LaCl3-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries.

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl3-based Na+ superionic conductor (Na1-xZrxLa1-xCl4) with high ionic conductivity of 2.9 × 10-4 S cm-1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na2Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P63/m) of Na1-xZrxLa1-xCl4, with Na+ ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na1-xZrxLa1-xCl4 is mainly determined by the size of Na+-channels and the Na+/La3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO2||Na0.7Zr0.3La0.7Cl4||Na3PS4||Na2Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g-1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g-1 can be maintained at 1 C current density.

Effect of Electrochemical Pre-Lithiation on Layered Oxide Cathodes for Anode-Free Lithium-metal Batteries.

Due to high energy density and lower manufacturing cost, anode-free lithium-metal batteries (AFLMBs) are attracting increasing attention. The challenges for developing them lie in inferior Coulombic efficiency and short cycle life due to the highly reactive lithium metal. Herein, an electrochemical pre-lithiation strategy is applied to layered oxide cathodes, specifically LiNiO2 and LiCoO2 , aiming to provide an additional lithium source and understand the effect on the cathode structure for AFLMBs. The mechanism for accommodating the excess Li depends on the structural stability of the cathodes where LiNiO2 forms lithiated Li2 NiO2 with the excess lithium in the crystalline lattice while the excess lithium in LiCoO2 forms a Li2 O phase. More importantly, an optimal amount of Li excess is necessary to maintain decent cycle stability and specific capacity in AFLMB, with 40% excess Li for LiNiO2 and 150% for LiCoO2 . While the pre-lithiation process causes particle pulverization depending on the amount of Li excess, LiCoO2 offers a much better cycle performance than LiNiO2 with a promising capacity retention of 80% after 300 cycles in AFLMB (vs 76% after 100 cycles for 40% Li excess in LiNiO2 ). This study provides a promising avenue for developing tailor-made layered oxide cathodes for AFLMBs.

Delineating the Impact of Transition-Metal Crossover on Solid-Electrolyte Interphase Formation with Ion Mass Spectrometry.

Lithium-metal batteries (LMB) employing cobalt-free layered-oxide cathodes are a sustainable path forward to achieving high energy densities, but these cathodes exhibit substantial transition-metal dissolution during high-voltage cycling. While transition-metal crossover is recognized to disrupt solid-electrolyte interphase (SEI) formation on graphite anodes, experimental evidence is necessary to demonstrate this for lithium-metal anodes. In this work, advanced high-resolution 3D chemical analysis is conducted with time-of-flight secondary-ion mass spectrometry (TOF-SIMS) to establish spatial correlations between the transition metals and electrolyte decomposition products found on cycled lithium-metal anodes. Insights into the localization of various chemistries linked to crucial processes that define LMB performance, such as lithium deposition, SEI growth, and transition-metal deposition are deduced from a precise elemental and spatial analysis of the SEI. Heterogenous transition-metal deposition is found to perpetuate both heterogeneous SEI growth and lithium deposition on lithium-metal anodes. These correlations are confirmed across various lithium-metal anodes that are cycled with different cobalt-free cathodes and electrolytes. An advanced electrolyte that is stable to higher voltages is shown to minimize transition-metal crossover and its effects on lithium-metal anodes. Overall, these results highlight the importance of maintaining uniform SEI coverage on lithium-metal anodes, which is disrupted by transition-metal crossover during operation at high voltages.

Intercalation-type catalyst for non-aqueous room temperature sodium-sulfur batteries.

