Inorganic electrolytes for solid state batteries with Li metallic anodes must combine properties such as high ionic conductivity, chemical stability, and resistance to failure due to propagation of Li dendrites. Abundance of experimental evidence suggests that cracking of the solid electrolytes due to pressure exerted by lithium plating into the material defects is the primary source of failure [1]. This is due to inherent brittleness of the ceramic ionic conductors, i.e. their inability to reduce stress by means other than fracture. Unlike ceramics, plastic deformation in glass can be achieved via shear and (or) by densification. Both mechanisms can be operational in glasses with reduced content of glass formers relative to the content of glass modifiers – i.e. inverted glasses. Using the example of lithium phosphorous oxynitride, Lipon, we demonstrate how these two mechanisms are capable of accommodating applied stress while avoiding creation of new surfaces by cracking. We investigate the resistance to fracture in Lipon-like glasses and the underlying connection to their composition via instrumented nano-indentation, Raman spectroscopy, and numerical simulations. We observe enhancement of isochoric shear with increase of Li content, similarly to the reports of increased plasticity in sodium aluminoborate glases with high alkali content [2]. Nano-indentation demonstrates that Lipon is extremely resistant to fracture, compared to other inorganic solid electrolytes [3]. [1] Porz, T. Swamy, B.W. Sheldon, D. Rettenwander, T. Fromling, H.L. Thaman, S. Berendts, R. Uecker, W.C. Carter, Y.-M. Chiang, Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017) [2] Sellappan, T. Rouxel, F. Celarie, E. Becker, P. Houizot, R. Conradt, Composition dependence of indentation deformation and indentation cracking in glass. Acta Mater. 61, 5949–5965 (2013) [3] Kalnaus, A. Westover, M. Kornbluth, E.J. Herbert, N.J. Dudney, Resistance to fracture in the glassy solid electrolyte Lipon. J. Mater. Research, 36, 787-795 (2021)

Composite electrolytes for lithium batteries typically combine materials with very different mechanical properties and ionic transport mechanisms and the degree to which these two phases affect each other is not well understood. In this work we used numerical simulations and experiments to investigate the transport in composite electrolytes consisting of polyethylene oxide (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) and Li1.3Al0.3Ti1.7(PO4)3 (LATP) lithium ion conducting glass-ceramic particles. In particular we are interested in how the introduction of a single ion conductor (SIC) changes the salt concentration gradients in the polymer electrolyte (PE) under applied potential. To study this, we performed numerical simulations and chronoamperometry experiments in electrolytes with different arrangements of the SIC and PE phases, i.e. layers and particulate composites. The results show that the particulate composites have the highest concentration gradients and take the longest time to reach steady state current. The best arrangement appears to have a layer of SIC impenetrable to anions in the polymer phase within the electrolyte membrane.

A high temperature multibeam-optical-stress sensor (HTMOSS) was used to characterize the coefficient of thermal expansion (CTE) and yield stress of 1-micron thick Lipon films.

Solid-state batteries with lithium metal anodes have the potential for higher energy density, longer lifetime, wider operating temperature, and increased safety. Although the bulk of the research has focused on improving transport kinetics and electrochemical stability of the materials and interfaces, there are also critical challenges that require investigation of the mechanics of materials. In batteries with solid-solid interfaces, mechanical contacts, and the development of stresses during operation of the solid-state batteries, become as critical as the electrochemical stability to keep steady charge transfer at these interfaces. This review will focus on stress and strain that result from normal and extended battery cycling and the associated mechanisms for stress relief, some of which lead to failure of these batteries.

Here, we provide an in-depth structural characterization of the amorphous ionic glasses LiPON and LiSiPON with high Li content. Based on ab initio molecular dynamics simulations, the structure of these materials is an inverted structure with either isolated polyanion tetrahedra or polyanion dimers in a Li+ matrix. Based on neutron scattering data, this type of inverted structure leads to a significant amount of medium-range ordering in the structure, as demonstrated by two sharp diffraction peaks and a periodic structural oscillation in the density function G(r). While this medium-range ordering is commonly observed in liquids and metallic glasses, it has not previously been observed in oxides. On a local scale, adding N and Si increases the number of anion bridges and polyanion dimer structures, leading to higher ionic conductivity. In the medium-range ordering, the addition of Si leads to more disorder in the polyanion substructure but a significant increase in the ordering of the O substructure. Finally, we demonstrate that this inverted structure with medium-range ordering results in a glassy material that is both mechanically stiff and ductile on the nanoscale.

