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Transition metal fluoride (TMF) conversion-type cathodes promise up to 4 times higher gravimetric energy densities compared to those of common intercalation-type cathodes. However, TMF cathodes demonstrate sluggish kinetics, poor efficiencies, and incompatibility with many liquid electrolytes. In this work, coevaporated heterostructured iron and lithium fluoride (Fe-LiF) cathodes are investigated in thin-film solid-state batteries with a LiPON electrolyte and a lithium metal anode. The cells were cycled 2000 times at a cycling rate of 6C. They show a gradual improvement in voltaic efficiency (37-53%) and specific capacity (146-216 mAh/g) during cycling. After 2000 cycles, the cathode capacity reaches 480 mAh/g at a cycling rate of C/3.6, close to its theoretical capacity of 498 mAh/g, at room temperature conditions. This capacity gain is correlated with an observed electrochemically activated nanorestructuring of the cathode, characterized by cycling-induced coarsening (from 2.8 to 4.2 nm) of the metallic iron phase and its accumulation near the current collector interface, as well as lithium fluoride phase accumulation near the LiPON interface.

Thin films of solid-state lithium-ion electrolytes show promise for use in small-sized autonomous power sources for micro- and nanoelectronic elements. The high rate of vacuum-plasma synthesis (~0.5 μm/h) of lithium phosphor-oxynitride (LiPON) films with an ionic conductivity of ~2·10 -6 S/cm is achieved through anodic evaporation of Li 3 PO 4 in a low-pressure arc. The microstructure and ionic conductivity of LiPON films are influenced by the proportion of free lithium in the vapor flow. This paper presents the results of a study on the plasma composition during anodic evaporation of Li 3 PO 4 in a discharge with a self-heating hollow cathode and a crucible anode. A method is proposed for adjusting the free lithium concentration in the gas-vapor (Li 3 PO 4 + N 2 /Ar) discharge plasma based on changing the frequency of collisions of electrons with Li 3 PO 4 vapor in the anodic region of the discharge. It is demonstrated that an increase in the proportion of free lithium in the flow of deposited particles leads to an enhancement in the concentration and mobility of lithium ions in the deposited films and, subsequently, an improvement in the ionic conductivity of LiPON films.

Redox reactions of the Li + insertion/extraction from one to two interlayers of graphene (Gr) on area-defined single-crystalline SiC substrates are investigated using lithium phosphorus oxynitride glass (LiPON) as the solid-state electrolyte. Unlike an organic liquid electrolyte, this glassy electrolyte does not induce a reduction current and excludes the desolvation reaction of Li + . Gr electrodes with less than two Gr layers show a single reduction peak and one or two oxidation peaks below +0.21 V (vs Li + /Li), differing distinctly from those of graphite and multilayer Gr, which display multiple peaks (multiple stage transitions). However, this finding aligns with the conventional understanding that graphite stage structure transitions proceed with stepwise increases or decreases in the number of Gr layers between adjacent Li-inserted interlayers. Cyclic voltammetry measurements indicate the presence of surface capacity due to Li + adsorption/desorption at the LiPON/Gr interface. Moreover, Li + insertion and extraction induce different charge transfer resistances at the level of a single interlayer. These sensitive measurements are achieved using high-quality epitaxial Gr and LiPON electrolyte, which prevent the formation of a solid electrolyte interphase and the desolvation reaction of Li + . Similar measurements using bilayer Gr produced by chemical vapor deposition coupled with a Gr transfer method and an ethylene carbonate/dimethyl carbonate liquid electrolyte are not reliable. Thus, the proposed method is effective for electrochemical measurement of Gr electrodes with a controlled number of layers.

