6,7Li NMR study of ion mobility on the molecular scale in lithated imidazole complexes

Two model compounds, lithium imidazolium (LiIm) and lithium 2-undecylimidazolium (und-LiIm), were synthesized. These materials are chosen as models of potential lithium ion conductors for use as electrolytes in lithium batteries. Solid-state NMR was used to provide information on the microscopic interactions including ionic mobility and ring reorientations which govern the efficiency of conductivity. Lithium imidazolium was mixed with lithium methylsulfonate, generating a doped complex in which a doubly lithiated imidazole ring was inferred based on the ⁷Li NMR chemical shifts. Our research includes ^6,7Li variable temperature MAS NMR experiments at intermediate spinning speeds, relaxation studies to determine spin-lattice relaxation times (T₁) of lithium ion hopping, and 2D exchange spectroscopy to determine possible chemical exchange processes. The possibility of 2-site ring reorientation for the doubly lithiated imidazole ring was supported by exchange spectroscopy. Comparisons of spin-lattice relaxation times and corresponding activation energies of the lithium imidazolium and the doped complex point to a higher degree of mobility in the latter.Lithium 2-undecylimidazolium was prepared and exhibited a lower melting point than the parent lithium imidazolium, as expected. This small molecule was chosen as representative of a side-chain functionalized polyethylene-based material. ⁷Li MAS spectra show mainly the presence of the doubly lithiated imidazole ring in pure und-LiIm, and in the LiCH₃SO₃–und-LiIm mixture. The data clearly indicate local mobility of the lithium ions in the materials.     

Ionic Pathways in Li13Si4 investigated by 6Li and 7Li solid state NMR experiments

Local environments and dynamics of lithium ions in the binary lithium silicide Li₁₃Si₄ have been studied by ⁶Li MAS-NMR, ⁷Li spin-lattice relaxation time and site-resolved ⁷Li 2D exchange NMR measurements as a function of mixing time. Variable temperature experiments result in distinct differences in activation energies characterizing the transfer rates between the different lithium sites. Based on this information, a comprehensive picture of the preferred ionic transfer pathways in this silicide has been developed. With respect to local mobility, the results of the present study suggests the ordering Li6/Li7>Li5>Li1>Li4 >Li2/Li3. Mobility within the z=0.5 plane is distinctly higher than within the z=0 plane, and the ionic transfer between the planes is most facile via Li1/Li5 exchange. The lithium ionic mobility can be rationalized on the basis of the type of the coordinating silicide anions and the lithium-lithium distances within the structure. Lithium ions strongly interacting with the isolated Si⁴⁻ anions have distinctly lower mobility than those the coordination of which is dominated by Si₂⁶⁻ dumbbells.     

结晶型PEO8∶NaPF6聚电解质中晶区链段的运动

利用固体NMR 研究了高度结晶的聚氧乙烯(PEO)/六氟磷酸钠(NaPF6)（按照氧钠摩尔比8∶1 描述为PEO8∶NaPF6,分子量Mw = 1 000 和6 000 g/mol）固体聚电解质晶区链段的结构和运动．对于纯PEO 来说,晶区链段的构象交换或大角度再取向促使其¹³C 粉末线形从低温的非轴对称(δ₃₃ <δ₂₂ <δ₁₁)变成高温的轴对称线形(δ₁₁ =δ₂₂ >δ₃₃)．通过变温的¹³C 粉末线形和243 K 下的二维交换谱,PEO8∶NaPF6 晶区链段同样存在大角度再取向,且开启温度也很低(~243 K)与PEO 接近．这种长程的运动使得PEO8∶NaPF6 从低温的类轴对称(δ₃₃ <δ₂₂ <δ₁₁)变成高温的轴对称线形(δ₃₃ >δ₂₂ =δ₁₁),高温线形是PEO 高温线形的翻转．与其它PEO/Na(Li)固体聚电解质不同,PEO8∶NaPF6 中晶区链段与Na+络合后仍具有很高的运动性（与纯PEO 链段的运动性相当）,这种高分子链段和Na+协同运动促使Na+沿PEO 分子链轴向迁移,提高电导率．     

