The work takes advantage of a newly developed measurement system which enables to investigate the thermodynamic properties of thin films including battery layer sequences. This technique, Thin-Film Calorimetry (TFC), is based on the detection of resonance frequency shifts of bulk acoustic wave resonators. Thin films with a thickness of several micrometers of the material of interest are deposited on the resonators. By measuring the temperature dependent shift of the resonance frequency, the device is working as a precise temperature sensor. The production or consumption of latent heat by the active layer(s) results in temperature fluctuations with respect to the furnace where the sensor is placed. Those information enable to extract the temperature and time dependence of phase transformations as well as the associated enthalpies. To cover a temperature range from -20 to 900 °C high-temperature stable piezoelectric resonators made of langasite crystals (La3Ga5SiO14) are applied.

Initially, metallic layers of tin and aluminum are used to test and verify this approach. The temperatures and enthalpies of solid-liquid as well as of solid-solid phase transformation are observed in the correct manner. Further, the thermodynamic data of the battery materials Li(Ni0.8Co0.15Al0.05)O2-δ (NCA) and LiMn2O4-δ (LMO) obtained by TFC are determined and discussed. Both cathode materials are amorphous after deposition and show crystallization during heating at 460 °C (NCA) and 600 °C (LMO). The associated enthalpies are 5.3 kJ/mol (55 J/g) and 17.3 kJ/mol (96 J/g), respectively.

We have studied CuLi0.08Mg1.92 and determined that the compound reacts with hydrogen to form CuLi0.08Mg1.92H5 [1]. Additionally, we have proposed the compound as a negative electrode material which is the main purpose of the present study. Moreover, we have observed that the latter compound acts as a catalyst in the formation of MgH2, LiH, TiH2 [2] and hydrogen desorption. In this work, first principles and phonon calculations were performed in order to establish the reactions occurring at the negative electrode of a Li conversion battery in presence of CuLi0.08Mg1.92H5 and (Li) – solid solution of Mg in Li – approximately Li2Mg3. We have calculated the minimum theoretical specific capacity to be 1156 mAh/g (for an anode with 100% of CuLi0.08Mg1.92H5) and the △Eeq = 0.81 V (vs. Li+/Li) at 298 K. Furthermore, we have determined all the reactions occurring in the referred system and its sequence using Inelastic Incoherent Neutron Scattering (IINS) and X-Ray Diffraction (XRD).

Using first-principles calculations, we investigate lithium vacancy and interstitial defects in lithium phosphate (γ-Li3PO4) and in its interface with metallic Li. We find that γ-Li3PO4 is good electronic insulator with a wide band gap of 6 eV. The calculated formation energies of Li vacancies are higher than those of Li interstitials, which indicate that the ionic conductivity is determined by the migration of Li interstitial defects in bulk electrolyte. The Li vacancy-interstitial pair defect formation energy in the Li/γ-Li3PO4 interface is comparable to the sum of Li vacancy defect at the electrode and Li ion interstitial defect in the electrolyte. Our calculation indicates that the low ionic conductivity of Li/electrolyte interface is associated with the high Li ion defect formation energy. Our study provides some useful insights on Li defect formation and migration mechanisms at the electrode-electrolyte interface and, hence, a research direction for designing future Li-ion batteries.

Garnet-type electrolytes are currently receiving much attention for applications in Li-ion batteries, as they possess high ionic conductivity and chemical stability. Doping the garnet structure has proved to be a good way to improve the Li ion conductivity and stability. The present study includes effects of Y- doping in Li5La3Nb2O12 on Li ion conductivity and stability of “Li5+2xLa3Nb2-xYxO12” (0.05 ≤ x ≤ 0.75) under various environments, as well as chemical stability studies of Li5+xBaxLa3-xM2O12 (M = Nb, Ta) in water. “Li6.5La3Nb1.25Y0.75O12” showed a very high ionic conductivity of 2.7 х 10−4 Scm−1 at 25 °C, which is comparable to the highest value reported for garnet-type compounds, e.g., Li7La3Zr2O12. The selected members show very good stability against high temperatures, water, Li battery cathode Li2CoMn3O8 and carbon. The Li5+xBaxLa3-xNb2O12 garnets have shown to readily undergo an ion-exchange (proton) reaction under water treatment at room temperature; however, the Ta-based garnet appears to exhibit considerably higher stability under the same conditions.

