12 research outputs found
Novel solid-state sodium electrolytes base on organic ionic plastic crystals
The focus of this sstudy was to develop safe, stable, highly conductive and high-performance solid-state electrolytes for Na battery devices based on organic ionic plastic crystals (OIPCs) with phosphonium cations, which have received less attention compared to other kinds of OIPCs and yet offer the possibility of enhanced electrochemical properties
The influence of interfacial interactions on the conductivity and phase behaviour of organic ionic plastic crystal/polymer nanoparticle composite electrolytes
Unformatted postprintOrganic ionic plastic crystals (OIPCs) have been recognised as promising solid-state electrolyte materials for next-generation energy storage devices. Recently, the addition of polymer nanofillers to OIPCs has led to the design of OIPC-based solid-state electrolytes with enhanced mechanical stability and ion conductivity. However, the mechanisms of enhancement and the influence of different polymer surface chemistries on the ion dynamics are not yet well understood, which has hindered the further development of high-performance OIPC-based electrolytes. In this work, we selected two different polymer nanoparticles, poly(vinylidene fluoride) (PVDF) and polystyrene (PS), and investigated the effects of the polymer surfaces on the thermal behaviour and ion transport properties of the OIPC, N-ethyl N-methyl pyrrolidinium bis(fluorosulfonyl)imide ([C2mpyr][FSI]). We found significantly different thermal behaviours, as well as ion transport properties in the OIPC/nanoparticle composites. Specifically, compared with pure [C2mpyr][FSI], the addition of PVDF nanoparticles effectively enhanced the ion conductivity of the OIPC composite, with the optimum achieved near the percolation threshold of PVDF nanoparticles.
In contrast, the addition of PS nanoparticles to the OIPC led to a slight enhancement at low concentrations and then a significant decrease in conductivity at higher concentrations. DSC, FTIR and EIS confirm that the interaction between the PVDF nanoparticles and the OIPC induces the formation of less ordered OIPC layers on the PVDF surfaces, leading to the conductivity enhancement. Finally, different structure models based on the results of this work are proposed, which provide principle guidelines for the design of future OIPC-based highly conductive electrolyte materials.The authors would like to thank Dr Wesley A. Henderson for his valuable discussion and the US Army Research Office (ARO) for financial support (W911NF1710560). The Australian Research Council (ARC) is acknowledged for support through the Australian Postgraduate Awards and Deakin University postgraduate research scholarships. L. P. received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie grant agreement No. 797295. Dr Ruhamah Yunis is also acknowledged for her help with plastic crystal synthesis
Electrolytes for sodium batteries
This chapter presents an overview of different liquid and solid electrolytes employed for sodium batteries. It covers the basics in more depth and discusses the current status of ionic liquid (IL)-based electrolytes. The chapter outlines the challenges that remain to be solved to enable the realization of sodium batteries based on such electrolytes. Organic liquid electrolytes for sodium batteries typically consist of one or more sodium salts dissolved in one or more organic solvents. Organic ionic plastic crystals, the solid-state analogues of ILs, are emerging solid-state electrolytes that have advantageous properties, similar to ILs. ILs-based electrolytes present some unique properties that endows significant safety enhancements in comparison with conventional organic solvents, mostly related to higher decomposition temperatures. The IL-based electrolytes must also show an economic viability in comparison with conventional organic liquid electrolytes
Stable High-Temperature Cycling of Na Metal Batteries on Na3V2(PO4)3 and Na2FeP2O7 Cathodes in NaFSI-Rich Organic Ionic Plastic Crystal Electrolytes
Phosphonium plastic crystal salt alloyed with a sodium salt as a solid-state electrolyte for sodium devices: phase behaviour and electrochemical performance
Beneficial effect of added water on sodium metal cycling in super concentrated ionic liquid sodium electrolytes
Mixed phase solid-state plastic crystal electrolytes based on a phosphonium cation for sodium devices
Na batteries are seen as a feasible alternative technology to lithium ion batteries due to the greater abundance of sodium and potentially similar electrochemical behavior. In this work, mixed phase electrolyte materials based on solid-state compositions of a trimethylisobutylphosphonium (P111i4) bis(trifluromethanesulphonyl)amide (NTf2) organic ionic plastic crystal (OIPC) and high concentration of NaNTf2 that support safe, sodium metal electrochemistry are demonstrated. A Na symmetric cell can be cycled efficiently, even in the solid state (at 50 °C and 60 °C), for a 25 mol% (P111i4NTf2)–75 mol% NaNTf2 composition at 0.1 mA cm−2 for 100 cycles. Thus, these mixed phase materials can be potentially used in Na-based devices under moderate temperature conditions. It is also investigated that the phase behavior, conductivity, and electrochemical properties of mixtures of NaNTf2 with this OIPC. It is observed that these mixtures have complex phase behavior. For high compositions of the Na salt, the materials are solid at room temperature and retain a soft solid consistency even at 50 °C with remarkably high conductivity, approaching that of the pure ionic liquid at 50 °C, i.e., 10−3–10−2 S cm−1
Exploration of Phase Diagram, Structural and Dynamic Behavior of [HMG][FSI] Mixtures with NaFSI across an Extended Composition Range.
International audienceHexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) has recently been shown to be a promising solid state organic ionic plastic crystal with potential application in advanced alkali metal batteries. This study provides a detailed exploration of the structural and dynamic behavior of [HMG][FSI] mixtures with the sodium salt NaFSI across the whole composition range from 0 to 100 mol%. All mixtures are solids at room temperature. A combination of differential scanning calorimetry (DSC), synchrotron X-ray diffraction (SXRD) and multinuclear solid state NMR spectroscopy is employed to identify a partial phase diagram. The 25 mol% NaFSI/75 mol% [HMG][FSI] composition presents as the eutectic composition with the eutectic transition temperature at 44 ° C. Both DSC and SXRD strongly support the formation of a new compound near 50 mol% NaFSI. Interestingly, the 53 mol% NaFSI [HMG][FSI] composition was consistently found to display features of a pure compound whereas the 50 mol% materials always showed a second phase. Many of the compositions examined showed unusual metastable behaviour. Moreover, the ion dynamics as determined by NMR, indicate that the Na(+) and FSI(-) anions are signifcantly more mobile than the HMG cation in the liquid state (including the metastable state) for these materials
Solid State Li Metal/LMO Batteries based on Ternary Triblock Copolymers and Ionic Binders
Triblock copolymers containing an ionophilic polymerized
ionic
liquid block, sandwiched between two ionophobic polystyrene blocks,
were investigated as solid polymer electrolytes (SPE) to simultaneously
provide mechanically robust, free-standing membranes with high lithium
conductivity and an optimized electrolyte composition. The conductivity
reached 8 × 10–5 S cm–1 and
6.5 × 10–4 S cm–1 at 30 and
80 °C, respectively, with an anodic stability above 4.5 V. Highly
stable Li metal symmetric cycling was demonstrated, with an overpotential
of 130 mV for over 300 h at 50 °C at a current density of 0.5
mA cm–2/0.5 mAh cm–2. Attempts
were also made to incorporate the SPE as the binder in an LMO cathode
formulation. The best cell performance, however, was obtained when
substituting the SPE in the LMO cathode formulation with a PMA solid-state
gel electrolyte, resulting in a high-performance solid-state Li|polymer
eletrolyte|LMO device with stable cycling at C/5, and an impressive
capacity retention (i.e., 105 mAh g–1 after 150
cycles at 0.1 mA cm–2) with a Coulombic efficiency
around 99.4%
Electrochemical characterization of hexamethylguanidinium bis(fluorosulfonyl)imide [HMG][FSI] based electrolyte and its application in sodium metal batteries
With the increasing energy demand for both electronic portable devices and energy storage for fluctuating renewable energy sources, there is a strong need for alternatives beyond lithium batteries. Sodium batteries have been attracting great attention recently due to the abundance and low supply cost of the raw materials. However, they require highly conductive, safe and electrochemically stable electrolytes in order to enable their practical realization. In this work we present the promising physicochemical properties of the electrolyte based on hexamethylguanidinium bis(fluorosulfonyl)imide [FSI] at a sodium concentration of 25 mol% NaFSI. The liquid-state electrolyte supports stable Na plating and stripping at 1 h polarization times at 0.5 mA cm ^−2 current density in a Na symmetrical coin cell at 50 °C, maintaining a low polarization potential of ≈45 mV throughout 160 cycles. Moreover, this electrolyte is characterized by relatively high Na-ion transference number of 0.36 ± 0.03 at 50 °C. A long cycle life of 300 cycles with 285 mAh g ^−1 is achieved in a half cell set up with hard carbon. The solid-electrolyte interphase layer on the anode, which contributes to this high capacity, is investigated by x-ray photoelectron spectroscopy and solid-state nuclear magnetic resonance spectroscopy. The long-term cycling performance of Na|NaFePO _4 cell is also demonstrated with a high specific capacity of 106 mAh g ^−1 and 80% capacity retention after 110 cycles