Structural Degradation of High Voltage Lithium Nickel Manganese Cobalt Oxide (NMC) Cathodes in Solid-State Batteries and Implications for Next Generation Energy Storage

In this study, we report the stability of the layered high voltage cathode NMC622 with respect to a standard liquid electrolyte and in an all solid-state configuration. NMC622 cathodes with a (104) orientation were found to suffer from degradation at high voltage (4.5 V vs Li/Li+) due to electrolyte-promoted degradation of the layered structure in a carbonate electrolyte. The lithium phosphorus oxynitride (LiPON) electrolyte was able to suppress the extent of this decomposition in solid-state cells but not totally prevent it from occurring. In the solid-state cells the capacity decreased from 203 to 93 mAh/g in the first cycle and from 93 to 79 mAh/g over the subsequent 99 cycles, whereas, after 20 cycles, the liquid cell charge capacity was dominated by the irreversible electrolyte degradation. The interfacial resistances of the solid-state cells were stable with cycling, suggesting minimal degradation of the NMC622/LiPON interface and incumbent losses due to structural evolution associated with cathode orientation. This data indicates that accessing stable high voltage capacity in NMCs will not be enabled by simply stabilizing the cathode–electrolyte interface. Optimizing cathode crystallographic orientation may be the key to accessing this high voltage regime

Deposition and Confinement of Li Metal along an Artificial Lipon–Lipon Interface

Lithium phosphorus oxynitride (Lipon) is an amorphous solid-state electrolyte that can completely suppress Li penetration from the anode to the cathode, commonly referred to as dendrites. The key to the Lipon performance is thought to be its homogeneous and pore-free morphology. To test this, we present a modified thin film battery configuration with a lithium cobalt oxide cathode, a Lipon electrolyte, and a top layer with a copper current collector and an artificial Lipon–Lipon interface parallel to the cathode. Upon electrochemical cycling, Li metal rapidly deposits at the edge of this Cu current collector and then proceeds to plate along the 2D Lipon–Lipon interface. As the Li is confined to this 2D plane, it confirms the ability of Lipon to suppress Li penetration. It also demonstrates that the homogeneous interface-free morphology of Lipon is key to its performance

Plasma Synthesis of Spherical Crystalline and Amorphous Electrolyte Nanopowders for Solid-State Batteries

Here, we demonstrate the theory-guided plasma synthesis of high purity nanocrystalline Li3.5Si0.5P0.5O4 and fully amorphous Li2.7Si0.7P0.3O3.17N0.22. 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 Li3.5Si0.5P0.5O4 powder

Comparing the Purity of Rolled versus Evaporated Lithium Metal Films Using X‑ray Microtomography

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

From the Junkyard to the Power Grid: Ambient Processing of Scrap Metals into Nanostructured Electrodes for Ultrafast Rechargeable Batteries

Here we present the first full cell battery device that is developed entirely from scrap metals of brass and steeltwo of the most commonly used and discarded metals. A room-temperature chemical process is developed to convert brass and steel into functional electrodes for rechargeable energy storage that transforms these multicomponent alloys into redox-active iron oxide and copper oxide materials. The resulting steel–brass battery exhibits cell voltages up to 1.8 V, energy density up to 20 Wh/kg, power density up to 20 kW/kg, and stable cycling over 5000 cycles in alkaline electrolytes. Further, we show the versatility of this technique to enable processing of steel and brass materials of different shapes, sizes, and purity, such as screws and shavings, to produce functional battery components. The simplicity of this approach, building from chemicals commonly available in a household, enables a simple pathway to the local recovery, processing, and assembly of storage systems based on materials that would otherwise be discarded

Synthesis of Ni-Rich Thin-Film Cathode as Model System for Lithium Ion Batteries

We demonstrate a process to prepare model electrodes of the Ni-rich layered compound LiNi0.6Mn0.2Co0.2O2. These thin-film cathodes are compared with the composite materials to demonstrate the system is a viable platform for isolating interfacial phenomena between the electrolyte and active material without the influence of binders and conductive additives. The appropriate choice of heterolayers was found to influence the preferential orientation of the (101) and (104) planes relative to the (003) plane of the layered R-3m crystal structure, enhancing Li+ diffusion and improving electrochemical performance. The addition of a Co interlayer between the Pt current collecting layer and alumina substrate increased the (101) and (104) texturing of the 500 nm Ni-rich film and allowed cells to deliver greater than 50% of their theoretical capacity. This work provides an architecture for isolating complex mechanisms of active materials that suffer from surface reconstruction and degradation in electrochemical cells

Noncovalent Pi–Pi Stacking at the Carbon–Electrolyte Interface: Controlling the Voltage Window of Electrochemical Supercapacitors

A key parameter in the operation of an electrochemical double-layer capacitor is the voltage window, which dictates the device energy density and power density. Here we demonstrate experimental evidence that π–π stacking at a carbon–ionic liquid interface can modify the operation voltage of a supercapacitor device by up to 30%, and this can be recovered by steric hindrance at the electrode–electrolyte interface introduced by poly­(ethylene oxide) polymer electrolyte additives. This observation is supported by Raman spectroscopy, electrochemical impedance spectroscopy, and differential scanning calorimetry that each independently elucidates the signature of π–π stacking between imidazole groups in the ionic liquid and the carbon surface and the role this plays to lower the energy barrier for charge transfer at the electrode–electrolyte interface. This effect is further observed universally across two separate ionic liquid electrolyte systems and is validated by control experiments showing an invariant electrochemical window in the absence of a carbon–ionic liquid electrode–electrolyte interface. As interfacial or noncovalent interactions are usually neglected in the mechanistic picture of double-layer capacitors, this work highlights the importance of understanding chemical properties at supercapacitor interfaces to engineer voltage and energy capability

All Silicon Electrode Photocapacitor for Integrated Energy Storage and Conversion

We demonstrate a simple wafer-scale process by which an individual silicon wafer can be processed into a multifunctional platform where one side is adapted to replace platinum and enable triiodide reduction in a dye-sensitized solar cell and the other side provides on-board charge storage as an electrochemical supercapacitor. This builds upon electrochemical fabrication of dual-sided porous silicon and subsequent carbon surface passivation for silicon electrochemical stability. The utilization of this silicon multifunctional platform as a combined energy storage and conversion system yields a total device efficiency of 2.1%, where the high frequency discharge capability of the integrated supercapacitor gives promise for dynamic load-leveling operations to overcome current and voltage fluctuations during solar energy harvesting

Medium-Range Ordering in the Ionic Glass Electrolytes LiPON and LiSiPON

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