Amorphous lithium phosphorus oxynitrides (LiPON), prepared by reactive magnetron sputtering, have become the electrolytes of choice for all-solid-state thin film microbatteries since its discovery in early 1990s. Nevertheless, there is still a lack of understanding of their atomic-level structure and its influence on ionic conductivity. Solid-state NMR spectroscopy represents a promising technique to determine the atomic-level structure of LiPON glasses but is challenging owing to its low sensitivity in the case of thin film materials. Recently, 31 P solid-state NMR spectra of LiPON thin films were acquired under magic-angle spinning (MAS) conditions and assigned with the help of density functional theory (DFT) calculations of NMR parameters. However, the identification of the different P local environments in these materials is still a challenge owing to their amorphous structure and the lack of resolution of the 31 P MAS NMR spectra. We show herein how the NMR observation of internuclear proximities helps to establish the nature of P sites in LiPON thin films. The 31 P- 14 N proximities are probed by a transfer of population in double resonance (TRAPDOR) experiment, whereas 31 P- 31 P proximities are observed using one-dimensional (1D) 31 P double-quantum (DQ)-filtered and two-dimensional (2D) 31 P homonuclear correlation spectra as well as dipolar dephasing experiments using DQ-DRENAR (DQ-based dipolar-recoupling effects nuclear alignment reduction) technique. The obtained NMR data further support the recently proposed assignment of 31 P NMR signals of LiPON thin films. With the help of this assignment, the simulation of the quantitative 1D 31 P NMR spectrum indicates that PO 4 orthophosphate anions prevail in LiPON thin films and N atoms are mainly incorporated in [O 3- orthophosphate anions prevail in LiPON thin films and N atoms are mainly incorporated in [O 3 PNPO 3 ] 5- dimeric anions. PO 3 N 4- isolated tetrahedra and [O 3 POPO 3 ] 4- anions are also present but in smaller amounts., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: [Olivier Lafon reports financial support was provided by French National Research Agency.]., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Amorphous lithium phosphorus oxynitride (LIPON) has emerged as a promising solid electrolyte for all-solid-state thin-film lithium batteries. In this context, the use of theoretical modeling to characterize, understand, or screen material properties is becoming increasingly important to complement experimental analysis or elucidate features at atomistic level that are difficult to obtain through experimental studies. Density functional theory (DFT) is the method of choice for quantum mechanical material modeling at the atomistic scale. The current state of the art represents DFT values, such as the formation or migration energies relevant for bulk phase of materials, as absolute numbers. Estimating the accuracy or fluctuation range of the different density functionals is challenging. In order to investigate the thermodynamic and kinetic properties of LIPON by DFT, an approach to describe the fluctuation range caused by the choice of the exchange-correlation (XC) functional is developed. Three different model systems were chosen to characterize various structural features of amorphous LIPON, which are distinguished by the cross-linking of the PO u N 4-u -structural units. The uncertainty Ũ is introduced as a parameter describing the fluctuation range of energy values. The uncertainty approach does not determine the accuracy of DFT results, but rather a fluctuation range in the DFT results without the need for a reference value from a higher level of theory or experiment. The uncertainty was determined for both the thermodynamic Li-vacancy formation energies and the kinetic Li-vacancy migration energies in LIPON. We assume that the uncertainty approach can be applied to different material systems with different density functionals., (© 2021 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

In accordance with the fourth industrial revolution (4IR), thin-film all-solid-state batteries (TF-ASSBs) are being revived as the most promising energy source to power small electronic devices. However, current TF-ASSBs still suffer from the perpetual necessity of high-performance battery components. While every component, a series of a TF solid electrolyte ( i.e ., lithium phosphorus oxynitride (LiPON)) and electrodes (cathode and Li metal anode), has been considered vital, the lack of understanding of and ability to ameliorate the cathode (or anode)-electrolyte interface (CEI) (or AEI) has impeded the development of TF-ASSBs. In this work, we suggest an ensemble design of TF-ASSBs using LiPON (500 nm), an amorphous TF-V 2 O 5- x cathode with oxygen vacancies (O vacancy ), a thin evaporated Li anode (evp-Li) with a thickness of 1 μm, and an artificial ultrathin Al 2 O 3 layer between evp-Li and LiPON. Well-defined O vacancy sites, such as O(II) vacancy and O(III) vacancy , in amorphous TF-V 2 O 5- x not only allow isotropic Li + diffusion at the CEI but also enhance both the ionic and electronic conductivities. For the AEI, we employed protective Al 2 O 3 , which was specially sputtered using the facing target sputtering (FTS) method to form a homogeneous layer without damage from plasma. In regard to the contact with evp-Li, interfacial stability, electrochemical impedance, and battery performance, the nanometric Al 2 O 3 layers (1 nm) were optimized at different temperatures (40, 60, and 80 °C). The TF-ASSB cell containing Al 2 O 3 (1 nm) delivers a high specific capacity of 474.01 mAh cm -3 under 60 °C at 2 C for the 400th cycle, and it achieves a long lifespan as well as ultrafast rate capability levels, even at 100 C; these results were comparable to those of TF Li-ion battery cells using a liquid electrolyte. We demonstrated the reaction mechanism at the AEI utilizing time-of-flight secondary ion mass spectrometry (TOF-SIMS) and molecular dynamics (MD) simulations for a better understanding. Our design provides a signpost for future research on the rational structure of TF-LIBs.