Structural Nature of 7Li and 11B Sites by Static NMR and MAS NMR in Nonlinear Optical Material LiCsB6O10

The relationship between structure and nonlinear optical properties in LiCsB₆O₁₀ is characterized using single-crystal nuclear magnetic resonance (NMR) and magic-angle spinning (MAS) NMR. Although the quadrupole parameters for B(1) and B(2) sites were obtained using single-crystal NMR, the T ₁ values for these atomic sites could not be distinguished in this way. Thus, the structural nature of lithium and boron sites in LiCsB₆O₁₀ was investigated using MAS NMR. B(1) and B(2) sites could be distinguished based on the spectrum and T _1ρ obtained from ¹¹B MAS NMR. In addition, the T ₁ and T _1ρ values and activation energies for ⁷Li and ¹¹B are compared. No significant changes were seen in the T _1ρ at the lithium and boron nuclei in LiCsB₆O₁₀.     

One- and two-dimensional 15N exchange CP/MAS NMR studies of the structure and electronic properties of the intermolecular N-H...N hydrogen bond in imidazole crystal

The hydrogen bond of the type N-H...N in imidazole crystal has been studied by one and two-dimensional 15N exchange CP/MAS NMR measurements as well as the powder NMR spectrum. The chemical shift anisotropies for -N= and -N< were determined from the powder 1D spectrum. In 2D exchange CP/MAS NMR spectrum, the cross peaks between the 15N main resonance peaks for -N= and -N< were observed, implying that magnetization exchange between -N= and -N< takes place. The 1D exchange CP/MAS NMR measurements determined the exchange rate of magnetization at 289 K to be 1.3 and 1.5 s(-1) for -N= and -N<, respectively. The proton-driven spin-diffusion model interprets the experimental values, and the exchange rate depends strongly on the RF power of the proton decoupling field, suggesting that the magnetization transfer between -N= and -N< takes place by the 1H-driven spin-diffusion mechanism.     

Correlation between 31P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18 x 3H2O and Li6P6O18

To understand the surprising behavior between the variations of the P'-P-P" angles and the correlated variations of the O'-P-O" ones, two lithium cyclohexaphosphate compounds Li6P6O18 x 3H2O and Li6P6O18 are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P6O18]6- ring anions but with 3m or 1 internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of 7Li and 31P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for 7Li or 31P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the 31P chemical shift tensor is dependent on the deviations of the O-P-O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P'-P-P" and the ones of the O'-P-O" is related to the overall charge on the PO4 group. We also find the positions of the isotropic lines for 7Li essentially depend on the site co-ordination of this nuclei.     

Metallic Li colloids studied by 7 Li MAS NMR in electron-irradiated LiF

7 Li MAS NMR spectra of 2.5 v MeV electron-irradiated LiF crystals have been measured in a field of 9.4 v T. Besides the resonance line of the ionic compound, a second well-separated spectrum is observed in the region of the Knight shift value for metallic lithium. At room temperature, the latter can be decomposed into two components with different Knight shift and linewidth values. When the temperature is increased, line narrowing takes place at first, indicating shortening of correlation times for self-diffusion, independently in both components. Above 370 v K, both lines broaden and approach each other before collapsing into a single line. The high ppm component disappears after crossing the melting temperature of metallic lithium (454 v K). The two lines are attributed to different types of metallic Li: one to bulk-like metal, the other to Li present initially under pressure and relaxing to the former under thermal treatment.     

锂离子电池掺钴正极材料电子结构的DV-Xα研究

采用原子基表示的第一原理赝势方法 ,计算了正极材料LiMn2 O4的电子结构 ,发现LiMn2 O4的价带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)、O(6 )、O(4 )的 2p轨道构成 ,导带主要是由Mn(8)和Mn(9)的 3d轨道和O(7)的 2 p轨道构成 .通过计算Li5Mn7CoO8的电子结构 ,发现在LiMn2 O4中用钴离子取代 16d位锰离子将使电极材料的费米能减小 ,放电电压降低 ;锂离子的净电荷增大 ,锂离子与氧离子的相互作用增强 ,可逆容量降低 ;同时由于价带宽度变窄 ,Co-O键间的相互作用比Mn -O键间的相互作用强 ,所以 ,结构稳定性增加 ,电极循环性能改善 .     

