Forming a stable solid electrolyte interphase (SEI) is critical for rechargeable batteries' performance and lifetime. Understanding its formation requires analytical techniques that provide molecular-level insight. Here, dynamic nuclear polarization (DNP) is utilized for the first time to enhance the sensitivity of solid-state NMR (ssNMR) spectroscopy to the SEI. The approach is demonstrated on reduced graphene oxide (rGO) cycled in Li-ion cells in natural abundance and C-13-enriched electrolyte solvents. Our results indicate that DNP enhances the signal of outer SEI layers, enabling detection of natural abundance C-13 spectra from this component of the SEI on reasonable time frames. Furthermore, C-13-enriched electrolyte measurements at 100 K provide ample sensitivity without DNP due to the vast amount of SEI filling the rGO pores, thereby allowing differentiation of the inner and outer SEI layer composition. Developing this approach further will benefit the study of many electrode materials, equipping ssNMR with the necessary sensitivity to probe the SEI efficiently.
The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention because of the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95, 1) are electro-chemically cycled is reported here using in situ X-ray diffraction (XRD) data and supporting ex situ P-31 NMR spectra. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)(x)(Co2+)(1-x)PO4 for 0
We present a Floquet theory approach for the analysis of homonuclear recoupling assisted by radio frequency (RF) irradiation of surrounding heteronuclear spins. This description covers a broad range of systems from fully protonated to deuterated proteins, focusing in detail on recoupling via protons and deuterons separately as well as simultaneously by the double nucleus enhanced recoupling (DONER) scheme. The theoretical description, supported by numerical simulations and compared to experimental results from a partially deuterated model compound, indicates that in perdeuterated systems setting the RF amplitude equal to the magic angle spinning (MAS) frequency is not necessarily optimal for recoupling via (1)H and/or (2)H nuclei and modified recoupling conditions are identified. (C) 2011 Elsevier Inc. All rights reserved.
We present a rf scheme designed to excite triple quantum (TQ) coherences for proton solid state NMR. This recoupling scheme is based on the phase modulated Lee Goldburg sequence combined with echo pulses and applied nonsynchronous with the magic angle spinning period. Based on the effective bimodal Floquet Hamiltonian we optimize the conditions for TQ coherence excitation. Numerical simulations are used to further adjust the recoupling conditions as well as define the sequence limitations. Experimental TQ filtered one-dimensional spectra and two-dimensional correlations of TQ to single quantum coherences are presented for standard amino acids. These results are compared with the crystal structures showing that this scheme can aid in resonance assignments and in resolving local spin topologies.
Schemes such as phase-modulated Lee-Goldburg (PMLG) for homonuclear dipolar decoupling have been shown to yield high-resolution H-1 spectra at high magic-angle spinning (MAS) frequencies of 50-70 kHz. This is at variance to the commonly held notion that these methods require MAS frequencies not comparable to the cycle frequencies of the pulse schemes. Here. a theoretical argument, based on bimodal Floquet theory, is presented to explain this aspect together with conditions where PMLG type of schemes may be Successful at high MAS frequencies. (C) 2009 Elsevier Inc. All rights reserved.
A homonuclear dipolar decoupling scheme based on windowed phase-modulated Lee-Goldburg (wPMLG) pulse sequences that causes a"z-rotation" of the spins for high-resolution proton NMR spectroscopy of solids is described and analyzed. This supercycled scheme suppresses the effect of pulse imperfections on the spectra and significantly relaxes the off-resonance dependence of the line-narrowing efficiency and scale factor. This leads to a broad spectral window that is free of artifacts such as zero lines, image peaks, and localized rotor-radio-frequency resonances. High-resolution (1)H spectra and two-dimensional homonuclear (1)H-(1)H correlation spectra of standard amino acids, obtained by a combination of this supercycled scheme with magic angle spinning frequencies up to 25 kHz, are demonstrated. (c) 2008 American Institute of Physics.
We report here high-resolution H-1 solid-state nuclear magnetic resonance spectra acquired by a combination of magic-angle spinning (MAS) and radiofrequency pulse methods up to MAS frequencies of 65 kHz. The details of the pulse methods and experimental conditions are outlined together with spectra from model compounds. (C) 2008 Elsevier B.V. All rights reserved.
A theoretical treatment of heteronuclear dipolar decoupling in solid-state nuclear magnetic resonance is presented here based on bimodal Floquet theory. The conditions necessary for good heteronuclear decoupling are derived. An analysis of a few of the decoupling schemes implemented until date is presented with regard to satisfying such decoupling conditions and efficiency of decoupling. Resonance conditions for efficient heteronuclear dipolar decoupling are derived with and without the homonuclear H-1-H-1 dipolar couplings and their influence on heteronuclear dipolar decoupling is pointed out. The analysis points to the superior efficiency of the newly introduced swept two-pulse phase-modulation (SWf-TPPM) sequence. It is shown that the experimental robustness of SWf-TPPM as compared to the original TPPM sequence results from an adiabatic sweeping of the modulation frequencies. Based on this finding alternative strategies are compared here. The theoretical findings are corroborated by both numerical simulations and representative experiments. (C) 2007 American Institute of Physics.
High-resolution H-1 spectroscopy in solid-state NMR, rendered difficult due to the strong H-1-H-1 homonuclear dipolar coupling, has been made possible under magic-angle spinning with homonuclear dipolar decoupling schemes, such as windowed phase-modulated Lee-Goldburg. Here, we outline the theory and implementation of a modification of this scheme with which an effective z-rotation for the magnetisation is obtained over a wide range of spectral window. Experimental results are presented for samples, such as glycine, histidine, and tryosine. (C) 2007 Elsevier B.V. All rights reserved.
We present here a bimodal Floquet analysis of the windowed phase-modulated Lee-Goldburg (wPMLG) sequence for homonuclear dipolar decoupling. One of the main criteria for an efficient homonuclear dipolar decoupling scheme is an effective z-rotation condition. This is brought about by the presence of radio-frequency imperfections in the pulse sequence together with a systematic manipulation of the wPMLG pulses. Additional improvement in the H-1 spectral resolution was obtained by a proper understanding of the off-resonance dependence of the wPMLG irradiation scheme based on bimodal Floquet theory. Numerical investigations further corroborate both theoretical and experimental findings. Theoretical analysis points to accidental degeneracies between the cycle time of the wPMLG sequence and the rotor period leading to the experimentally observed off-resonance dependence of the resolution. Two-dimensional H-1-H-1 homonuclear single-quantum correlation spectra of model amino acids are also presented, highlighting the improved spectral resolution of wPMLG sequences. (c) 2006 American Institute of Physics.