Li phosphorus oxynitride (LiPON) is one of a very few solid electrolytes that have demonstrated high stability against Li metal and extended cyclability with high Coulombic efficiency for all solid-state batteries (ASSBs). However, theoretical calculations show that LiPON reacts with Li metal. Here, we utilize in situ electron microscopy to observe the dynamic evolutions at the LiPON-Li interface upon contacting and under biasing. We reveal that a thin interface layer (∼60 nm) develops at the LiPON-Li interface upon contact. This layer is composed of conductive binary compounds that show a unique spatial distribution that warrants an electrochemical stability of the interface, serving as an effective passivation layer. Our results explicate the excellent cyclability of LiPON and reconcile the existing debates regarding the stability of the LiPON-Li interface, demonstrating that, though glassy solid electrolytes may not have a perfect initial electrochemical window with Li metal, they may excel in future applications for ASSBs.

Lithium phosphorus oxynitride (LiPON) is an amorphous solid-state lithium ion conductor displaying exemplary cyclability against lithium metal anodes. There is no definitive explanation for this stability due to the limited understanding of the structure of LiPON. Herein, we provide a structural model of RF-sputtered LiPON. Information about the short-range structure results from 1D and 2D solid-state NMR experiments. These results are compared with first principles chemical shielding calculations of Li-P-O/N crystals and ab initio molecular dynamics-generated amorphous LiPON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with N incorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON's stability is a result of its glassy character. Free-standing LiPON films are produced that exhibit a high degree of flexibility, highlighting the unique mechanical properties of glassy materials., (© 2020 Wiley-VCH GmbH.)

Solid-state electrolytes are very promising to enhance the safety of lithium-ion batteries. Two classes of solid electrolytes, polymer and ceramic, can be combined to yield a hybrid electrolyte that can synergistically combine the properties of both materials. Chemical stability, thermal stability, and high mechanical modulus of ceramic electrolytes against dendrite penetration can be combined with the flexibility and ease of processing of polymer electrolytes. By coating a polymer electrolyte with a ceramic electrolyte, the stability of the solid electrolyte is expected to improve against lithium metal, and the ionic conductivity could remain close to the value of the original polymer electrolyte, as long as an appropriate thickness of the ceramic electrolyte is applied. Here, we report a bilayered lithium-ion conducting hybrid solid electrolyte consisting of a blended polymer electrolyte (BPE) coated with a thin layer of the inorganic solid electrolyte lithium phosphorous oxynitride (LiPON). The hybrid system was thoroughly studied. First, we investigated the influence of the polymer chain length and lithium salt ratio on the ionic conductivity of the BPE based on poly(ethylene oxide) (PEO) and poly(propylene carbonate) (PPC) with the salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The optimized BPE consisted of 100 k molecular weight PEO, 50 k molecular weight PPC, and 25(w/w)% LiTFSI, (denoted as PEO100PPC50LiTFSI25), which exhibited an ionic conductivity of 2.11 × 10 -5 S/cm, and the ionic conductivity showed no thermal memory effects as the PEO crystallites were well disrupted by PPC and LiTFSI. Second, the effects of LiPON coating on the BPE were evaluated as a function of thickness down to 20 nm. The resulting bilayer structure showed an increase in the voltage window from 5.2 to 5.5 V (vs Li/Li+) and thermal activation energies that approached the activation energy of the BPE when thinner LiPON layers were used, resulting in similar ionic conductivities for 30 nm LiPON coatings on PEO100PPC50LiTFSI25. Coating BPEs with a thin layer of LiPON is shown to be an effective strategy to improve the long-term stability against lithium.

