Viktor Epp

Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li2O2—the discharge product in lithium-air batteries

Understanding charge carrier transport in Li2O2, the storage material in the non-aqueous Li-O2 battery, is key to the development of this high-energy battery. Here, we studied ionic transport properties and Li self-diffusion in nanocrystalline Li2O2 by conductivity and temperature variable 7Li NMR spectroscopy. Nanostructured Li2O2, characterized by a mean crystallite size of less than 50 nm as estimated from X-ray diffraction peak broadening, was prepared by high-energy ball milling of microcrystalline lithium peroxide with μm sized crystallites. At room temperature the overall conductivity σ of the microcrystalline reference sample turned out to be very low (3.4 × 10−13 S cm−1) which is in agreement with results from temperature-variable 7Li NMR line shape measurements. Ball-milling, however, leads to an increase of σ by approximately two orders of magnitude (1.1 × 10−10 S cm−1); correspondingly, the activation energy decreases from 0.89 eV to 0.82 eV. The electronic contribution σeon, however, is in the order of 9 × 10−12 S cm−1 which makes less than 10% of the total value. Interestingly, 7Li NMR lines of nano-Li2O2 undergo pronounced heterogeneous motional narrowing which manifests in a two-component line shape emerging with increasing temperatures. Most likely, the enhancement in σ can be traced back to the generation of a spin reservoir with highly mobile Li ions; these are expected to reside in the nearest neighbourhood of defects generated or near the structurally disordered and defect-rich interfacial regions formed during mechanical treatment.

Macroscopic and microscopic Li+ transport parameters in cubic garnet-type “Li6.5La2.5Ba0.5ZrTaO12” as probed by impedance spectroscopy and NMR

The garnet-type “Li6.5La2.5Ba0.5ZrTaO12”, crystallizing with cubic symmetry was prepared according to a conventional solid state synthesis method using metal oxides and salt precursors of high purity. The formation of the “single-phase” garnet-type structure was studied by powder X-ray diffraction (PXRD). Electron microprobe analysis (EMPA) coupled with a wavelength-dispersive spectrometer (WDS) showed a rather homogeneous distribution of Ta ions and Zr ions compared to that of Ba ions and La ions in “Li6.5La2.5Ba0.5ZrTaO12”. Li ion dynamics were complementarily studied using variable-temperature AC-impedance spectroscopy and 7Li NMR measurements. The bulk (ion) conductivities probed are in very good agreement with results reported earlier, illustrating the excellent reproducibility of the Li transport properties of “Li6.5La2.5Ba0.5ZrTaO12”. In particular, AC impedance and NMR results indicate that the Li transport process studied is of long-range nature. Finally, the chemical compatibility of the electrolyte “Li6.5La2.5Ba0.5ZrTaO12” was tested with Li2FeMn3O8, being a high-voltage cathode material. As shown by variable-temperature PXRD measurements, the garnet-type structure (bulk) was found to be stable up to 673 K.

Microscopic Li self-diffusion parameters in the lithiated anode material Li4+xTi5O12 (0 ≤x≤ 3) measured by 7Li solid state NMR

The microscopic Li diffusion parameters in the lithiated spinel Li4 + xTi5O12, which is on its way to become a commercially used anode material in Li ion batteries, are probed for the first time via nuclear magnetic resonance spectroscopy.

Order vs. disorder—a huge increase in ionic conductivity of nanocrystalline LiAlO2 embedded in an amorphous-like matrix of lithium aluminate

Coarse grained, well crystalline γ-LiAlO2 (P43212) is known as an electronic insulator and a very poor ion conductor with the lithium ions occupying tetrahedral voids in the oxide structure. The introduction of structural disorder such as point defects or higher-dimensional defects, however, may greatly affect ionic conduction on both short-range as well as long-range length scales. In the present study, we used high-energy ball milling to prepare defect-rich, nanocrystalline LiAlO2 that was characterized from a structural point of view by powder X-ray diffraction, TEM as well as small angle X-ray scattering (SAXS). Temperature-dependent conductivity spectroscopy revealed an increase of the room-temperature ionic conduction by several orders of magnitude when going from microcrystalline γ-LiAlO2 to its nanocrystalline form. The enhanced ion transport found is ascribed to the increase of Li ions near defective sites both in the bulk as well as in the large volume fraction of interfacial regions in nano-LiAlO2. The nanocrystalline ceramic prepared at long milling times is a mixture of γ-LiAlO2 and the high-pressure phase δ-LiAlO2; it adapts an amorphous like structure after it has been treated in a planetary mill under extremely harsh conditions.

