Chemical and Electrochemical Characterization of Hot-Pressed Li6PS5Cl Solid State Electrolyte: Operating Pressure-Invariant High Ionic Conductivity.

Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li6PS5X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10-2 S cm-1) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250 °C. Moreover, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa.

Assessing the Thermal Safety of a Li Metal Solid-State Battery Material Set Using Differential Scanning Calorimetry.

At the earliest stage of battery development, differential scanning calorimetry (DSC) of a sample with all battery cell stack materials can provide quantitative data on the reaction thermochemistry. The resulting quantitative thermochemical map of expected reactions upon heating can then guide chemistry and component development toward improved cell safety. In this work, we construct Li0.43CoO2 + C + PVDF|Li6.4La3Zr1.4Ta0.6O12|Li microcell DSC samples with capacity-matched electrodes and test to 500 °C. Notable observations are: (1) ∼74% of the O2 released from the Li0.43CoO2 cathode reacts with C to form CO2 rather than with molten Li to produce Li2O, (2) PVDF pyrolysis (>400 °C) releases HF gas that exothermically reacts with Li to form LiF, and (3) reactions involving oxygen (e.g., CO2 and Li2O formation) account for ∼60% of the total heat released, and reactions involving HF (e.g., LiF formation) account for ∼36% of the total heat released.

Reference Electrode Reveals Insights on Sodium Metal/Solid Electrolyte Interface Cycling and Voiding Behaviors at High Current Densities and Areal Capacities.

Plating and stripping processes at solid metal electrode/solid electrolyte interfaces are of great significance for high-energy, solid-state batteries. Here, we introduce a Na metal reference electrode to a symmetric Na metal/sodium ß″ alumina/Na metal cell and study both cycling and unidirectional protocols with a focus on high current density and areal capacity. For example, in a current ramp test at 5 mAh cm-2 we find a shift from stable to unstable interfacial polarization during stripping at ≳3 mA cm-2, and at 7.5 mA cm-2 we measure 100s of mV of voltage magnitude rise at the stripping electrode and 10s of mV of voltage changes at the plating electrode. In unidirectional testing (i.e., passing current in a single direction until cell failure), at 1.2 mA cm-2 we find only ∼40% of the initial Na foil could be transferred through the solid electrolyte and again observe 100s of mV (and larger) voltage magnitude rise at the stripping electrode and 10s of mV of voltage change at the plating electrode. This test also shows that the 100s of mV of interfacial polarization can be sustained for hours (at 1.2 mA cm-2) to tens of hours (in a test at 0.3 mA cm-2). Hence, across several test protocols we find a Na metal reference electrode provides quantitative insights on electrochemical interfacial behavior that are not revealed in two-electrode testing. We also built a two-dimensional model of our three-electrode symmetric cell to quantify the link between the measured interfacial potentials in our testing and changes in electrochemically active interfacial contact and find that 100s of mV of interfacial potential rise indicates loss of electrochemically active contact area of >80%. Our work provides a promising approach to clarify the coupled interfacial electrochemical and contact mechanics processes at solid metal electrode/solid electrolyte interfaces.

In Situ Raman Mapping of Si Island Electrodes and Stress Modeling as a Function of Lithiation and Size.

Si is known for cracking and delamination during electrochemical cycling of a battery due to the large volume change associated with Li insertion and extraction. However, it has been found experimentally that patterned Si island electrodes that are 200 nm thick and less than 7 µm wide can deform in a purely elastic manner. Inspired by this, we performed in situ Raman stress characterization of model poly-crystalline Si island electrodes using an electrochemical cell coupled with an immersion objective lens and designed for a short working distance. A 5 µm wide Si island electrode showed a parabolic stress profile during lithiation, while for a 15 µm Si island electrode, a stress plateau in the center of the electrode was observed. A continuum model with coupled electro-chemo-mechanical (ECM) physics was established to understand the stress measurement. A qualitative agreement was reached between modeling and experimental data, and the critical size effect could be explained by the Li diffusive flux as governed by competition between the Li concentration and hydrostatic stress gradients. Below the critical size, the stress gradient drives Li toward the edges, where the electrode volume is free to expand, while above the critical size, the stress plateau inhibits Li diffusion to the edge and forces destructive stress relief by cracking. This work represents a promising methodology for in situ characterization of ECM coupling in battery electrodes, with suggestions provided for further improvement.

Micro-Raman Stress Characterization of Crystalline Si as a Function of the Lithiation State.

This work presents a stress characterization of crystalline Si electrodes using micro-Raman spectroscopy. First, the phase heterogeneity in the c-Si electrodes after initial lithiation was investigated by scanning electron microscopy (SEM) and other complementary techniques. A surprising three-phase layer structure, with a-LixSi (x = 2.5), c-LixSi (x = 0.3-2.5), and c-Si layers, was observed, and its origin was attributed to the electro-chemo-mechanical (ECM) coupling effect in the c-Si electrodes. Then, a Raman scan was performed to characterize stress distribution in lithiated c-Si electrodes. The results showed that the maximum tensile stress occurred at the interface between c-LixSi and c-Si layers, indicating a plastic flow behavior. The yield stress increased with total lithium charge, and the relationship showed consistency with a prior multibeam optical sensor (MOS) study. Lastly, stress distribution and structural integrity of the c-Si electrodes after initial delithiation and further cycling were studied, and a comprehensive picture of the failure mechanism of the c-Si electrode was obtained.