High temperature multi-optical-stress sensor (HTMOSS) has been used to characterize the coefficient of thermal expansion (CTE) and yield stress of 1-micron thick LiPON films. Six fully dense, amorphous films were deposited on glass and sapphire substrates. The films were then annealed at temperatures ranging from 80 to 200 C for 3 hours. The CTE of LiPON is found to be approximately 4.1e-6, and argued to be independent of the substrate type. Because of this intermediate CTE value, by varying the substrate, we could impose either tension and compression due to thermal mismatch to the film. We observed further that the yield stress of the film is approximately 60 MPa under compression and 100 MPa under tension. Using constant-load hold at and beyond yield point, the films were found to relieve the stress developed during heating with visco-plastic deformation, which led to permanent residual stress during cooling as high as 120 MPa in either tension or compression depending on substrate type. We also found that at annealing temperature higher than 140 C LiPON lost ductility which could be due to composition changes as indicated by XPS measurement. The stress-relief mechanism at constant-load indicates that LiPON may be beneficial as a protective layer against dendrites penetration. Moreover our experimental platform proves that it's an effective method to engineer strain into thin-film solid electrolytes that could be extended to other materials like LLZO or sulfide electrolyte.

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). However, over 3 orders of magnitude of discrepancy in ionic conductivity has been reported in PAN-based SPEs, in both the low salt concentration and the high salt concentration regimes. This discrepancy originates from different film processing conditions. In this study, we rigorously examine how processing conditions, including solution mixing, casting, and drying conditions affect the morphology, ion transport, solvation structure, Li and oxidative stability of PAN based electrolytes. It is found that the ion transport, lithium stability and the oxidative stability of PAN-based SPEs are critically dependent on the residual dimethylformamide (DMF) solvent content. We systematically study four different drying conditions and the resulting residual solvent is quantified by infrared spectroscopy. We demonstrate that conductivity variation across 5 orders of magnitude can be obtained depending on the drying conditions. Furthermore, the effects of residual DMF solvent on the ion transport mechanism, stability against lithium and the oxidative stability are elucidated. This thorough study lays the groundwork for future development of PAN based electrolytes.

intercalation and deintercalation into the carbon fiber may occur when they are cycled at high potentials >4.5 V.

The next generation of high energy batteries using Li metal as an anode and utilizing a solid electrolyte requires good interfacial stability, reasonable ionic conductivity, and most importantly the ability to eliminate dendrites.i While most solid-state electrolytes suffer from both interfacial instability and Li penetration resulting in cell shorting,ii,iii The solid electrolyte Lipon has a remarkable ability to suppress dendrites, and enable solid state batteries that can cycle for more than 1000 cycles and support current densities as high as 10 mA/cm2.iii,iv Recent efforts have started to illuminate the origin of Lipon’s ability to enable high-energy solid-state Li metal batteries. This presentation will highlight the unique structure of Lipon and Lipon like materials, the interfacial structure of Lipon with Li metal, and the mechanics that enable high quality performance in Lipon based solid-state batteries.v,vi,vii Finally, the presentation will connect these findings from Lipon to outline key underlying principles that answer the question, how do we enable high energy Li metal batteries? Acknowledgements: Work for this presentation was funded by ARPA-E under contract #DE-AR0000775, and the US Department of Energy Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office’s US-German Cooperation on Energy Storage: Interfaces and Interphases In Rechargeable Li-metal based Batteries Program and the Battery Materials Research Program under program managers Tien Duong and Simon Thompson. P. Albertus et al., “Challenges for and pathways toward Li-metal-based all-solid-state batteries”, ACS Energy Letters, 6, 4, 1399-1404, Mar. 2021. Fudong Han, Andrew S Westover, Jie Yue, Xiulin Fan, Fei Wang, Miaofang Chi, Donovan N Leonard, Nancy J Dudney, Howard Wang, Chunsheng Wang, “High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes”, Nature Energy, 1, Jan. 2019. Andrew S Westover, Nancy J Dudney, Robert L Sacci, Sergiy Kalnaus, “Deposition and Confinement of Li Metal along an Artificial Lipon–Lipon Interface”, ACS Energy Letters, 4, 651-655, Feb. 2019. Juchuan Li, Cheng Ma, Miaofang Chi, Chengdu Liang, and Nancy J. Dudney. "Solid electrolyte: the key for high‐voltage lithium batteries." Advanced Energy Materials5, 4, 1401408, 2015. Andrew S Westover* Valentina Lacivita,* , Andrew Kercher, Nathan D Phillip, Guang Yang, Gabriel Veith, Gerbrand Ceder, Nancy J Dudney, “Resolving the amorphous structure of lithium phosphorus oxynitride (Lipon)”, Journal of the American Chemical Society 140 (35), 11029-11038, July 2018. Andrew S Westover, Robert L Sacci, Nancy Dudney, “Electroanalytical measurement of interphase formation at a Li metal–solid electrolyte interface”, ACS Energy Letters, 5, 12, 3860-3867, Nov. 2020. Sergiy Kalnaus, Andrew S Westover, Mordechai Kornbluth, Erik Herbert, Nancy J Dudney, “Resistance to fracture in the glassy solid electrolyte Lipon”, Journal of Materials Research, 36, 4, 787-796, Feb. 2021.