This study reports the effect of temperature on Li nucleation at the Cu/LiPON interface. Galvanostatic Li plating is performed on LiPON glass electrolytes at different temperatures ranging from 25 to 100 °C. At any temperature, the negative voltage peak appears, indicating Li nucleation, immediately after starting Li plating. The nucleation overpotential and nucleation number density decrease with increasing temperature. This is because the diffusivity of Li adatoms/ions along the Cu/LiPON interface increases with temperature, resulting in an increase in the amount of Li atoms incorporated into a single Li nucleus. The critical nucleation area also extends with increasing temperature. It is found that the activation energy for the interfacial diffusion of Li adatoms/ions along the Cu/LiPON interface is 51 kJ mol -1 (0.53 eV), which is close to the activation energy for Li + conduction in LiPON.

We report here efforts to synthesize free-standing, dry polymer electrolytes that exhibit superior ionic conductivities at ambient for Li-S batteries. Co-dissolution of poly(ethylene oxide) (PEO) ( M n 900k) with Li x PON and Li x SiPON polymer systems at a ratio of approximately 3:2 followed by casting provides transparent, solid-solution films 25-50 μm thick, lowering PEO crystallinity, and providing measured impedance values of 0.1-2.8 × 10 -3 S/cm at ambient. These values are much higher than simple PEO/Li + salt systems. These solid-solution polymer electrolytes (PEs) are (1) thermally stable to 100 °C; (2) offer activation energies of 0.2-0.5 eV; (3) suppress dendrite formation; and (4) enable the use of lithium anodes at current densities as high as 3.5 mAh/cm 2 . Galvanostatic cycling of SPAN/PEs/Li cell (SPAN = sulfurized, carbonized polyacrylonitrile) shows discharge capacities of 1000 mAh/g sulfur at 0.25C and 800 mAh/g sulfur at 1C with high coulumbic efficiency over 100 cycles.

Here, we demonstrate the theory-guided plasma synthesis of high purity nanocrystalline Li 3.5 Si 0.5 P 0.5 O 4 and fully amorphous Li 2.7 Si 0.7 P 0.3 O 3.17 N 0.22 . The synthesis involves the injection of single or mixed phase precursors directly into a plasma torch. As the material exits the plasma torch, it is quenched into spherical nanocrystalline or amorphous nanopowders. This process has virtually zero Li loss and allows for the inclusion of N, which is not accessible with traditional synthesis methods. We further demonstrate the ability to sinter the crystalline nanopowder into a dense electrolyte membrane at 800 °C, well below the traditional 1000 °C required for a conventional Li 3.5 Si 0.5 P 0.5 O 4 powder.

Most commercial lithium-ion batteries and other types of batteries rely on liquid electrolytes, which are preferred because of their high ionic conductivity, and facilitate fast charge-transfer kinetics at the electrodes. On the other hand, hybrid battery concepts that combine solid and liquid electrolytes might be needed to suppress unwanted shuttle effects in liquid electrolyte-only systems, in particular if mobile redox systems are involved in the cell chemistry. However, at the then newly introduced interface between liquid and solid electrolytes, a solid-liquid electrolyte interphase forms. In this study, we analyze the formation of such an interphase between the solid electrolyte lithium phosphorous oxide nitride (Li x PO y N z , "LiPON") and various liquid electrolytes using in situ neutron reflectometry, quartz crystal microbalance, and atomic force microscopy measurements. Our results show that the interphase consists of two layers: a nonconducting layer directly in contact with "LiPON" and a lithium-rich outer layer. Initially, a fast growth of the solid-liquid electrolyte interphase is observed, which slows down significantly afterward, resulting in a thickness of about 20 nm eventually. Here, a formation mechanism is proposed, which describes the solid-liquid electrolyte interphase growth as the fast deposition of a film, which mostly covers the "LiPON", with only a little degree of remaining porosity. The residual void space is then slowly filled, thus blocking the remaining channels for ionic conduction, which leads to increasing resistance of the interphase. The results obtained imply that hybrid battery concepts with liquid electrolyte and solid electrolyte can be hampered by highly resistive interphases, whose formation cannot be simply slowed down or suppressed. Further research is required regarding possible countermeasures.

