scepticism of this claim in the academic community, and effectively led to the disqualification of the subject from further study. Motivated by the possibility that such judgement might have been premature, we embarked on a multi-institution programme to re-evaluate cold fusion to a high standard of scientific rigour. Here we describe our efforts, which have yet to yield any evidence of such an effect. Nonetheless, a by-product of our investigations has been to provide new insights into highly hydrided metals and low-energy nuclear reactions, and we contend that there remains much interesting science to be done in this underexplored parameter space.

Structural Complexities in Sodium Ion Conductive Antiperovskite Revealed by Cryogenic Transmission Electron Microscopy.

We use low-dose cryogenic transmission electron microscopy (cryo-TEM) to investigate the atomic-scale structure of antiperovskite Na2NH2BH4 crystals by preserving the room-temperature cubic phase and carefully monitoring the electron dose. Via quantitative analysis of electron beam damage using selected area electron diffraction, we find cryogenic imaging provides 6-fold improvement in beam stability for this solid electrolyte. Cryo-TEM images obtained from flat crystals revealed the presence of a new, long-range-ordered supercell with a cubic phase. The supercell exhibits doubled unit cell dimensions of 9.4 Å × 9.4 Å as compared to the cubic lattice structure revealed by X-ray crystallography of 4.7 Å × 4.7 Å. The comparison between the experimental image and simulated potential map indicates the origin of the supercell is a vacancy ordering of sodium atoms. This work demonstrates the potential of using cryo-TEM imaging to study the atomic-scale structure of air- and electron-beam-sensitive antiperovskite-type solid electrolytes.

Synthesis and Characterization of Dense Carbon Films as Model Surfaces to Estimate Electron Transfer Kinetics on Redox Flow Battery Electrodes.

Redox flow batteries (RFBs) are a promising electrochemical technology for the efficient and reliable delivery of electricity, providing opportunities to integrate intermittent renewable resources and to support unreliable and/or aging grid infrastructure. Within the RFB, porous carbonaceous electrodes facilitate the electrochemical reactions, distribute the flowing electrolyte, and conduct electrons. Understanding electrode reaction kinetics is crucial for improving RFB performance and lowering costs. However, assessing reaction kinetics on porous electrodes is challenging as their complex structure frustrates canonical electroanalytical techniques used to quantify performance descriptors. Here, we outline a strategy to estimate electron transfer kinetics on planar electrode materials of similar surface chemistry to those used in RFBs. First, we describe a bottom-up synthetic process to produce flat, dense carbon films to enable the evaluation of electron transfer kinetics using traditional electrochemical approaches. Next, we characterize the physicochemical properties of the films using a suite of spectroscopic methods, confirming that their surface characteristics align with those of widely used porous electrodes. Last, we study the electrochemical performance of the films in a custom-designed cell architecture, extracting intrinsic heterogeneous kinetic rate constants for two iron-based redox couples in aqueous electrolytes using standard electrochemical methods (i.e., cyclic voltammetry, electrochemical impedance, and spectroscopy). We anticipate that the synthetic methods and experimental protocols described here are applicable to a range of electrocatalysts and redox couples.

Toward electrochemical synthesis of cement-An electrolyzer-based process for decarbonating CaCO3 while producing useful gas streams.

Cement production is currently the largest single industrial emitter of CO2, accounting for ∼8% (2.8 Gtons/y) of global CO2 emissions. Deep decarbonization of cement manufacturing will require remediation of both the CO2 emissions due to the decomposition of CaCO3 to CaO and that due to combustion of fossil fuels (primarily coal) in calcining (∼900 °C) and sintering (∼1,450 °C). Here, we demonstrate an electrochemical process that uses neutral water electrolysis to produce a pH gradient in which CaCO3 is decarbonated at low pH and Ca(OH)2 is precipitated at high pH, concurrently producing a high-purity O2/CO2 gas mixture (1:2 molar ratio at stoichiometric operation) at the anode and H2 at the cathode. We show that the solid Ca(OH)2 product readily decomposes and reacts with SiO2 to form alite, the majority cementitious phase in Portland cement. Electrochemical calcination produces concentrated gas streams from which CO2 may be readily separated and sequestered, H2 and/or O2 may be used to generate electric power via fuel cells or combustors, O2 may be used as a component of oxyfuel in the cement kiln to improve efficiency and lower CO2 emissions, or the output gases may be used for other value-added processes such as liquid fuel production. Analysis shows that if the hydrogen produced by the reactor were combusted to heat the high-temperature kiln, the electrochemical cement process could be powered solely by renewable electricity.

Design principles for self-forming interfaces enabling stable lithium-metal anodes.

