Sodium ion dynamics in a sulfonate based ionomer system studied by 23Na solid-state nuclear magnetic resonance and impedance spectroscopy

A poly(2-acrylamido-2-methyl-1-propane-sulphonate) (PAMPS) ionomer containing both sodium and quaternary ammonium cations functionalised with an ether group, has been characterised in terms of its thermal properties, ionic conductivity and sodium ion dynamics. The ether oxygen was incorporated to reduce the Na+ association with the anionic sulfonate groups tethered to the polymer backbone, thereby promoting ion dissociation and ultimately enhancing the ionic conductivity. This functionalised ammonium cation led to a significant reduction in the ionomer Tg compared to an analogue system without an ether group, resulting in an increase in ionic conductivity of approximately four orders of magnitude. The sodium ion dynamics were probed by 23Na solid-state NMR, which allowed the signals from the dissociated (mobile) and bound Na+ cations to be distinguished. This demonstrates the utility of 23Na solid-state NMR as a probe of sodium dynamics in ionomer systems.

Solid-state NMR as a probe of anion binding: molecular dynamics and associations in a [5]polynorbornane bisurea host complexed with terephthalate

A range of solid-state NMR techniques is used to characterise a molecular host:guest complex consisting of a [5]polynorbornane bisurea host binding a terephthalate dianion guest. Detailed information is obtained on the molecular dynamics and associations from the point of view of both the host and guest molecules. The formation of the complex in the solid state is confirmed using (1)H 2D exchange NMR, and the 180° flipping of the (2)H-labelled terephthalate guest and its eventual expulsion from the complex at elevated temperatures are quantified using variable-temperature (2)H spin-echo experiments. Two-dimensional (1)H-(13)C HETCOR spectra obtained under fast magic angle spinning conditions (60 kHz) show a high resolution despite the poor crystallinity of the solid complex, and clearly reveal changes in the rigidity of the host molecule when complexed. Short-range intra- and intermolecular (1)H-(1)H proximities are also detected using 2D SQ-DQ correlation methods, providing insight into the molecular packing in the solid phase.

High-performance flexible all-solid-state supercapacitor from large free-standing graphene-PEDOT/PSS films

Although great attention has been paid to wearable electronic devices in recent years, flexible lightweight batteries or supercapacitors with high performance are still not readily available due to the limitations of the flexible electrode inventory. In this work, highly flexible, bendable and conductive rGO-PEDOT/PSS films were prepared using a simple bar-coating method. The assembled device using rGO-PEDOT/PSS electrode could be bent and rolled up without any decrease in electrochemical performance. A relatively high areal capacitance of 448 mF cm(-2) was achieved at a scan rate of 10 mV s(-1) using the composite electrode with a high mass loading (8.49 mg cm(-2)), indicating the potential to be used in practical applications. To demonstrate this applicability, a roll-up supercapacitor device was constructed, which illustrated the operation of a green LED light for 20 seconds when fully charged.

Ultra-wideline 14N solid-state NMR as a method for differentiating polymorphs: glycine as a case study

Nitrogen-14 solid-state NMR (SSNMR) is utilized to differentiate three polymorphic forms and a hydrochloride (HCl) salt of the amino acid glycine. Frequency-swept Wideband, Uniform Rate, Smooth Truncated (WURST) pulses were used in conjunction with Carr-Purcell Meiboom-Gill refocusing, in the form of the WURST-CPMG pulse sequence, for all spectral acquisitions. The ¹⁴N quadrupolar interaction is shown to be very sensitive to variations in the local electric field gradients (EFGs) about the ¹⁴N nucleus; hence, differentiation of the samples is accomplished through determination of the quadrupolar parameters CQ and ηQ, which are obtained from analytical simulations of the ¹⁴N SSNMR powder patterns of stationary samples (i.e., static NMR spectra). Additionally, differentiation of the polymorphs is also possible via the measurement of ¹⁴N effective transverse relaxation time constants, T^eff2(¹⁴N). Plane-wave density functional theory (DFT) calculations, which exploit the periodicity of crystal lattices, are utilized to confirm the experimentally determined quadrupolar parameters as well as to determine the orientation of the ¹⁴N EFG tensors in the molecular frames. Several signal-enhancement techniques are also discussed to help improve the sensitivity of the ¹⁴N SSNMR acquisition method, including the use of selective deuteration, the application of the BRoadband Adiabatic INversion Cross-Polarization (BRAIN-CP) technique, and the use of variable-temperature (VT) experiments. Finally, we examine several cases where ¹⁴N VT experiments employing Carr-Purcell-Meiboom-Gill (CPMG) refocusing are used to approximate the rotational energy barriers for RNH3⁺ groups.