Lightweight hydrogen-storage material Mg(0.65)Sc(0.35)D2 studied with 2H and 2H-{45Sc} MAS NMR exchange spectroscopy

Using double-quantum (2)H MAS NMR with (45)Sc recoupling and Bloch-Siegert compensated (2)H-{(45)Sc} TRAPDOR we have identified the overlapping NMR signals of deuterium with and without scandium neighbors in Mg(0.65)Sc(0.35)D(2), a candidate lightweight material for hydrogen storage. At room temperature we also observe a third type of mobile deuterium. Deuterium mobility among the three NMR-distinct sites has been investigated by means of one-and two-dimensional exchange spectroscopy (Exsy). Complete deuterium exchange within 0.1s is observed, which indicates that the three NMR-distinct sites are close together in the crystal lattice. The weak temperature- and MAS-rate dependences observed in Exsy are indicative for a combination of chemical exchange and spin diffusion.     

CO吸附和加氢反应过程的原位高压MAS NMR研究

应用原位变温高压MAS核磁共振技术,对比研究了CO在不同Rh基催化剂上的吸附和加氢反应过程. ²⁹Si MAS NMR研究结果表明：Rh基催化剂中加入金属助剂后,载体Silicate-1上的表面硅羟基减少,助剂金属与硅羟基作用锚锭在载体表面.¹³C MAS NMR研究结果表明：当引入CO/H2混合气后,在Rh/Silicate-1催化剂上只能观测到气相CO、线式吸附CO和孪式吸附CO的快速交换信号;而在Rh-Mn/Silicate-1和Rh-Mn-Li/Silicate-1催化剂上,还观测到了倾斜式吸附的CO共振信号,表明助剂Mn或Mn-Li的加入促进了CO的吸附. 随着反应温度升高,CO/H₂在Rh/Silicate-1催化剂上转化生成CO_²,进一步升高温度会有CH₄生成;而CO/H₂在RhMnLi/Silicate-1催化剂上反应活性更高,在较低的温度下就会转化生成CO₂,但未观测到甲烷的生成. ¹H MAS NMR 谱显示,反应后载体Silicate-1上硅羟基的量会减少,表明CO与载体部分表面硅羟基反应生成了CO₂.     

MAS-NMR at very high temperatures

We report MAS-NMR experiments at temperatures of approx. 1200 K using a CO(2) laser as the heating device. An internal NMR thermometer based on the (7)Li T1 data of Li(0.24)La(0.54)TiO(3) is used for temperature calibration. Using this setup, temperatures as high as 1191 K could be reached under MAS conditions as confirmed by the melting of Li(2)B(4)O(7) at 1191 K which could be followed by (7)Li-MAS-NMR.     

6Li and 7Li MAS NMR spectra of complex lyonsite-type Li2Zn2(MoO4)3 and LiRb3Hf2(MoO4)6 lithium molybdates

⁶Li and ⁷Li MAS NMR spectra of complex Li₂Zn₂(MoO₄)₃ and LiRb₃Hf₂(MoO₄)₆ molybdates of lyonsite-type structure are studied at temperatures ranging from 25 to 100°C. NMR signals are attributed to their sources. It is shown that the presence of a transition metal such as Hf in the +4 oxidation state in the structure of lyonsite contributes to the increased mobility of lithium ions along the channels of the crystal structure.     

Characterization of the surface of positive electrodes for Li-ion batteries using 7Li MAS NMR

The growth and evolution of the interphase, due to contact with the ambient atmosphere or electrolyte, are followed using ⁷Li magic-angle spinning nuclear magnetic resonance (MAS NMR) in the case of two materials amongst the most promising candidates for positive electrodes for lithium batteries: LiFePO₄ and LiMn_0.5Ni_0.5O₂. The use of appropriate experimental conditions to acquire the NMR signal allows observing only the «diamagnetic» lithium species at the surface of the grains of active material. The reaction of LiMn_0.5Ni_0.5O₂ with the ambient atmosphere or LiPF₆ (1 M in Ethylene Carbonated/DiMéthyl Carbonate (EC/DMC)) electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species compared to what can be observed in the case of LiFePO₄. The two studied materials display a completely different surface chemistry in terms of reactivity and/or kinetics of the surface towards electrolyte. Moreover, these results show that MAS NMR is a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte.     