The path toward Li-ion batteries with higher energy densities will likely involve use of thin lithium (Li)-metal anode (<50 µm thickness), whose cyclability today remains limited by dendrite formation and low coulombic efficiency (CE). Previous studies have shown that the solid-electrolyte interface (SEI) of the Li metal plays a crucial role in Li-electrodeposition and -stripping behavior. However, design rules for optimal SEIs are not well established. Here, using integrated experimental and modeling studies on a series of structurally similar SEI-modifying model compounds, we reveal the relationship between SEI compositions, Li deposition morphology, and CE and identify two key descriptors for the fraction of ionic compounds and compactness, leading to high-performance SEIs. We further demonstrate one of the longest cycle lives to date (350 cycles for 80% capacity retention) for a high specific-energy Li||LiCoO2 full cell (projected >350 watt hours [Wh]/kg) at practical current densities. Our results provide guidance for rational design of the SEI to further improve Li-metal anodes.

Energy storage emerging: A perspective from the Joint Center for Energy Storage Research.

Energy storage is an integral part of modern society. A contemporary example is the lithium (Li)-ion battery, which enabled the launch of the personal electronics revolution in 1991 and the first commercial electric vehicles in 2010. Most recently, Li-ion batteries have expanded into the electricity grid to firm variable renewable generation, increasing the efficiency and effectiveness of transmission and distribution. Important applications continue to emerge including decarbonization of heavy-duty vehicles, rail, maritime shipping, and aviation and the growth of renewable electricity and storage on the grid. This perspective compares energy storage needs and priorities in 2010 with those now and those emerging over the next few decades. The diversity of demands for energy storage requires a diversity of purpose-built batteries designed to meet disparate applications. Advances in the frontier of battery research to achieve transformative performance spanning energy and power density, capacity, charge/discharge times, cost, lifetime, and safety are highlighted, along with strategic research refinements made by the Joint Center for Energy Storage Research (JCESR) and the broader community to accommodate the changing storage needs and priorities. Innovative experimental tools with higher spatial and temporal resolution, in situ and operando characterization, first-principles simulation, high throughput computation, machine learning, and artificial intelligence work collectively to reveal the origins of the electrochemical phenomena that enable new means of energy storage. This knowledge allows a constructionist approach to materials, chemistries, and architectures, where each atom or molecule plays a prescribed role in realizing batteries with unique performance profiles suitable for emergent demands.

Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4.

Virtually all intercalation compounds exhibit significant changes in unit cell volume as the working ion concentration varies. NaxFePO4 (0 < x < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries, is a model for topotactic, high-strain systems as it exhibits one of the largest discontinuous volume changes (∼17% by volume) during its first-order transition between two otherwise isostructural phases. Using synchrotron radiation powder X-ray diffraction (PXD) and pair distribution function (PDF) analysis, we discover a new strain-accommodation mechanism wherein a third, amorphous phase forms to buffer the large lattice mismatch between primary phases. The amorphous phase has short-range order over ∼1nm domains that is characterized by a and b parameters matching one crystalline end-member phase and a c parameter matching the other, but is not detectable by powder diffraction alone. We suggest that this strain-accommodation mechanism may generally apply to systems with large transformation strains.

Engineering the Transformation Strain in LiMnyFe1-yPO4 Olivines for Ultrahigh Rate Battery Cathodes.

Alkali ion intercalation compounds used as battery electrodes often exhibit first-order phase transitions during electrochemical cycling, accompanied by significant transformation strains. Despite ∼30 years of research into the behavior of such compounds, the relationship between transformation strain and electrode performance, especially the rate at which working ions (e.g., Li) can be intercalated and deintercalated, is still absent. In this work, we use the LiMnyFe1-yPO4 system for a systematic study, and measure using operando synchrotron radiation powder X-ray diffraction (SR-PXD) the dynamic strain behavior as a function of the Mn content (y) in powders of ∼50 nm average diameter. The dynamically produced strain deviates significantly from what is expected from the equilibrium phase diagrams and demonstrates metastability but nonetheless spans a wide range from 0 to 8 vol % with y. For the first time, we show that the discharge capacity at high C-rates (20-50C rate) varies in inverse proportion to the transformation strain, implying that engineering electrode materials for reduced strain can be used to maximize the power capability of batteries.

Three-Dimensional Growth of Li2S in Lithium-Sulfur Batteries Promoted by a Redox Mediator.

