Softening of PEO-LiTFSI/LLZTO Composite Polymer Electrolytes for Solid-State Batteries under Cyclic Compression.

Composite polymer electrolytes (CPEs) strike an effective balance between ionic conductivity and mechanical flexibility for lithium-ion solid-state batteries. Long-term performance, however, is limited by capacity fading after hundreds of charge and discharge cycles. The causes of performance degradation include multiple contributing factors such as dendrite formation, physicochemical changes in electrolytes, and structural remodeling of porous electrodes. Among the many factors that contribute to performance degradation, the effect of stress specifically on the composite electrolyte is not well understood. This study examines the mechanical changes in a poly(ethylene oxide) electrolyte with bis(trifluoromethane) sulfonimide. Two different sizes of Li6.4La3Zr1.4Ta0.6O12 particles (500 nm and 5 µm) are compared to evaluate the effect of the surface-to-volume ratio of the ion-conducting fillers within the composite. Cyclic compression was applied to mimic stress cycling in the electrolyte, which would be caused by asymmetric volume changes that occur during charging and discharging cycles. The electrolytes exhibited fatigue softening, whereby the compressive modulus gradually decreased with an increase in the number of cycles. When the electrolyte was tested for 500 cycles at 30% compressive strain, the compressive modulus of the electrolyte was reduced to approximately 80% of the modulus before cycling. While the extent of softening was similar regardless of particle size, CPEs with 500 nm particles exhibited a significant reduction in ionic conductivity after cyclic compression (1.4 × 10-7 ± 2.3 × 10-8 vs 1.1 × 10-7 ± 2.0 × 10-8 S/cm, mean ± standard deviation, n = 4), whereas there was no significant change in ionic conductivity for CPEs with 5 µm particles. These observations -performed deliberately in the absence of charge-discharge cycles -show that repetitive mechanical stresses can play a significant role in altering the performance of CPEs, thereby revealing another possible mechanism for performance degradation in all-solid-state batteries.

Microbe-Assisted Nanocomposite Anodes for Aqueous Li-Ion Batteries.

With the rapid increase in the use of lithium-ion batteries (LIBs), the development of safe LIBs has become an important social issue. Replacing flammable organic liquid electrolytes in current LIBs with water can be an alternative route to resolve this safety concern. The water-in-salt (WIS) electrolytes received great attention as next-generation electrolytes due to their large electrochemical stability window. However, their high cathodic limit remains as a challenge, impeding the use of low-potential anodes. Here, we report the first biodirected synthesis of carbonaceous layers on anodes to use them as interlayers that prevent a direct contact of water molecules to anode particles. High-aspect ratio microbes are utilized as precursors of carbonaceous layers on TiO2 nanoparticles (m-TiO2) to enhance the conductivity and to reduce the electrolysis of WIS electrolytes. We selected the cylindrical shape of microbes that offers geometric diversity, providing us a toolkit to investigate the effect of microbe length in forming the network in binary composites and their impacts on the battery performance with WIS electrolytes. Using microbes with varying aspect ratios, the optimal microbe size to maximize the battery performance is determined. The effects of storage time on microbe size are also studied. Compared to uncoated TiO2 anodes, m-TiO2 exhibited 49% higher capacity at the 40th cycle and enhanced the cycle life close to anodes made with a conventional carbon precursor while using an 11% less amount of carbon. We performed density functional theory calculations to unravel the underlying mechanism of the performance improvement using microbe-derived carbon layers. Computational results show that high amounts of pyridinic nitrogen present in the peptide bonds in microbes are expected to slow down the water diffusion. Our findings provide key insights into the design of an interlayer for WIS anodes and open an avenue to fabricate energy storage materials using biomaterials.

Carbon-based artificial SEI layers for aqueous lithium-ion battery anodes.

Replacing flammable organic electrolytes with aqueous electrolytes in lithium-ion batteries (LIB) can greatly enhance the safety of next-generation energy storage systems. With the extended electrochemical stability window of electrolytes, 'water-in-salt' (WIS) electrolytes containing LIB presented significant performance improvements. However, the solubility limits of lithium salts in water restrain the extent of kinetic protection offered by the high salt concentration. Here, we report design strategies of anode structure to improve the cycle life of LIB with WIS electrolytes. We introduced partially graphitic protective carbon layers on anode particles using a versatile coating method. This protective layer not only improved charge transfer kinetics but also minimized the exposure of anode surface for water electrolysis. The effectiveness of anode structure developed in this study was exemplified on TiO2 anodes, where cycle performance and coulombic efficiency improved by 11 times and 29% respectively over the base anode material.

Flat Monolayer Graphene Cathodes for Li-Oxygen Microbatteries.