Dual processing of two-dimensional exchange data in magic angle spinning NMR of solids.

We discuss procedures for processing data in rotor-synchronized two-dimensional magic angle spinning (2D MAS) NMR exchange measurements for both structural and dynamical studies. We show, both mathematically and experimentally, that there are two distinct data processing procedures that lead to 2D MAS exchange spectra with purely absorptive crosspeaks. One procedure is that described previously by Hagemeyer, Schmidt-Rohr, and Spiess (HSS). The other procedure is related, but different, and leads to crosspeak intensities given by the formulae of Herzfeld, Roberts, and Griffin (HRG). In 2D MAS exchange experiments on doubly (13)C-labeled l-alanylglycylglycine, we demonstrate that the HSS and HRG crosspeak intensities can be extracted separately from the same data set and contain independent information. Processing and analysis of 2D MAS exchange data with both the HSS and the HRG procedures may enhance utilization of the information content of 2D MAS exchange measurements.     

Weak ferromagnetism of LiMnPO4

Structural and magnetic properties of the novel materials for lithium batteries LiFePO₄ and LiMnPO₄ were studied by X-ray diffraction, SQUID magnetometry and EPR spectroscopy. LiMnPO₄ has an olivine-type structure with a Mn-ion square lattice in the b-c plane. The occupation factors for Li and those oxygen atoms, which bridge Mn ions in the b-c plane showed noticeable deviation from the stoichiometry. In addition, the oxygen atoms, which are in the same layer as Li ions, exhibit a remarkable mean-square displacement in LiMnPO₄ but not in LiFePO₄. The olivine structure suggests quasi-two-dimensional (quasi-2D) antiferromagnetic structure of Mn(II) ions (S=5/2) with sizable interlayer exchange interactions. Magnetization measurements clearly revealed a transition to a weak ferromagnetic state below T_N=45 K. On the other hand we find that LiFePO₄ orders antiferromagnetically below 50 K. The difference in the magnetic properties of LiMnPO₄ and LiFePO₄ reflect the differences in the electronic states between these two compounds and may be very important for the electrochemical inactivity of LiMnPO₄. EPR measurements also suggest that at temperatures above T_N the low-energy magnetic excitations in LiMnPO₄ are characteristic for the quasi-2D magnetic structure with the soliton excitation energy E_S=139 K.     

6Li and 7li solid-state NMR spectroscopy of nitrogen ceramic phases

Two nitrogen ceramic phases, the oxynitride LiSiON and the nitride LiSi2N3, have been studied by 6Li and 7Li NMR. Magic angle spinning (MAS) NMR experiments have been carried out at two magnetic field strengths (7.05 and 14.1 T). The spectra give evidence of the relative effects of the quadrupolar and chemical shift interactions. The electric field gradient tensor of both phases has been determined accurately by iterative fitting of the 6Li and 7Li MAS NMR line shapes at the two magnetic field strengths. Due to the fact that for 7Li the quadrupolar interaction is much larger than the chemical shift interaction, it is shown that neither the small chemical shift anisotropy nor the relative orientation of the two interaction tensors can be determined accurately by 7Li MAS NMR. For 6Li, the two interactions are comparable and the value of these parameters obtained from the fits of the 6Li experimental MAS line shapes are therefore much more reliable.     