During the discharge of a lithium-sulfur (Li-S) battery, an electronically insulating 2D layer of Li2S is electrodeposited onto the current collector. Once the current collector is enveloped, the overpotential of the cell increases, and its discharge is arrested, often before reaching the full capacity of the active material. Guided by a new computational platform known as the Electrolyte Genome, we advance and apply benzo[ghi]peryleneimide (BPI) as a redox mediator for the reduction of dissolved polysulfides to Li2S. With BPI present, we show that it is now possible to electrodeposit Li2S as porous, 3D deposits onto carbon current collectors during cell discharge. As a result, sulfur utilization improved 220% due to a 6-fold increase in Li2S formation. To understand the growth mechanism, electrodeposition of Li2S was carried out under both galvanostatic and potentiostatic control. The observed kinetics under potentiostatic control were modeled using modified Avrami phase transformation kinetics, which showed that BPI slows the impingement of insulating Li2S islands on carbon. Conceptually, the pairing of conductive carbons with BPI can be viewed as a vascular approach to the design of current collectors for energy storage devices: here, conductive carbon "arteries" dominate long-range electron transport, while BPI "capillaries" mediate short-range transport and electron transfer between the storage materials and the carbon electrode.

Improving the capacity of sodium ion battery using a virus-templated nanostructured composite cathode.

In this work we investigated an energy-efficient biotemplated route to synthesize nanostructured FePO4 for sodium-based batteries. Self-assembled M13 viruses and single wall carbon nanotubes (SWCNTs) have been used as a template to grow amorphous FePO4 nanoparticles at room temperature (the active composite is denoted as Bio-FePO4-CNT) to enhance the electronic conductivity of the active material. Preliminary tests demonstrate a discharge capacity as high as 166 mAh/g at C/10 rate, corresponding to composition Na0.9FePO4, which along with higher C-rate tests show this material to have the highest capacity and power performance reported for amorphous FePO4 electrodes to date.

Mitigating mechanical failure of crystalline silicon electrodes for lithium batteries by morphological design.

Although crystalline silicon (c-Si) anodes promise very high energy densities in Li-ion batteries, their practical use is complicated by amorphization, large volume expansion and severe plastic deformation upon lithium insertion. Recent experiments have revealed the existence of a sharp interface between crystalline Si (c-Si) and the amorphous LixSi alloy during lithiation, which propagates with a velocity that is orientation dependent; the resulting anisotropic swelling generates substantial strain concentrations that initiate cracks even in nanostructured Si. Here we describe a novel strategy to mitigate lithiation-induced fracture by using pristine c-Si structures with engineered anisometric morphologies that are deliberately designed to counteract the anisotropy in the crystalline/amorphous interface velocity. This produces a much more uniform volume expansion, significantly reducing strain concentration. Based on a new, validated methodology that improves previous models of anisotropic swelling of c-Si, we propose optimal morphological designs for c-Si pillars and particles. The advantages of the new morphologies are clearly demonstrated by mesoscale simulations and verified by experiments on engineered c-Si micropillars. The results of this study illustrate that morphological design is effective in improving the fracture resistance of micron-sized Si electrodes, which will facilitate their practical application in next-generation Li-ion batteries. The model and design approach present in this paper also have general implications for the study and mitigation of mechanical failure of electrode materials that undergo large anisotropic volume change upon ion insertion and extraction.

In situ observation of random solid solution zone in LiFePO4 electrode.

Nanostructured LiFePO4 (LFP) electrodes have attracted great interest in the Li-ion battery field. Recently there have been debates on the presence and role of metastable phases during lithiation/delithiation, originating from the apparent high rate capability of LFP batteries despite poor electronic/ionic conductivities of bulk LFP and FePO4 (FP) phases. Here we report a potentiostatic in situ transmission electron microscopy (TEM) study of LFP electrode kinetics during delithiation. Using in situ high-resolution TEM, a Li-sublattice disordered solid solution zone (SSZ) is observed to form quickly and reach 10-25 nm × 20-40 nm in size, different from the sharp LFP|FP interface observed under other conditions. This 20 nm scale SSZ is quite stable and persists for hundreds of seconds at room temperature during our experiments. In contrast to the nanoscopically sharp LFP|FP interface, the wider SSZ seen here contains no dislocations, so reduced fatigue and enhanced cycle life can be expected along with enhanced rate capability. Our findings suggest that the disordered SSZ could dominate phase transformation behavior at nonequilibrium condition when high current/voltage is applied; for larger particles, the SSZ could still be important as it provides out-of-equilibrium but atomically wide avenues for Li(+)/e(-) transport.

Polysulfide flow batteries enabled by percolating nanoscale conductor networks.

A new approach to flow battery design is demonstrated wherein diffusion-limited aggregation of nanoscale conductor particles at ∼1 vol % concentration is used to impart mixed electronic-ionic conductivity to redox solutions, forming flow electrodes with embedded current collector networks that self-heal after shear. Lithium polysulfide flow cathodes of this architecture exhibit electrochemical activity that is distributed throughout the volume of flow electrodes rather than being confined to surfaces of stationary current collectors. The nanoscale network architecture enables cycling of polysulfide solutions deep into precipitation regimes that historically have shown poor capacity utilization and reversibility and may thereby enable new flow battery designs of higher energy density and lower system cost. Lithium polysulfide half-flow cells operating in both continuous and intermittent flow mode are demonstrated for the first time.