Transparent electrochemical energy storage devices have attracted extensive attention for the power supply of next-generation transparent electronics. In this paper, semitransparent thin film batteries (TFBs) with a grid-structured design have been fabricated on glass substrates using specific photolithography and etching processes to achieve LiCoO 2 /LiPON/Si structures below human eye resolution. UV-vis transmittances up to 60% have been measured for the obtained TFBs. A discharge capacity as high as 0.15 mAh has been recorded upon galvanostatic cycling at the C/2 rate within 4.2-3 V voltage range for the highest transmittances. The capacity variation trend exhibits an initial phase of a gradual decrease with an average capacity loss of 0.15% per cycle and thereafter a second phase with almost stable capacity. Particular attention has been given to the effects of architecture parameters on the TFB optical and electrochemical properties. To the best of our knowledge, this work is the first demonstration of transparent, all inorganic, thin film lithium ion batteries. While reported studies are limited to battery structures involving liquid or polymer materials, our devices will contribute to improve form factor freedom, extend operating ranges, enhance long-term stability, and will be relevant to the integration into various optoelectronic devices.

Detailed understanding of solid-solid interface structure-function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and Li x CoO 2 cathode, have been reported to generate solid-electrolyte interphase (SEI)-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy Li x CoO 2 (104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ultrathin lithium phosphorus oxynitride glass (LiPON) films with thicknesses down to 15 nm, deposited by reactive sputtering in nitrogen plasma, were found to be electronically insulating. Such ultrathin electrolyte layers could lead to high power outputs and increased battery energy densities. The effects of stoichiometry, film thickness, and substrate material on the ionic conductivity were investigated. As the amount of nitrogen in the layers increased, the activation energy of the ionic conductivity decreased from 0.63 to 0.53 eV, leading to a maximum conductivity of 1 × 10(-6) S/cm. No dependence of the ionic conductivity on the film thickness or substrate material could be established. A detailed analysis of the equivalent circuit model used to fit the impedance data is provided. Polarization measurements were performed to determine the electronic leakage in these ultrathin films. A 15-nm LiPON layer on a TiN substrate showed electronically insulating properties with electronic resistivity values around 10(15) Ω·cm. To our knowledge, this is the thinnest RF-sputtered LiPON layer shown to be electronically insulating while retaining good ionic conductivity.

Materials that undergo conversion reactions to form different materials upon lithiation typically offer high specific capacity for energy storage applications such as Li ion batteries. However, since the reaction products often involve complex mixtures of electrically insulating and conducting particles and significant changes in volume and phase, the reversibility of conversion reactions is poor, preventing their use in rechargeable (secondary) batteries. In this paper, we fabricate and protect 3D conversion electrodes by first coating multiwalled carbon nanotubes (MWCNT) with a model conversion material, RuO2, and subsequently protecting them with conformal thin-film lithium phosphous oxynitride (LiPON), a well-known solid-state electrolyte. Atomic layer deposition is used to deposit the RuO2 and the LiPON, thus forming core double-shell MWCNT@RuO2@LiPON electrodes as a model system. We find that the LiPON protection layer enhances cyclability of the conversion electrode, which we attribute to two factors. (1) The LiPON layer provides high Li ion conductivity at the interface between the electrolyte and the electrode. (2) By constraining the electrode materials mechanically, the LiPON protection layer ensures electronic connectivity and thus conductivity during lithiation/delithiation cycles. These two mechanisms are striking in their ability to preserve capacity despite the profound changes in structure and composition intrinsic to conversion electrode materials. This LiPON-protected structure exhibits superior cycling stability and reversibility as well as decreased overpotentials compared to the unprotected core-shell structure. Furthermore, even at very low lithiation potential (0.05 V), the LiPON-protected electrode largely reduces the formation of a solid electrolyte interphase.