Direct Determination of Motional Correlation Times by 1D MAS and 2D Exchange NMR Techniques

One- and two-dimensional static and magic-angle spinning (MAS) exchange NMR experiments for quantifying slow (τ_c> 1 ms) molecular reorientation dynamics are analyzed, emphasizing the extent to which motional correlation times can be extracteddirectlyfrom the experimental data. The static two-dimensional (2D) exchange NMR experiment provides geometric information, as well as exchange time scales via straightforward and model-free application of Legendre-type orientational autocorrelation functions, particularly for axially symmetric interaction tensors, as often encountered in solid-state²H and¹³C NMR. Under conditions of MAS, increased sensitivity yields higher signal-to-noise spectra, with concomitant improvement in the precision and speed of correlation time measurements, although at the expense of reduced angular (geometric) resolution. For random jump motions, one-dimensional (1D)exchange-inducedsidebands (EIS)¹³C NMR and the recently developed ODESSA and time-reverse ODESSA experiments complement the static and MAS two-dimensional exchange NMR experiments by providing faster means of obtaining motional correlation times. For each of these experiments, the correlation time of a dynamic process may be obtained from a simple exponential fit to the integrated peak intensities measured as a function of mixing time. This is demonstrated on polycrystalline dimethylsulfone, where the reorientation rates from EIS, ODESSA, time-reverse ODESSA, and 2D exchange are shown to be equivalent and consistent with literature values. In the analysis, the advantages and limitations of the different methods are compared and discussed.     

第一性原理计算：锰酸锂掺杂Fe和Co的性质研究

文章基于密度泛函理论的第一性原理计算,研究了LiMn2O4电池材料在掺杂Fe和Co离子时的电子结构和电化学性能。发现Fe\Co取代Mn3+在热力学上是会更加稳定,提升电化学性能。掺杂Fe后,LiMn2O4电池材料晶格参数减小(约0.3%);掺杂Co后,LiMn2O4电池材料晶格参数减小(约0.5%)。这两种掺杂方式让与之相邻的Mn3+被氧化成Mn4+,从而降低了Jahn-Teller畸变情况产生可能性。对于掺Fe尖晶石型锰酸锂(Li8Mn15FeO32),Mn环境中的Li离子会更容易被提取,第一次放电电压从原来的3.7V增加至4.623V;对于掺Co尖晶石型锰酸锂(Li8Mn15CoO32),第一次放电电压从原来的3.7V增加至4.101V。研究为锂电池电容量研究提供理论数据的参考。     

NMR studies of cation transport in the crystalline ion conductors MCF3SO3 (M = Li,Na) and Li7TaO6

In this contribution we present studies on the mechanism of ion transport in crystalline solid electrolytes employing a range of different solid state nuclear magnetic resonance (NMR) experiments. The first part is devoted to the elucidation of a possible correlation of cation transport and anion reorientation in the dynamically disordered rotor phases of alkali trifluoromethane sulfonates MCF₃SO₃ (M = Li, Na) employing ⁷Li, ¹³C, ¹⁷O and ²³Na NMR line shape analysis, whereas the second part focuses on the tracking of cation diffusion pathways in the hexaoxometalate Li₇TaO₆ utilizing ⁶Li 1D and 2D exchange MAS NMR approaches.     

Multinuclear MAS NMR study of the microporous aluminophosphate AlPO4-17 and the related silicoaluminophosphate SAPO-17.

AlPO4-17 and SAPO-17 in their as-synthesized, calcined, and calcined and subsequently rehydrated forms have been studied by 27Al and 31P MAS NMR. Pronounced structural changes caused by template removal and rehydration can unambiguously be attributed to a change in the coordination number (on calcination: 5-->4, on rehydration/dehydration: 4<-->6) of part of the framework aluminium atoms. The different resonance lines can be assigned to crystallographically inequivalent sites present in the modified ERI framework. 27Al quadrupolar coupling parameters of the two aluminium sites in the calcined AlPO4-17 (CQ = 4.4 MHz and 2.1 MHz) were determined by recording spectra at different field strengths. The isotropic chemical shifts were obtained from rotation sidebands of the (+/- 3/2, +/- 1/2) satellite transitions. 2D 27Al nutation MAS NMR was used to corroborate the line assignment for the as-synthesized and the rehydrated AlPO4-17. By using 13C MAS NMR it was shown that the occluded template (cyclohexylamine) is present as ions. For the first time, a splitting of the 29Si NMR line caused by crystallographically inequivalent sites in a SAPO-type material is reported. The line splitting of 4.3 ppm is comparable with that observed for isostructural aluminosilicate erionite.