Separating bulk from grain boundary Li ion conductivity in the sol–gel prepared solid electrolyte Li1.5Al0.5Ti1.5(PO4)3

Lithium aluminium titanium phosphate (LATP) belongs to one of the most promising solid electrolytes. Besides sufficiently high electrochemical stability, its use in lithium-based all-solid-state batteries crucially depends on the ionic transport properties. While many impedance studies can be found in literature that report on overall ion conductivities, a discrimination of bulk and grain boundary electrical responses via conductivity spectroscopy has rarely been reported so far. Here, we took advantage of impedance measurements that were carried out at low temperatures to separate bulk contributions from the grain boundary responses. It turned out that bulk ion conductivity is by at least three orders of magnitude higher than ion transport across the grain boundary regions. At temperatures well below ambient long-range Li ion dynamics is governed by activation energies ranging from 0.26 to 0.29 eV depending on the sintering conditions. As an example, at temperatures as low as 173 K, the bulk ion conductivity, measured in N2 inert gas atmosphere, is in the order of 8.1 × 10−6 S cm−1. Extrapolating this value to room temperature yields ca. 3.4 × 10−3 S cm−1 at 293 K. Interestingly, exposing the dense pellets to air atmosphere over a long period of time causes a significant decrease of bulk ion transport. This process can be reversed if the phosphate is calcined at elevated temperatures again.

Spin-alignment echo NMR: probing Li+ hopping motion in the solid electrolyte Li7La3Zr2O12 with garnet-type tetragonal structure *

(7)Li spin-alignment echo (SAE) nuclear magnetic resonance (NMR) spectroscopy has been used to measure single-spin hopping correlation functions of polycrystalline Li(7)La(3)Zr(2)O(12). Damping of the echo amplitude S(2)(t(m),t(p)), recorded at variable mixing time t(m) but fixed preparation time t(p), turns out to be solely controlled by slow Li jump processes taking place in the garnet-like structure. The decay rates τ(SAE)(-1) directly obtained by parametrizing the curves S(2)(t(m),t(p)) with stretched exponential functions show Arrhenius behaviour pointing to an activation energy of approximately 0.5 eV. This value, probed by employing an atomic-scale NMR method, is in very good agreement with that deduced from impedance spectroscopy used to measure macroscopic Li transport parameters. Most likely, the two methods are sensitive to the same hopping correlation function although Li dynamics are probed in a quite different manner.

Fast Li ion dynamics in the solid electrolyte Li7 P3 S11 as probed by (6,7) Li NMR spin-lattice relaxation.

The development of safe and long-lasting all-solid-state batteries with high energy density requires a thorough characterization of ion dynamics in solid electrolytes. Commonly, conductivity spectroscopy is used to study ion transport; much less frequently, however, atomic-scale methods such as nuclear magnetic resonance (NMR) are employed. Here, we studied long-range as well as short-range Li ion dynamics in the glass-ceramic Li7 P3 S11 . Li(+) diffusivity was probed by using a combination of different NMR techniques; the results are compared with those obtained from electrical conductivity measurements. Our NMR relaxometry data clearly reveal a very high Li(+) diffusivity, which is reflected in a so-called diffusion-induced (6) Li NMR spin-lattice relaxation peak showing up at temperatures as low as 313 K. At this temperature, the mean residence time between two successful Li jumps is in the order of 3×10(8) s(-1) , which corresponds to a Li(+) ion conductivity in the order of 10(-4) to 10(-3) S cm(-1) . Such a value is in perfect agreement with expectations for the crystalline but metastable glass ceramic Li7 P3 S11 . In contrast to conductivity measurements, NMR analysis reveals a range of activation energies with values ranging from 0.17 to 0.26 eV, characterizing Li diffusivity in the bulk. In our case, through-going Li ion transport, when probed by using macroscopic conductivity spectroscopy, however, seems to be influenced by blocking grain boundaries including, for example, amorphous regions surrounding the Li7 P3 S11 crystallites. As a result of this, long-range ion transport as seen by impedance spectroscopy is governed by an activation energy of approximately 0.38 eV. The findings emphasize how surface and grain boundary effects can drastically affect long-range ionic conduction. If we are to succeed in solid-state battery technology, such effects have to be brought under control by, for example, sophisticated densification or through the preparation of samples that are free of any amorphous regions that block fast ion transport.