Miniature batteries can accelerate the development of mobile electronics by providing sufficient energy to power small devices. Typical microbatteries commonly use thin-film inorganic electrodes based on Li-ion insertion reaction. However, they rely on the complicated thin-film synthesis method of inorganics containing many elements. Graphene, one atomic layer thick carbon sheet, has diverse physical and chemical properties and is compatible with conventional micron-scale device fabrication. Here, we study the use of chemical vapor deposition (CVD) grown monolayer graphene in a two-dimensional configuration, as a future Li-oxygen microbattery cathode. By maximizing the dissolution of discharge intermediates, we obtain 2610 Ah/ggraphene of capacity corresponding to 20% higher areal cathode energy density and 2.7 times higher cathode specific energy than that can be derived from the same volume or mass of conventional Li-ion battery cathode material. Furthermore, a clear observation on the discharge reaction on composite electrodes and their role in the charging reaction was made, thanks to the two-dimensional monolayer graphene Li-oxygen battery cathode. We demonstrate an easy integration of two-dimensional CVD graphene cathode into microscale devices by simply transferring or coating the target device substrate with flexible graphene layers. The ability to integrate and use monolayer graphene on arbitrary device substrates as well as precise control over a chemical derivation of the carbon interface can have a radical impact on future energy-storage devices.

How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

Biotemplating pores with size and shape diversity for Li-oxygen Battery Cathodes.

Synthetic porogens provide an easy way to create porous structures, but their usage is limited due to synthetic difficulties, process complexities and prohibitive costs. Here we investigate the use of bacteria, sustainable and naturally abundant materials, as a pore template. The bacteria require no chemical synthesis, come in variable sizes and shapes, degrade easier and are approximately a million times cheaper than conventional porogens. We fabricate free standing porous multiwalled carbon nanotube (MWCNT) films using cultured, harmless bacteria as porogens, and demonstrate substantial Li-oxygen battery performance improvement by porosity control. Pore volume as well as shape in the cathodes were easily tuned to improve oxygen evolution efficiency by 30% and double the full discharge capacity in repeated cycles compared to the compact MWCNT electrode films. The interconnected pores produced by the templates greatly improve the accessibility of reactants allowing the achievement of 4,942 W/kg (8,649 Wh/kg) at 2 A/ge (1.7 mA/cm2).

M13 virus-directed synthesis of nanostructured metal oxides for lithium-oxygen batteries.

Transition metal oxides are promising electrocatalysts for both water oxidations and metal-air batteries. Here, we report the virus-mediated synthesis of cobalt manganese oxide nanowires (NWs) to fabricate high capacity Li-O2 battery electrodes. Furthermore, we hybridized Ni nanoparticles (NPs) on bio Co3O4 NWs to improve the round trip efficiency as well as the cycle life of Li-O2 batteries. This biomolecular directed synthesis method is expected to provide a selection platform for future energy storage electrocatalysts.

Biologically enhanced cathode design for improved capacity and cycle life for lithium-oxygen batteries.

Lithium-oxygen batteries have a great potential to enhance the gravimetric energy density of fully packaged batteries by two to three times that of lithium ion cells. Recent studies have focused on finding stable electrolytes to address poor cycling capability and improve practical limitations of current lithium-oxygen batteries. In this study, the catalyst electrode, where discharge products are deposited and decomposed, was investigated as it has a critical role in the operation of rechargeable lithium-oxygen batteries. Here we report the electrode design principle to improve specific capacity and cycling performance of lithium-oxygen batteries by utilizing high-efficiency nanocatalysts assembled by M13 virus with earth-abundant elements such as manganese oxides. By incorporating only 3-5 wt% of palladium nanoparticles in the electrode, this hybrid nanocatalyst achieves 13,350 mAh g(-1)(c) (7,340 mAh g(-1)(c+catalyst)) of specific capacity at 0.4 A g(-1)(c) and a stable cycle life up to 50 cycles (4,000 mAh g(-1)(c), 400 mAh g(-1)(c+catalyst)) at 1 A g(-1)(c).

Graphene sheets stabilized on genetically engineered M13 viral templates as conducting frameworks for hybrid energy-storage materials.

Utilization of the material-specific peptide-substrate interactions of M13 virus broadens colloidal stability window of graphene. The homogeneous distribution of graphene is maintained in weak acids and increased ionic strengths by complexing with virus. This graphene/virus conducting template is utilized in the synthesis of energy-storage materials to increase the conductivity of the composite electrode. Successful formation of the hybrid biological template is demonstrated by the mineralization of bismuth oxyfluoride as a cathode material for lithium-ion batteries, with increased loading and improved electronic conductivity.

Biologically activated noble metal alloys at the nanoscale: for lithium ion battery anodes.

We report the synthesis and electrochemical activity of gold and silver noble metals and their alloy nanowires using multiple virus clones as anode materials for lithium ion batteries. Using two clones, one for specificity (p8#9 virus) and one versatility (E4 virus), noble metal nanowires of high-aspect ratio with diameters below 50 nm were successfully synthesized with control over particle sizes, morphologies, and compositions. The biologically derived noble metal alloy nanowires showed electrochemical activities toward lithium even when the electrodes were prepared from bulk powder forms. The improvement in capacity retention was accomplished by alloy formation and surface stabilization. Although the cost of noble metals renders them a less ideal choice for lithium ion batteries, these noble metal/alloy nanowires serve as great model systems to study electrochemically induced transformation at the nanoscale. Given the demonstration of the electrochemical activity of noble metal alloy nanowires with various compositions, the M13 biological toolkit extended its utility for the study on the basic electrochemical property of materials.