In situ MRI of operating solid-state Lithium metal cells based on ionic plastic crystal electrolytes

Solid-state ion conductors based on organic ionic plastic crystals (OIPCs) are a promising alternative to conventional liquid electrolytes in lithium battery applications. The OIPC-based electrolytes are safe (nonflammable) and flexible in terms of design and operating conditions. Magnetic resonance imaging (MRI) is a powerful noninvasive method enabling visualization of various chemical phenomena. Here, we report a first quantitative in situ MRI study of operating solid-state lithium cells. Lithium ion transfer into the OIPC matrix during the ongoing discharge of the anode results in partial liquefaction of the electrolyte at the metal interface. The developed liquid component enhances the ion transport across the interface and overall battery performance. Displacement of the liquefaction front is accompanied by a faster Li transfer through the grain boundaries and depletion at the cathode. The demonstrated solid-liquid hybrid properties, inherent in many OIPCs, combine benefits of highly conductive ionic liquids with safety and flexibility of solids.

A potential novel rapid screening NMR approach to boundary film formation at solid interfaces in contact with ionic liquids

The boundary films generated on a series of inorganic compounds, typical of native films on metal and ceramic surfaces, when exposed to various ionic liquids (ILs) based on the trihexyl(tetradecyl)phosphonium cation have been characterized using multinuclear solid-state NMR. The NMR results indicate that SiO₂ and Mg(OH)₂ interact strongly with the anion and cation of each IL through a mechanism of adsorption of the anion and subsequent close proximity of the cation in a surface double layer (as observed through ¹H−²⁹Si cross polarization experiments). In contrast, Al₂O₃, MgO, ZnO, and ZrO₂ appear less active, strongly suggesting the necessity of hydroxylated surface groups in order to enhance the generation of these interfacial films. Using solid-state NMR to characterize such interfaces not only has the potential to elucidate mechanisms of wear resistance and corrosion protection via ILs, but is also likely to allow their rapid screening for such durability applications.

NMR studies of modified nasicon-like, lithium conducting solid electrolytes*1

²⁷Al, ³¹P and ⁷Li NMR measurements have been performed on lithium conducting ceramics based on the LiTi₂(PO₄)₃ structure with Al, V and Nb metal ions substituted for either Ti or P within the framework NASICON structure. The ²⁷Al magic angle spinning NMR measurements have revealed that, although Al is intended to substitute for octahedral Ti sites, additional substitution into tetrahedral environments (presumably phosphorous sites) occurs with increasing amount of Al addition. This tetrahedral substitution appears to occur more readily in the presence of vanadium, in Li_1+xAl_xTi_2−x(PO₄)_2.9(VO₄)_0.1, whereas similar niobium additions (in place of vanadium) appear to stifle tetrahedral substitution. ⁷Li static NMR spectra reveal quadrupolar structure with C_q approximately 42 kHz, largely independent of substitution. Measurement of the ⁷Li central transition linewidth at room temperature reveals a relatively mobile lithium species (300–900 Hz) with linewidth tending to decrease with Al substitution and increase with increasing V or Nb. This new structural information is discussed in the context of ionic conduction in these ceramics.

N,N-Dimethylpyrrolidinium hydroxide : a highly conductive solid material at ambient temperature

N,N-Dimethylpyrrolidinium hydroxide (P₁₁OH·4H₂O) was found to exhibit high ionic conductivity in the solid state (7 × 10⁻³ S cm⁻¹ at 25°C) and unusual thermal properties, and ²H solid state NMR measurements indicate liquid-like mobility of the deuterium species in the solid state of P₁₁OD·4.5D₂O.

Scalable Solid-Template Reduction for Designed Reduced Graphene Oxide Architectures

Herein, we report a solid-state reduction process (in contrast to solution-based approach) by using an environmentally friendly reductant, such as vitamin C (denoted VC), to be directly employed to solid-state graphene oxide (GO) templates to give the highly active rGO architecture with a sheet resistance of as low as 10 Ω sq–1. In addition, predesigned rGO patterns/tracks with tunable resistivity can be directly “written” on a preprepared solid GO film via the inkjet-printing technique using VC/H2O as the printing-ink. This advanced reduction process allows foreign active materials to be preincorporated into the GO matrix to form quality active composite architectures.

New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

Enhancement of ‘dry’ proton conductivity by self-assembled nanochannels in all-solid polyelectrolytes

Proton transport has been recognized as an essential process in many biological systems, as well as electrochemical devices including fuel cells and redox flow batteries. In the present study, we address the pressing need for solvent-free proton conducting polymer electrolytes for high-temperature PEM fuel cell applications by developing a novel all-solid polyelectrolyte membrane with a self-assembled proton-channel structure. We show that this self-assembled nanostructure endows the material with exciting ‘dry’ proton conductivity at elevated temperatures, as high as 0.3 mS cm−1 at 120 °C, making it an attractive candidate for high-temperature PEM fuel cell applications. Based on the combined investigation of solid-state NMR, FTIR and conductivity measurements, we propose that both molecular design and nano-scale structures are essential for obtaining highly conductive anhydrous proton conductors.