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). In this study, we systematically investigate the processing of PAN based SPEs containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, using dimethylformamide (DMF) as the solvent. The effects of PAN processing procedure including solution mixing, casting, and drying on the morphology, ion transport, solvation structure, Li and oxidative stability of PAN electrolytes are thoroughly examined. In particular, four drying conditions are investigated and the amount of residual DMF is accurately determined using infrared (IR) spectroscopy. Varying the drying conditions can lead to five orders of magnitude decrease in the ionic conductivity. As DMF content decreases, the SPE's stability again Li metal dramatically improves. The practical oxidative stability is also strongly affected by the residual DMF content, ranging from 2.5 V to 3.5 V, much lower than reported values. Finally, the role of the residual DMF solvent is elucidated. DMF content vitally influences ion solvation structure at different concentration regimes, which ultimately dictates the ion conduction mechanism and oxidative stability of PAN based SPEs. This thorough study lays the groundwork for future development of PAN based electrolytes.

AbstractWe discuss polymer electrolytes for use in rechargeable lithium batteries. Polymer electrolytes have the potential to enable batteries with lithium metal anodes. These batteries have significantly higher theoretical energy densities than current lithium‐ion batteries. We consider binary mixtures of polymers and salts. We also cover more complex systems such as polymer electrolytes swollen with a solvent (gel polymer electrolytes) and microphase separated polymer electrolytes. By covalently attaching the anions to the chains in a polymer solid, one obtains a single‐ion conductor. We mainly focus on experiments wherein the polymer electrolyte is placed between two lithium metal electrodes. These experiments enable the determination of three transport parameters, ionic conductivity, salt diffusion coefficient, and transference number, and the thermodynamic factor. The properties of dry polymer electrolytes are contrasted with those of gel polymer electrolytes. The gel systems exhibit higher conductivity while the dry systems exhibit superior mechanical properties. We discuss interfacial impedance when lithium metal is contacted with polymer electrolytes and the importance of coulombic efficiency.

Here, we present a comparison of lithium metal films produced via rolling and thermal evaporation using synchrotron hard X-ray microtomography. In past studies of rolled lithium metal foils, a large number of C, O, and N impurities were found and identified as the key cause for failure in lithium metal cells. In this comparison, the X-ray tomography data show that the evaporated lithium metal films have an average impurity concentration of 19 particles/mm3 in comparison to 1350 particles/mm3 in the rolled lithium metal. An analysis of the inner substrate/lithium interface and outer lithium surface of the thermally evaporated film shows a much greater concentration of impurities at these interfaces, further emphasizing the importance of interface engineering in producing high-quality lithium metal batteries. We show that, if surface contamination can be avoided, it is possible to obtain lithium films with no impurities detectable by synchrotron hard X-ray tomography.

Solid-state lithium metal batteries (SSLMBs) containing polyethylene oxide (PEO)-derived polymer electrolytes and high-voltage (> 4 V vs. Li/Li+) cathode materials suffer from three sources of failure: (1) instability between the polymer electrolyte and cathode at high voltage, (2) instability of the polymer electrolyte with Li metal, and (3) poorly-designed cathodes. In this study, these three sources of failure are deconvoluted by studying Ni-rich LiNixMnyC1-x-yO2 (NMC, x >= 0.6) cathodes and a gel polymer electrolyte (GPE) derived from PEO. Initial cycling data reveals that rapid capacity fade occurs regardless of whether soft short circuits form due to Li dendrites. Cyclic voltammetry scans on cells featuring a Li metal electrode, GPE, and a NMC811 electrode free of additives suggest that there are no runaway reactions between the GPE and NMC811 up to 4.5 V vs. Li/Li+. Cathode/cathode symmetric cell cycling demonstrates that Li metal reactivity is a prime source of failure, though a poorly-designed cathode leads to subpar performance. A cathode with single-crystal NMC particles was demonstrated to achieve better initial capacity and longer cycle life, indicating room for improvement in SSLMB cathode design. Therefore, the sources of failure as enumerated may be ranked as follows from most to least concerning: 2 > 3 > 1. (C) 2021 Elsevier Ltd. All rights reserved.