Ambient-temperature sodium-sulfur (Na-S) batteries are potential attractive alternatives to lithium-ion batteries owing to their high theoretical specific energy of 1,274 Wh kg-1 based on the mass of Na2S and abundant sulfur resources. However, their practical viability is impeded by sodium polysulfide shuttling. Here, we report an intercalation-conversion hybrid positive electrode material by coupling the intercalation-type catalyst, MoTe2, with the conversion-type active material, sulfur. In addition, MoTe2 nanosheets vertically grown on graphene flakes offer abundant active catalytic sites, further boosting the catalytic activity for sulfur redox. When used as a composite positive electrode and assembled in a coin cell with excess Na, a discharge capacity of 1,081 mA h gs-1 based on the mass of S with a capacity fade rate of 0.05% per cycle over 350 cycles at 0.1 C rate in a voltage range of 0.8 to 2.8 V is realized under a high sulfur loading of 3.5 mg cm-2 and a lean electrolyte condition with an electrolyte-to-sulfur ratio of 7 µL mg-1. A fundamental understanding of the electrocatalysis of MoTe2 is further revealed by in-situ synchrotron-based operando X-ray diffraction and ex-situ time-of-flight secondary ion mass spectrometry.

Battery Charge Curve Prediction via Feature Extraction and Supervised Machine Learning.

Real-time onboard state monitoring and estimation of a battery over its lifetime is indispensable for the safe and durable operation of battery-powered devices. In this study, a methodology to predict the entire constant-current cycling curve with limited input information that can be collected in a short period of time is developed. A total of 10 066 charge curves of LiNiO2 -based batteries at a constant C-rate are collected. With the combination of a feature extraction step and a multiple linear regression step, the method can accurately predict an entire battery charge curve with an error of < 2% using only 10% of the charge curve as the input information. The method is further validated across other battery chemistries (LiCoO2 -based) using open-access datasets. The prediction error of the charge curves for the LiCoO2 -based battery is around 2% with only 5% of the charge curve as the input information, indicating the generalization of the developed methodology for predicting battery cycling curves. The developed method paves the way for fast onboard health status monitoring and estimation for batteries during practical applications.

Operation of Layered LiCoO2 to Higher Voltages with a Localized Saturated Electrolyte.

The commercialization of lithium-ion batteries started with a layered LiCoO2 (LCO) cathode for portable electronics, but only 50% of its theoretical capacity can be used in practical cells due to detrimental surface and bulk degradations when charged to high voltages. We demonstrate here that the stability of the electrolyte plays a critical role in the performance of LCO at high voltages by employing a localized saturated electrolyte (LSE). With a cutoff voltage of 4.5 V, LCO achieves an initial 1 C discharge capacity of 176 mA h g-1 and a capacity retention of 80% over 230 cycles. Even with a cutoff voltage of 4.6 V, LCO with 2% aluminum doping displays an initial discharge capacity of 189 mA h g-1 at 1 C rate with 80% capacity retention over 137 cycles. With extensive analytical characterization, we show that the improved cycling stability stems from a suppression of the O3 to H1-3 phase transition as well as a robust inorganic-rich cathode-electrolyte interphase (CEI) facilitated by the LSE. This work highlights the importance of protecting the surface as well as the bulk with appropriate electrolytes for the high-voltage, higher-energy-density operation of LCO.

Designing reliable electrochemical cells for operando lithium-ion battery study.

Operando experiments attract increasing attention in lithium-ion batteries (LIBs) studies for their ability to capture non-equilibrium and fast-transient processes during electrochemical reactions. They provide valuable information and mechanisms that cannot be obtained from ex-situ methods. Designing a suitable and reliable electrochemical cell is the first crucial step for most operando studies. A poorly designed in-situ cell introduces artifacts into the data and might lead to misleading results. Even though many in-situ cells have been designed and applied for operando studies, designing a reliable cell is not trivial, especially for long-term cycling experiments. This study introduces the steps and details of a specific type of in-situ cell, i.e., modified coin cell, that can be applied reliably in various operando experiments. The reliability of the modified coin cell is demonstrated by comparing its electrochemical performance with the standard coin cell. The modified coin cell is then applied in various operando experiments, including operando transmission X-ray microscopy and operando synchrotron X-ray scattering.•Sealing the cell casing window with metal films maintains the overall electrochemical performance of electrodes.•Depending on the operando experiment, the type of the coin cell and the window shape must be selected carefully.

Tailoring Electrode-Electrolyte Interfaces in Lithium-Ion Batteries Using Molecularly Engineered Functional Polymers.

