Porous Mixed Ionic Electronic Conductor Interlayers for Solid-State BatteriesRead the full article
The Open Access journal Energy Material Advances, published in association with BIT, is an interdisciplinary platform for research in multiple fields from cutting-edge material to energy science.
Energy Material Advances’ editorial board is led by Feng Wu (Beijing Institute of Technology) and Jun Liu (University of Washington) and is comprised of experts who have made significant and well recognized contributions to the field.
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Air-Resistant Lead Halide Perovskite Nanocrystals Embedded into Polyimide of Intrinsic Microporosity
Although cesium lead halide perovskite (CsPbX3, X = Cl, Br, or I) nanocrystals (PNCs) have been rapidly developed for multiple optoelectronic applications due to their outstanding optical and transport properties, their device fabrication and commercialization have been limited by their low structural stability, especially under environmental conditions. In this work, a new approach has been developed to protect the surface of these nanocrystals, which results in enhanced chemical stability and optical properties. This method is based on the encapsulation of CsPbX3 NCs into a polyimide with intrinsic microporosity (PIM-PI), 4,4-(hexafluoroisopropylidene)diphthalic anhydride reacted with 2,4,6-trimethyl-m-phenylenediamine (6FDA-TrMPD). The presence of 6FDA-TrMPD as a protective layer can efficiently isolate NCs from an air environment and subsequently enhance their optical and photoluminescence stability. More specifically, comparing NCs treated with a polymer to as-synthesized nanocrystals after 168 h, we observe that the PL intensity decreased by 70% and 20% for the NCs before and after polymer treatment. In addition, the PNC film with a polymer shows a much longer excited-state lifetime than the as-synthesized nanocrystals, indicating that the surface trap states are significantly reduced in the treated PNCs. The enhancement in chemical and air stability, as well as optical behavior, will further improve the performance of CsPbBr3 PNCs yielding promising optical devices and paving the way for their production and implementation at a large scale.
Microscopic Insight to Nonlinear Voltage Dependence of Charge in Carbon-Ionic Liquid Supercapacitors
The impact of cell voltage on the capacitance of practical electrochemical supercapacitors is a phenomenon observed experimentally, which lacks a solid theoretical explanation. Herein, we provide combined experimental and molecular dynamics investigation of the relation between voltage and capacitance. We have studied this relation in supercapacitor cells comprising of activated carbon material as the active electrode material, and neat ionic liquids (ILs), and a mixture of ILs as the electrolyte. It has been observed that the increase of accumulative charge impacts the conformation and packing of the cations in the anode, which determines its nonlinear behavior with increasing voltage. It has also been shown that for the mixture IL with two types of cations, the contribution of each type of cation to the overall capacitance is highly dependent on the different pore sizes in the system. The smaller tetramethylammonium (TMA+) shows tendency for more efficient adsorption in the mesopores, while 1-Ethyl-3-methylimidazolium (EMIM+) is found to be present almost exclusively in the micropores where TMA+ is present in small quantities. Such microscopic insights from computer simulations of the molecular phenomena affecting the overall performance in supercapacitors can help to design more efficient electrolytes and devices.
Efficient Stabilization of Na Storage Reversibility by Ti Integration into O3-Type NaMnO2
The development of an energy storage system with abundant elements is a key challenge for a sustainable society, and the interest of Na intercalation chemistry is extending throughout the research community. Herein, the impact of Ti integration into NaMnO2 in a binary system of NaMnO2–() TiO2 () is systematically examined for rechargeable Na battery applications. Stoichiometric NaMnO2, which is classified as an in-plane distorted O3-type layered structure, delivers a large initial discharge capacity of approximately 200 mAh g-1, but insufficient capacity retention is observed, most probably associated with dissolution of Mn ions on electrochemical cycles. Ti-substituted samples show highly improved electrode performance as electrode materials. However, the appearance of a sodium-deficient phase, Na4Mn4Ti5O18 with a tunnel-type structure, is observed for Ti-rich phases. Among the samples in this binary system, Na0.8Mn0.8Ti0.2O2 (), which is a mixture of a partially Ti-substituted O3-type layered oxide (Na0.88Mn0.88Ti0.12O2) and tunnel-type Na4Mn4Ti5O18 as a minor phase elucidated by Rietveld analysis on both neutron and X-ray diffraction patterns, shows good electrode performance on the basis of energy density and cyclability. Both phases are electrochemically active as evidenced by in situ X-ray diffraction study, and the improvement of reversibility originates from the suppression of Mn dissolution on electrochemical cycles. From these results, the feasibility of Mn-based electrode materials for high-energy rechargeable Na batteries made from only abundant elements is discussed in detail.
Hunting Sodium Dendrites in NASICON-Based Solid-State Electrolytes
NASICON- (Na superionic conductor-) based solid-state electrolytes (SSEs) are believed to be attracting candidates for solid-state sodium batteries due to their high ionic conductivity and prospectively reliable stability. However, the poor interface compatibility and the formation of Na dendrites inhibit their practical application. Herein, we directly observed the propagation of Na dendrites through NASICON-based Na3.1Zr2Si2.1P0.9O12 SSE for the first time. Moreover, a fluorinated amorphous carbon (FAC) interfacial layer on the ceramic surface was simply developed by in situ carbonization of PVDF to improve the compatibility between Na metal and SSEs. Surprisingly, Na dendrites were effectively suppressed due to the formation of NaF in the interface when molten Na metal contacts with the FAC layer. Benefiting from the optimized interface, both the Na||Na symmetric cells and Na3V2(PO4)3||Na solid-state sodium batteries deliver remarkably electrochemical stability. These results offer benign reference to the maturation of NASICON-based solid-state sodium batteries.
Intrinsic and Extrinsic Exciton Recombination Pathways in AgInS2 Colloidal Nanocrystals
Ternary I-III-VI2 nanocrystals (NCs), such as AgInS2 and CuInS2, are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.
Porous Mixed Ionic Electronic Conductor Interlayers for Solid-State Batteries
Rechargeable solid-state batteries (SSBs) have emerged as the next-generation energy storage device based on lowered fire hazard and the potential of realizing advanced battery chemistries, such as alkali metal anodes. However, ceramic solid electrolytes (SEs) generally have limited capability in relieving mechanical stress and are not chemically stable against body-centered cubic alkali metals or their alloys with minor solute elements (β-phase). Swelling-then-retreating of β-phase often causes instabilities such as SE fracture and corrosion as well as the loss of electronic/ionic contact, which leads to high charge-transfer resistance, short-circuiting, etc. These challenges have called for the cooperation from other classes of materials and novel nanocomposite architectures in relieving stress and preserving essential contacts while minimizing detrimental disruptions. In this review, we summarize recent progress in addressing these issues by incorporating other classes of materials such as mixed ion-electron conductor (MIEC) porous interlayers and ion-electron insulator (IEI) binders, in addition to SE and metals (e.g., β-phase and current collectors) that are the traditional SSB components. In particular, we focus on providing theoretical interpretations on how open nanoporous MIEC interlayers manipulate β-phase deposition and stripping behavior and thereby suppress such instabilities, referring to the fundamental thermodynamics and kinetics governing the nucleation and growth of the β-phase. The review concludes by describing avenues for the future design of porous MIEC interlayers for SSBs.