Quantifying inactive lithium in lithium metal batteries.

Lithium metal anodes offer high theoretical capacities (3,860 milliampere-hours per gram)1, but rechargeable batteries built with such anodes suffer from dendrite growth and low Coulombic efficiency (the ratio of charge output to charge input), preventing their commercial adoption2,3. The formation of inactive ('dead') lithium- which consists of both (electro)chemically formed Li+ compounds in the solid electrolyte interphase and electrically isolated unreacted metallic Li0 (refs 4,5)-causes capacity loss and safety hazards. Quantitatively distinguishing between Li+ in components of the solid electrolyte interphase and unreacted metallic Li0 has not been possible, owing to the lack of effective diagnostic tools. Optical microscopy6, in situ environmental transmission electron microscopy7,8, X-ray microtomography9 and magnetic resonance imaging10 provide a morphological perspective with little chemical information. Nuclear magnetic resonance11, X-ray photoelectron spectroscopy12 and cryogenic transmission electron microscopy13,14 can distinguish between Li+ in the solid electrolyte interphase and metallic Li0, but their detection ranges are limited to surfaces or local regions. Here we establish the analytical method of titration gas chromatography to quantify the contribution of unreacted metallic Li0 to the total amount of inactive lithium. We identify the unreacted metallic Li0, not the (electro)chemically formed Li+ in the solid electrolyte interphase, as the dominant source of inactive lithium and capacity loss. By coupling the unreacted metallic Li0 content to observations of its local microstructure and nanostructure by cryogenic electron microscopy (both scanning and transmission), we also establish the formation mechanism of inactive lithium in different types of electrolytes and determine the underlying cause of low Coulombic efficiency in plating and stripping (the charge and discharge processes, respectively, in a full cell) of lithium metal anodes. We propose strategies for making lithium plating and stripping more efficient so that lithium metal anodes can be used for next-generation high-energy batteries.

Nearly polarization-insensitive angular filters enabled by metal-dielectric photonic crystal in the visible region.

We report on the design and fabrication of nearly polarization-insensitive angular filters, which have been developed through the optimization of one-dimensional A g/M g F 2 photonic crystals (PCs). We evaluate different initial systems for optimization and compare their results in terms of both the wavelength and angular selectivity. Our findings reveal that relaxing the strict periodic condition of initial photonic crystals with a small number of lattices has enabled improvement in the angular selectivity via Fabry-Perot resonances in dielectric layers, achieving a transmission as high as 81% at normal incidence by optimizing the dielectric layer thickness. The simulation results demonstrate that the transmitted beam through the angular filtering sample at 633 nm has allowable angles within 29° and 33° for TE and TM polarization, respectively, with a transmission over 80% at normal incidence. This proposed and demonstrated angular filter represents what we believe is a novel way to utilize 1D metal-dielectric PCs as polarization-insensitive angular filters, overcoming the main drawback of a low transmission. This angular filter will have significant applications in lighting, beam manipulation, optical coupling, and optical detectors.

Structural Transformation in a Sulfurized Polymer Cathode to Enable Long-Life Rechargeable Lithium-Sulfur Batteries.

Sulfurized polyacrylonitrile (SPAN) represents a class of sulfur-bonded polymers, which have shown thousands of stable cycles as a cathode in lithium-sulfur batteries. However, the exact molecular structure and its electrochemical reaction mechanism remain unclear. Most significantly, SPAN shows an over 25% 1st cycle irreversible capacity loss before exhibiting perfect reversibility for subsequent cycles. Here, with a SPAN thin-film platform and an array of analytical tools, we show that the SPAN capacity loss is associated with intramolecular dehydrogenation along with the loss of sulfur. This results in an increase in the aromaticity of the structure, which is corroborated by a >100× increase in electronic conductivity. We also discovered that the conductive carbon additive in the cathode is instrumental in driving the reaction to completion. Based on the proposed mechanism, we have developed a synthesis procedure to eliminate more than 50% of the irreversible capacity loss. Our insights into the reaction mechanism provide a blueprint for the design of high-performance sulfurized polymer cathode materials.

Glassy Li metal anode for high-performance rechargeable Li batteries.