High-areal-capacity cathodes are needed for energy-dense solid-state batteries. Here, we demonstrate a bilayer polymer electrolyte design for cycling 3-6 mAh/cm(2) NMC811 composite cathodes. The bilayer electrolyte comprises a cross-linked poly(ethylene oxide) (PEO)-based electrolyte layer and a linear-PEO-based electrolyte layer. The former provides dendritic resistance, and the latter provides a seamless interface with the cathode during cycling. Using a single layer of either membrane led to severe shorting or extremely low Coulombic efficiency (CE) in the first cycle. The general concept of a rigid dendrites-inhibiting electrolyte facing Li anode and a softer, cathode-integrated electrolyte that ensures contact with the cathodes during cycling may present a pattern for enabling high-energy-density cathodes.

We report on the mechanical behavior of a solid Li-ion conductor, lithium phosphorous oxynitride (Lipon), for solid-state batteries. In particular, the purpose of this investigation was to quantify the resistance to cracking (fracture toughness) of this material by nanoindentation. We observed surprising ductility and the ability to recover in Lipon. We were unsuccessful in inducing cracks in Lipon and observed accommodation of stress via pile-up and densification rather than by cracking at various strain rates. Simulations demonstrate that both deformation and densification depend on the alkali content. Densification appears to be recoverable at room temperature. We discuss the findings in comparison with nanoindentation-induced cracking in other inorganic solid electrolyte materials and provide possible explanations for high resistance of Lipon to Li filament propagation.

This work reports carbon fibers as an electrode material and current collector for dual‐carbon and lithium‐ion batteries. Fully graphitic and semigraphitic carbon fibers undergo anion intercalation beyond 4.5 V versus Li/Li+. Symmetric dual‐carbon full cells using a pitch‐coated fully graphitic carbon fiber mat as both cathode and anode delivers an energy‐density of 276 and 322 Wh kg−1 at 342 W kg−1 power density in the voltage range of 3.0–5.0 and 3.0–5.2 V, respectively. On the other hand, nongraphitic carbon fibers do not exhibit anion intercalation up to 5.2 V and can be used as a current collector. They also possess a larger number of Li+ storage sites in their randomly oriented microstructure when used as an anode. A lithium‐ion full cell with double carbon‐coated C‐LiFePO4 loaded on nongraphitic carbon fiber as a cathode and pitch‐coated nongraphitic carbon fiber as an anode exhibits 202.6 and 75.2 Wh kg−1 energy density at power densities of 46.75 W kg−1 and 11.7 kW kg−1, respectively in 2.0–3.5 V range. This pitch‐coated carbon fiber‐based battery configuration eliminates the need for metal foils and costly fluorinated binders, lowers overall weight of the cell, and is capable of sustaining mechanical stress and thermal shock.

Solid electrolytes hold great promise for enabling the use of Li metal anodes. The main problem is that during cycling, Li can infiltrate along grain boundaries and cause short circuits, resulting in potentially catastrophic battery failure. At present, this phenomenon is not well understood. Here, through electron microscopy measurements on a representative system, Li 7 La 3 Zr 2 O 12 , we discover that Li infiltration in solid oxide electrolytes is strongly associated with local electronic band structure. About half of the Li 7 La 3 Zr 2 O 12 grain boundaries were found to have a reduced bandgap, around 1–3 eV, making them potential channels for leakage current. Instead of combining with electrons at the cathode, Li + ions are hence prematurely reduced by electrons at grain boundaries, forming local Li filaments. The eventual interconnection of these filaments results in a short circuit. Our discovery reveals that the grain-boundary electronic conductivity must be a primary concern for optimization in future solid-state battery design.

Recent advancements in Li and Li-ion based energy storage resulted in development of novel electrode materials for higher energy density which are finding their applications in transportation. There appears to be a limitation in improvement of specific energy of the system based solely on design of material compositions for multivalent intercalation compounds. In addition, higher energy stored by the system implies need for addressing safety concerns especially when it comes to large automotive battery packs. New approaches for improvement of both energy density and safety of batteries are emerging, where multifunctionality of the materials and/or architectures is utilized. This article presents a review for such approaches from multifunctional current collectors to design of batteries capable of supporting mechanical loads and thus possessing ability to be used as a structural component.