Aqueous semi-solid flow cell: demonstration and analysis.

An aqueous Li-ion flow cell using suspension-based flow electrodes based on the LiTi2(PO4)3-LiFePO4 couple is demonstrated. Unlike conventional flow batteries, the semi-solid approach utilizes fluid electrodes that are electronically conductive. A model of simultaneous advection and electrochemical transport is developed and used to separate flow-induced losses from those due to underlying side reactions. The importance of plug flow to achieving high energy efficiency in flow batteries utilizing highly non-Newtonian flow electrodes is emphasized.

Ultrahigh Areal Capacity Li Electrodeposition at Metal-Solid Electrolyte Interfaces under Minimal Stack Pressures Enabled by Interfacial Na-K Liquids.

The need for higher energy density rechargeable batteries has generated interest in metallic electrodes paired with solid electrolytes. However, impedance growth at the Li metal-solid electrolyte interface due to void formation during cycling at practical current densities and areal capacities, e.g., greater than 0.5 mA cm-2 and 1.5 mAh cm-2 respectively, remains a significant barrier. Here, we show that introducing a wetting interfacial film of Na-K liquid between the Li metal and the Li6.75La3Zr1.75Ta0.25O12 (LLZTO) solid electrolyte permits reversible stripping and plating of up to 150 µm of Li (30 mAh cm-2), approximately 10 times the areal capacity of today's lithium-ion batteries, at current densities above 0.5 mA cm-2 and stack pressures below 75 kPa, all with minimal changes in cell impedance. We further show that this increase in the accessible areal capacity at high stripping current densities is due to the presence of Na-K liquid at the Li stripping interface; this performance improvement is not enabled in the absence of the Na-K liquid. This design approach holds promise for overcoming interfacial stability issues that have heretofore limited the performance of solid-state metal batteries.

Bayesian-Optimization-Assisted Laser Reduction of Poly(acrylonitrile) for Electrochemical Applications.

Laser reduction of polymers has recently been explored to rapidly and inexpensively synthesize high-quality graphitic and carbonaceous materials. However, in past work, laser-induced graphene has been restricted to semiaromatic polymers and graphene oxide; in particular, poly(acrylonitrile) (PAN) is claimed to be a polymer that cannot be laser-reduced successfully to form electrochemically active material. In this work, three strategies to surmount this barrier are employed: (1) thermal stabilization of PAN to increase its sp2 content for improved laser processability, (2) prelaser treatment microstructuring to reduce the effects of thermal stresses, and (3) Bayesian optimization to search the parameter space of laser processing to improve performance and discover morphologies. Based on these approaches, we successfully synthesize laser-reduced PAN with a low sheet resistance (6.5 Ω sq-1) in a single lasing step. The resulting materials are tested electrochemically, and their applicability as membrane electrodes for vanadium redox flow batteries is demonstrated. This work demonstrates electrodes that are processed in air, below 300 °C, which are cycled stably over 2 weeks at 40 mA cm-2, motivating further development of laser reduction of porous polymers for membrane electrode applications such as RFBs.

Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li2OHCl.

Li2OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having ∼1/3 of the Li sites vacant, while the presence of the OH- anion introduces the possibility of rotational disorder that may be coupled to cation migration. Here, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li2OHCl, which undergoes an orthorhombic to cubic phase transition near 311 K (≈38 °C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 × 10-5mS/cm at 37 °C to 1.4 × 10-3 mS/cm at 39 °C). X-ray and neutron experiments conducted over the temperature range 20-200 °C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to "paddlewheel" rotation of the dynamic OH- anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility.

Stamped microbattery electrodes based on self-assembled M13 viruses.

The fabrication and spatial positioning of electrodes are becoming central issues in battery technology because of emerging needs for small scale power sources, including those embedded in flexible substrates and textiles. More generally, novel electrode positioning methods could enable the use of nanostructured electrodes and multidimensional architectures in new battery designs having improved electrochemical performance. Here, we demonstrate the synergistic use of biological and nonbiological assembly methods for fabricating and positioning small battery components that may enable high performance microbatteries with complex architectures. A self-assembled layer of virus-templated cobalt oxide nanowires serving as the active anode material in the battery anode was formed on top of microscale islands of polyelectrolyte multilayers serving as the battery electrolyte, and this assembly was stamped onto platinum microband current collectors. The resulting electrode arrays exhibit full electrochemical functionality. This versatile approach for fabricating and positioning electrodes may provide greater flexibility for implementing advanced battery designs such as those with interdigitated microelectrodes or 3D architectures.