Electrode-electrolyte interfaces (EEIs) affect the rate capability, cycling stability, and thermal safety of lithium-ion batteries (LIBs). Designing stable EEIs with fast Li+ transport is crucial for developing advanced LIBs. Here, we study Li+ kinetics at EEIs tailored by three nanoscale polymer thin films via chemical vapor deposition (CVD) polymerization. Small binding energy with Li+ and the presence of sufficient binding sites for Li+ allow poly(3,4-ethylenedioxythiophene) (PEDOT) based artificial coatings to enable fast charging of LiCoO2. Operando synchrotron X-ray diffraction experiments suggest that the superior Li+ transport property in PEDOT further improves current homogeneity in the LiCoO2 electrode during cycling. PEDOT also forms chemical bonds with LiCoO2, which reduces Co dissolution and inhibits electrolyte decomposition. As a result, the LiCoO2 4.5 V cycle life tested at C/2 increases over 1700% after PEDOT coating. In comparison, the other two polymer coatings show undesirable effects on LiCoO2 performance. These insights provide us with rules for selecting/designing polymers to engineer EEIs in advanced LIBs.

Surface Engineering of a LiMn2O4 Electrode Using Nanoscale Polymer Thin Films via Chemical Vapor Deposition Polymerization.

Surface engineering is a critical technique for improving the performance of lithium-ion batteries (LIBs). Here, we introduce a novel vapor-based technique, namely, chemical vapor deposition polymerization, that can engineer nanoscale polymer thin films with controllable thickness and composition on the surface of battery electrodes. This technique enables us to, for the first time, systematically compare the effects of a conducting poly(3,4-ethylenedioxythiophene) (PEDOT) polymer and an insulating poly(divinylbenzene) (PDVB) polymer on the performance of a LiMn2O4 electrode in LIBs. Our results show that conducting PEDOT coatings improve both the rate and the cycling performance of LiMn2O4 electrodes, whereas insulating PDVB coatings have little effect on these performances. The PEDOT coating increases 10 C rate capacity by 83% at 25 °C (from 23 to 42 mA h/g) and by 30% at 50 °C (from 64 to 83 mA h/g). Furthermore, the PEDOT coating extends the high-temperature (50 °C) cycling life of LiMn2O4 by over 60%. A model is developed, which can precisely describe the capacity degradation exhibited by the different types of cells, based on the aging mechanisms of Mn dissolution and solid-electrolyte interphase growth. Results from X-ray photoelectron spectroscopy suggest that chemical or coordination bonds form between Mn in LiMn2O4 and O and S in the PEDOT film. These bonds stabilize the surface of LiMn2O4 and thus improve the cycling performance. In contrast, no bonds form between Mn and the elements in the PDVB film. We further demonstrate that this vapor-based technique can be extended to other cathodes for advanced LIBs.

Thermal conductivity of poly(3,4-ethylenedioxythiophene) films engineered by oxidative chemical vapor deposition (oCVD).

Oxidative chemical vapor deposition (oCVD) is a versatile technique that can simultaneously tailor properties (e.g., electrical, thermal conductivity) and morphology of polymer films at the nanoscale. In this work, we report the thermal conductivity of nanoscale oCVD grown poly(3,4-ethylenedioxythiophene) (PEDOT) films for the first time. Measurements as low as 0.16 W m-1 K-1 are obtained at room temperature for PEDOT films with thicknesses ranging from 50-100 nm. These values are lower than those for solution processed PEDOT films doped with the solubilizing agent PSS (polystyrene sulfonate). The thermal conductivity of oCVD grown PEDOT films show no clear dependence on electrical conductivity, which ranges from 1 S cm-1 to 30 S cm-1. It is suspected that at these electrical conductivities, the electronic contribution to the thermal conductivity is extremely small and that phonon transport is dominant. Our findings suggest that CVD polymerization is a promising route towards engineering polymer films that combine low thermal conductivity with relatively high electrical conductivity values.