Lithium metal has been considered an ideal anode for high-energy rechargeable Li batteries, although its nucleation and growth process remains mysterious, especially at the nanoscale. Here, cryogenic transmission electron microscopy was used to reveal the evolving nanostructure of Li metal deposits at various transient states in the nucleation and growth process, in which a disorder-order phase transition was observed as a function of current density and deposition time. The atomic interaction over wide spatial and temporal scales was depicted by reactive molecular dynamics simulations to assist in understanding the kinetics. Compared to crystalline Li, glassy Li outperforms in electrochemical reversibility, and it has a desired structure for high-energy rechargeable Li batteries. Our findings correlate the crystallinity of the nuclei with the subsequent growth of the nanostructure and morphology, and provide strategies to control and shape the mesostructure of Li metal to achieve high performance in rechargeable Li batteries.

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM.

Lithium metal has been considered the "holy grail" anode material for rechargeable batteries despite the fact that its dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanying solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and mesostructures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)-electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nanoscale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation-dominated EDLi (5 min at 0.5 mA cm-2) is amorphous, while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials but also yield crucial structural information on the EDLi evolution with and without electrolyte additives.

A free-standing lithium phosphorus oxynitride thin film electrolyte promotes uniformly dense lithium metal deposition with no external pressure.

Lithium phosphorus oxynitride (LiPON) is an amorphous solid electrolyte that has been extensively studied over the last three decades. Despite the promise of pairing it with various electrode materials, LiPON's rigidity and air sensitivity set limitations to understanding its intrinsic properties. Here we report a methodology to synthesize LiPON in a free-standing form that manifests remarkable flexibility and a Young's modulus of ∼33 GPa. We use solid-state nuclear magnetic resonance and differential scanning calorimetry to quantitatively reveal the chemistry of the Li/LiPON interface and the presence of a well-defined LiPON glass-transition temperature of 207 °C. Combining interfacial stress and a gold seeding layer, our free-standing LiPON shows a uniformly dense deposition of lithium metal without the aid of external pressure. This free-standing LiPON film offers opportunities to study fundamental properties of LiPON for interface engineering for solid-state batteries.

Bridging nano- and microscale X-ray tomography for battery research by leveraging artificial intelligence.

X-ray computed tomography (CT) is a non-destructive imaging technique in which contrast originates from the materials' absorption coefficient. The recent development of laboratory nanoscale CT (nano-CT) systems has pushed the spatial resolution for battery material imaging to voxel sizes of 50 nm, a limit previously achievable only with synchrotron facilities. Given the non-destructive nature of CT, in situ and operando studies have emerged as powerful methods to quantify morphological parameters, such as tortuosity factor, porosity, surface area and volume expansion, during battery operation or cycling. Combined with artificial intelligence and machine learning analysis techniques, nano-CT has enabled the development of predictive models to analyse the impact of the electrode microstructure on cell performances or the influence of material heterogeneities on electrochemical responses. In this Review, we discuss the role of X-ray CT and nano-CT experimentation in the battery field, discuss the incorporation of artificial intelligence and machine learning analyses and provide a perspective on how the combination of multiscale CT imaging techniques can expand the development of predictive multiscale battery behavioural models.

Continuously Quantifying Oral Chemicals Based on Flexible Hybrid Electronics for Clinical Diagnosis and Pathogenetic Study.

Simultaneous monitoring of diverse salivary parameters can reveal underlying mechanisms of intraoral biological processes and offer profound insights into the evolution of oral diseases. However, conventional analytical devices with bulky volumes, rigid formats, and discrete sensing mechanisms deviate from the requirements of continuous biophysiological quantification, resulting in huge difficulty in precise clinical diagnosis and pathogenetic study. Here, we present a flexible hybrid electronic system integrated with functional nanomaterials to continuously sense Ca2+, pH, and temperature for wireless real-time oral health monitoring. The miniaturized system with an island-bridge structure that is designed specifically to fit the teeth is only 0.4 g in weight and 31.5 × 8.5 × 1.35 mm3 in dimension, allowing effective integration with customized dental braces and comfort attachment on teeth. Characterization results indicate high sensitivities of 30.3 and 60.6 mV/decade for Ca2+ and pH with low potential drifts. The system has been applied in clinical studies to conduct Ca2+ and pH mappings on carious teeth, biophysiological monitoring for up to 12 h, and outcome evaluation of dental restoration, providing quantitative data to assist in the diagnosis and understanding of oral diseases. Notably, caries risk assessment of 10 human subjects using the flexible system validates the important role of saliva buffering capacity in caries pathogenesis. The proposed flexible system may offer an open platform to carry diverse components to support both clinical diagnosis and treatment as well as fundamental research for oral diseases and induced systemic diseases.

Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes.

The development of silicon anodes for lithium-ion batteries has been largely impeded by poor interfacial stability against liquid electrolytes. Here, we enabled the stable operation of a 99.9 weight % microsilicon anode by using the interface passivating properties of sulfide solid electrolytes. Bulk and surface characterization, and quantification of interfacial components, showed that such an approach eliminates continuous interfacial growth and irreversible lithium losses. Microsilicon full cells were assembled and found to achieve high areal current density, wide operating temperature range, and high areal loadings for the different cells. The promising performance can be attributed to both the desirable interfacial property between microsilicon and sulfide electrolytes and the distinctive chemomechanical behavior of the lithium-silicon alloy.

Side-polished flexible SPR sensor modified by graphene with in situ temperature self-compensation.

Fiber-based techniques make it possible to implant a miniaturized and flexible surface plasmon resonance (SPR) sensor into the human body. However, for implantable applications, the miniaturization of fiber SPR sensors results in low sensitivity compared with traditional prism-type SPR sensors due to limited space and the effects of temperature fluctuations. Therefore, it is necessary to compensate for temperature drift in the measurements, such as the case of the quantification of the relationship between glucose concentration and SPR resonance wavelength. In this report, we proposed a highly sensitive fiber SPR sensor based on a side-polished structure modified by graphene for implantable continuous glucose monitoring with in situ temperature self-compensation using a long-period fiber grating (LPFG). The results demonstrate that the sensor with monolayer graphene achieved the best sensitivity of 3058.22 nm/RIU, and the LPFG achieves a maximum resolution of 0.042 nm/°C. The proposed SPR sensor enabled the detection of hypoglycemia, which is still a significant challenge for continuous glucose monitoring in a clinical setting.

Sticker Microfluidics: A Method for Fabrication of Customized Monolithic Microfluidics.

This paper proposes a novel strategy and an all-in-one toolbox that allows instrument-free customization of integrated microfluidic systems. Unlike the modular design of combining multiple microfluidic chips in the previous literature, this work, for the first time, proposes a "template sticker" method, in which sacrificial templates for microfluidic components are batch-produced in the form of standardized stickers and packaged into a toolbox. To create a customized monolithic microfluidic system, the end users only need to select and combine various template stickers following formulated steps. The fabricated microfluidic devices have well-defined microscale features, while the fabrication process is inexpensive and time-saving. Various functional microfluidic devices were fabricated and tested using this toolbox. The capability to create microchannels on curved surfaces is also demonstrated. As a proof of concept, we developed with the proposed toolbox a colorimetric testing platform for the detection of nitrite ions. The sticker toolbox, as the first self-contained portable platform for microfluidic fabrication, allows prompt customization of monolithic devices, enabling deployment of microfluidics with both ideal performance and customizability.

An optofluidic system with volume measurement and surface plasmon resonance sensor for continuous glucose monitoring.

The traditional technology of glucose monitoring is painful and invasive because of the frequent blood collection. Nowadays, the enzyme electrode sensor is mainly used for continuous glucose monitoring in clinic, but it has inherent disadvantages of significant signal drift of current due to bioelectricity in body and the missing of hypoglycemia resulting from the irreversible consumption of glucose at the process of enzyme catalytic reaction. Interstitial fluid (ISF) transdermal extraction can be nearly unsensible which effectively reduces the pain caused by invasive detection so that it may provide a new way to monitor glucose. MEMS technology has been used to produce devices for transdermal ISF extraction, but there is a lack of on-chip ISF volume measurement capabilities, which are required to compensate skin permeability variations. This paper presents a lab-on-a-chip system for ISF transdermal extraction, ISF volume measurement, and optical glucose sensing towards the application of continuous glucose monitoring. The device significantly incorporates a MEMS volume sensor, which measures extracted ISF volume via conductance monitoring, and integrates a fiber-optic surface plasmon resonance sensor to measure glucose concentration in microchannel. The fiber-based technique provides an excellent approach to overcome the above two drawbacks of the enzyme electrode based glucose sensing. Six different volumes were tested, and the standard deviation of every sample is less than 0.05 µl, The resonance wavelength moves from 549.081 nm to 592.914 nm while the concentration ranges from 0 to 200 mg/dl. The feasibility of the single-chip device for accurate and continuous monitoring of subcutaneous ISF glucose concentrations is verified.