Imaging Phase Segregation in Nanoscale LixCoO2 Single Particles.

LixCoO2 (LCO) is a common battery cathode material that has recently emerged as a promising material for other applications including electrocatalysis and as electrochemical random access memory (ECRAM). During charge-discharge cycling LCO exhibits phase transformations that are significantly complicated by electron correlation. While the bulk phase diagram for an ensemble of battery particles has been studied extensively, it remains unclear how these phases scale to nanometer dimensions and the effects of strain and diffusional anisotropy at the single-particle scale. Understanding these effects is critical to modeling battery performance and for predicting the scalability and performance of electrocatalysts and ECRAM. Here we investigate isolated, epitaxial LiCoO2 islands grown by pulsed laser deposition. After electrochemical cycling of the islands, conductive atomic force microscopy (c-AFM) is used to image the spatial distribution of conductive and insulating phases. Above 20 nm island thicknesses, we observe a kinetically arrested state in which the phase boundary is perpendicular to the Li-planes; we propose a model and present image analysis results that show smaller LCO islands have a higher conductive fraction than larger area islands, and the overall conductive fraction is consistent with the lithiation state. Thinner islands (14 nm), with a larger surface to volume ratio, are found to exhibit a striping pattern, which suggests surface energy can dominate below a critical dimension. When increasing force is applied through the AFM tip to strain the LCO islands, significant shifts in current flow are observed, and underlying mechanisms for this behavior are discussed. The c-AFM images are compared with photoemission electron microscopy images, which are used to acquire statistics across hundreds of particles. The results indicate that strain and morphology become more critical to electrochemical performance as particles approach nanometer dimensions.

Rapid Pressureless Sintering of Glasses.

Silica glasses have wide applications in industrial fields due to their extraordinary properties, such as high transparency, low thermal expansion coefficient, and high hardness. However, current methods of fabricating silica glass generally require long thermal treatment time (up to hours) and complex setups, leading to high cost and slow manufacturing speed. Herein, to obtain high-quality glasses using a facile and rapid method, an ultrafast high-temperature sintering (UHS) technique is reported that requires no additional pressure. Using UHS, silica precursors can be densified in seconds due to the large heating rate (up to 102 K s-1 ) of closely placed carbon heaters. The typical sintering time is as short as ≈10 s, ≈1-3 orders of magnitude faster than other methods. The sintered glasses exhibit relative densities of > 98% and high visible transmittances of ≈90%. The powder-based sintering process also allows rapid doping of metal ions to fabricate colored glasses. The UHS is further extended to sinter other functional glasses such as indium tin oxide (ITO)-doped silica glass, and other transparent ceramics such as Gd-doped yttrium aluminum garnet. This study demonstrates an UHS proof-of-concept for the rapid fabrication of high-quality glass and opens an avenue toward rapid discovery of transparent materials.

Copper-coordinated cellulose ion conductors for solid-state batteries.

Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1-3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10-3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2-0.5 in other polymers2) and a wide window of electrochemical stability (0-4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries.

Enabling "lithium-free" manufacturing of pure lithium metal solid-state batteries through in situ plating.

The coupling of solid-state electrolytes with a Li-metal anode and state-of-the-art (SOA) cathode materials is a promising path to develop inherently safe batteries with high energy density (>1000 Wh L-1). However, integrating metallic Li with solid-electrolytes using scalable processes is not only challenging, but also adds extraneous volume since SOA cathodes are fully lithiated. Here we show the potential for "Li-free" battery manufacturing using the Li7La3Zr2O12 (LLZO) electrolyte. We demonstrate that Li-metal anodes >20 µm can be electroplated onto a current collector in situ without LLZO degradation and we propose a model to relate electrochemical and nucleation behavior. A full cell consisting of in situ formed Li, LLZO, and NCA is demonstrated, which exhibits stable cycling over 50 cycles with high Coulombic efficiencies. These findings demonstrate the viability of "Li-free" configurations using LLZO which may guide the design and manufacturing of high energy density solid-state batteries.

Batteries for electric and hybrid-electric vehicles.

Batteries have powered vehicles for more than a century, but recent advances, especially in lithium-ion (Li-ion) batteries, are bringing a new generation of electric-powered vehicles to the market. Key barriers to progress include system cost and lifetime, and derive from the difficulty of making a high-energy, high-power, and reversible electrochemical system. Indeed, although humans produce many mechanical and electrical systems, the number of reversible electrochemical systems is very limited. System costs may be brought down by using cathode materials less expensive than those presently employed (e.g., sulfur or air), but reversibility will remain a key challenge. Continued improvements in the ability to synthesize and characterize materials at desired length scales, as well as to use computations to predict new structures and their properties, are facilitating the development of a better understanding and improved systems. Battery research is a fascinating area for development as well as a key enabler for future technologies, including advanced transportation systems with minimal environmental impact.