Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon).

Lithium phosphorus oxynitride, also known as Lipon, solid-state electrolytes are at the center of the search for solid-state Li metal batteries. Key to the performance of Lipon is a combination of high Li content, amorphous character, and the incorporation of N into the structure. Despite the material's importance, our work presents the first study to fully resolve the structure of Lipon using a combination of  ab initio molecular dynamics, density functional theory, neutron scattering, and infrared spectroscopy. The modeled and experimental results have exceptional agreement in both neutron pair distribution function and infrared spectroscopy. Building on this synergy, the structural models show that N forms both bridges between two phosphate units and nonbridging apical N. We further show that as the Li content is increased the ratio of bridging to apical N shifts from being predominantly bridging at Li contents around 2.5:1 Li:P to only apical N at higher Li contents of 3.38:1 Li:P. This crossover from bridging to apical N appears to directly correlate with and explain both the increase in ionic conductivity with the incorporation of N and the ionic conductivity trends found in the literature.

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.

A multifunctional load-bearing solid-state supercapacitor.

A load-bearing, multifunctional material with the simultaneous capability to store energy and withstand static and dynamic mechanical stresses is demonstrated. This is produced using ion-conducting polymers infiltrated into nanoporous silicon that is etched directly into bulk conductive silicon. This device platform maintains energy densities near 10 W h/kg with Coulombic efficiency of 98% under exposure to over 300 kPa tensile stresses and 80 g vibratory accelerations, along with excellent performance in other shear, compression, and impact tests. This demonstrates performance feasibility as a structurally integrated energy storage material broadly applicable across renewable energy systems, transportation systems, and mobile electronics, among others.

Solid-state batteries: The critical role of mechanics.

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.

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.

Carbon Nanotube Reinforced Structural Composite Supercapacitor.

Carbon nanotubes exhibit mechanical properties ideally suited for reinforced structural composites and surface area and conductivity attractive for electrochemical capacitors. Here we demonstrate the multifunctional synergy between these properties in a composite material exhibiting simultaneous mechanical and energy storage properties. This involves a reinforcing electrode developed using dense, aligned carbon nanotubes grown on stainless steel mesh that is layered in an ion conducting epoxy electrolyte matrix with Kevlar or fiberglass mats. The resulting energy storage composites exhibit elastic modulus over 5 GPa, mechanical strength greater than 85 MPa, and energy density up to 3 mWh/kg for the total combined system including electrodes, current collector, Kevlar or fiberglass, and electrolyte matrix. Furthermore, findings from in-situ mechano-electro-chemical tests indicate simultaneous mechanical and electrochemical functionality with invariant and stable supercapacitor performance maintained throughout the elastic regime.

Particulate-free porous silicon networks for efficient capacitive deionization water desalination.

Energy efficient water desalination processes employing low-cost and earth-abundant materials is a critical step to sustainably manage future human needs for clean water resources. Here we demonstrate that porous silicon - a material harnessing earth abundance, cost, and environmental/biological compatibility is a candidate material for water desalination. With appropriate surface passivation of the porous silicon material to prevent surface corrosion in aqueous environments, we show that porous silicon templates can enable salt removal in capacitive deionization (CDI) ranging from 0.36% by mass at the onset from fresh to brackish water (10 mM, or 0.06% salinity) to 0.52% in ocean water salt concentrations (500 mM, or ~0.3% salinity). This is on par with reports of most carbon nanomaterial based CDI systems based on particulate electrodes and covers the full salinity range required of a CDI system with a total ocean-to-fresh water required energy input of ~1.45 Wh/L. The use of porous silicon for CDI enables new routes to directly couple water desalination technology with microfluidic systems and photovoltaics that natively use silicon materials, while mitigating adverse effects of water contamination occurring from nanoparticulate-based CDI electrodes.

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.

On-chip high power porous silicon lithium ion batteries with stable capacity over 10,000 cycles.

We demonstrate the operation of a graphene-passivated on-chip porous silicon material as a high rate lithium battery anode with over 50 X power density, and 100 X energy density improvement compared to identically prepared on-chip supercapacitors. We demonstrate this Faradaic storage behavior to occur at fast charging rates (1-10 mA cm(-2)) where lithium locally intercalates into the nanoporous silicon, preventing the degradation and poor cycling performance attributed to deep storage in the bulk silicon. This device exhibits cycling performance that exceeds 10,000 cycles with capacity above 0.1 mA h cm(-2) without notable capacity fade. This demonstrates a practical route toward high power, high energy, and long lifetime all-silicon on-chip storage systems relevant toward integration into electronics, photovoltaics, and other silicon-based platforms.

Assessing the improved performance of freestanding, flexible graphene and carbon nanotube hybrid foams for lithium ion battery anodes.

We demonstrate the fabrication of three-dimensional freestanding foams of hybrid graphene-single-walled carbon nanotube nanomanufactured materials with reversible capacities of 2640 mA h g(-1) at 0.186 A g(-1) and 236 mA h g(-1) at 27.9 A g(-1). The Li storage behavior of this material is compared against other nanostructures in similar flexible foam platforms including graphene, ultra-thin graphite, and single-walled carbon nanotubes (SWNTs), and we elucidate the improved hybrid material performance due to the decoupling of lithium storage reaction energetics dictated by the SWNTs from the total storage capacity of the hybrid material. This work demonstrates a route to develop mechanically robust all-carbon electrodes with the potential for reversible Li-ion storage capacity approaching silicon, power capability of the best supercapacitors, and based on a material simultaneously usable as a charge collector and anode.