Motion of Li+ in Nanoengineered LiBH4 and LiBH4:Al2O3 Comparison with the Microcrystalline Form

The introduction of structural disorder and large volume fractions of different kinds of interfaces enables the manipulation of ion dynamics in solids. Variable-temperature solid-state NMR relaxometry is highly useful to study Li(+) jump processes. If carried out as a function of frequency, the resulting NMR relaxation rates also contain information on the dimensionality (1D, 2D, or 3D) of the diffusion process. Recently, NMR relaxometry has revealed the 2D nature of Li hopping in LiBH4 , and thus this hydride is an interesting ion conductor for further diffusion studies on the spatially confined motion of Li spins. Here, nanocrystalline LiBH4 and the two-phase analogue LiBH4 :Al2 O3 , which are prepared by ball milling, serve as interesting model systems to track the changes in NMR relaxation rates with respect to coarse-grained, thermodynamically stable LiBH4 . This reveals that interface (nano)engineering influences the hexagonal-to-orthorhombic phase transition and thus alters the ion-transport properties of Li in one- and two-phase LiBH4 towards higher diffusivities at lower temperatures.

Ion dynamics in solid electrolytes for lithium batteries

All-solid-state batteries with ceramic electrolytes and lithium metal anodes represent an attractive alternative to conventional ion battery systems. Conventional batteries still rely on flammable liquids as electronic insulators. Despite the great efforts reported over the last years, the optimum solid electrolyte has, however, not been found yet. One of the most important properties which decides whether a ceramic is useful to work as electrolyte is ionic transport. The various time-domain nuclear magnetic resonance (NMR) techniques might help characterize and select the most suitable candidates. Together with conductivity measurements it is possible to analyze ion dynamics on different length-scales, i.e., to differentiate between local, within-site hopping processes from long-range ion transport. The latter needs to be sufficiently fast in the ceramic, in the best case competing with that of liquid electrolytes. In addition to conductivity spectroscopy, NMR can help understand the relationship between local structure and dynamic parameters. Besides information on activation energies and jump rates the data also contain suggestions about the relevant elementary steps of ion hopping and, thus, diffusion pathways through the crystal lattice. Recent progress in characterizing ion dynamics in ceramic electrolytes by NMR relaxometry will be briefly reviewed. Focus is put on presently discussed solid electrolytes such as garnets, phosphates and sulfides, which have so far been studied in our lab.

Two-dimensional diffusion in Li0.7NbS2 as directly probed by frequency-dependent 7Li NMR

Li ion diffusion in layer-structured Li0.7NbS2 has been complementary investigated by nuclear magnetic resonance (NMR) spectroscopy from an atomic scale point of view. In the present case, (7)Li NMR spin-lattice relaxation (SLR) rates R1ρ probed in the rotating frame of reference proved very informative in characterizing the Li self-diffusion process in the van der Waals gap between the NbS2 layers. While temperature-variable SLRρ measurements were used to determine dynamic parameters such as jump rates (τ(-1)) and the activation energy (Ea), frequency-dependent measurements were used to specify the dimensionality of the diffusion process. In particular, the effect of annealing, i.e., the distribution of Li ions between the layers, on overall Li dynamics has been studied. When plotted in an Arrhenius diagram, the R1ρ rates of an annealed sample, which were recorded at a locking frequency of 20 kHz, pass through a diffusion-induced relaxation peak whose maximum shows up at 320 K. Employing an appropriate diffusion model and appropriately accounting for a non-diffusive background relaxation, a Li jump rate τ(-1)(300 K) ≈ 1.3 × 10(5) s(-1) and an activation energy Ea of 0.43(2) eV can be deduced. Most importantly, in the high-T limit of the diffusion-induced rate peak, i.e., when ω1τ << 1 holds, the rates follow a logarithmic frequency dependence. This points to a diffusion process of low dimensionality and is in good agreement with predictions of relaxation models developed for 2D diffusion.