Large-area fast lithium ion conducting ceramic thin freestanding sheets was successfully prepared using a sheet forming technique. This ceramic sheet contains the crystalline phase of Li1+x+yAlxTi2-xSiyP3-yO12 with the NASICON type structure. The ceramic sheet showed maximum overall conductivity over 10−3 S cm−1 at room temperature. And, the developed thin ceramic sheet has sufficient flexibility against bending stress. Because a thin large-area ceramic electrolyte sheet was prepared using less energy compared with a conventional glass casting method, it is suitable for practical use.

Highly ion-conductive Li6PS5Cl Li-argyrodites were prepared through a high energy ball milling. Electrical and electrochemical properties were investigated. Ball-milled compounds exhibit a high conductivity of 1.33×10−4 S/cm with an activation energy of 0.3-0.4 eV and an electrochemical stability up to 7V vs. lithium. These results are obtained after only 10 hours of milling and with no additional heat treatment.

To validate the use of the Li6PS5Cl-based solid electrolyte, all-solid-state batteries using LiCoO2 and Li4Ti5O12 as active material have been realized. The optimization of the electrode composition led to a maximum of 46 and 27 mAh per gram of composite for LiCoO2 and Li4Ti5O12-based half-cells respectively. The assembled all-solid-state LiCoO2 / Li6PS5Cl / Li4Ti5O12 battery presents a sustainable reversible capacity of 27 mAh per gram of active material and a coulomb efficiency close to 99%.

Development of Al-stabilized Li7La3Zr2O12 (LLZO) fast Li ion conducting thin films was attempted by chemical solution deposition (CSD) method with the nominal composition of Li5.95Al0.35La3Zr2O12. The films were crystallized at 600°C on Pt-coated Si substrates in almost single phase without a preferred orientation to any crystallographic axis. Subsequent thermal annealing at 760°C improved packing of LLZO grains with the film thickness of 1.1μm. AC impedance measurements were conducted both with Li reversible and Au blocking microelectrodes deposited on the films annealed at 760°C. Total Li ion conductivity σtotal comprised of bulk and grain boundary contribution was studied. The temperature dependence of σtotal was described with single thermal activation process and σtotal∼2x10-5 S/cm and activation energy of Ea=0.58eV were estimated. These values may be attributed to tetragonal modification of LLZO crystal.

To enhance cycleability of LiMn2O4 at elevated-temperature we use atomic layer deposition (ALD) method to deposit a variety of ultrathin and highly conformal amphoteric oxide (ZnO, ZrO2, Al2O3) coatings for surface modification of LiMn2O4 electrodes. High-resolution transmission electron microscopic (HRTEM) images of ZnO, ZrO2 and Al2O3 ALD coated LiMn2O4 particles demonstrate the high qualities of ALD coatings with respect to remarkable conformity, homogeneity and uniformity. Two types of ALD-modified LiMn2O4 electrodes are fabricated: one is ALD-coated LiMn2O4 composite electrode, the other is electrode composed of ALD-coated LiMn2O4 particles and uncoated carbon/poly-vinylidenefluoride (PVDF) network. All LiMn2O4 electrodes modified with 6 oxide ALD layers (as thin as ∼1 nm) reveal significantly enhanced electrochemical performances than bare electrodes at both 25°C and 55°C. After 100 electrochemical cycles at 1 C at 55°C, the electrode consisting of LiMn2O4 particles coated with 6 ZnO ALD layers remains the highest capacity of 56.1 mAh/g, higher than 51.1 mAh/g of ZrO2 coated LiMn2O4 particles, 45.8 mAh/g of Al2O3 coated LiMn2O4 particles and 27.0 mAh/g of the bare composite electrode as well as 44.5 mAh/g of the composite electrode coated with 6 ZnO ALD layers. These results indicate that ZnO ALD coating is the most effective protective film for improved cycling stability, followed by ZrO2 and Al2O3. It is also found that amphoteric oxide coating on LiMn2O4 particles is more effective to enhance the cycleability of LiMn2O4 than coating on composite electrode. Furthermore, for coating either on composite electrode or on LiMn2O4 particles, the effect of ALD coating on improving capacity retention and increasing specific capacity of LiMn2O4 is more phenomenal at elevated temperature than at room temperature.

Molybdenum disulfide (MoS2) nanostructures with three different morphologies are synthesized and tested with respect to their applicability in lithium ion batteries. Thereby, electrolytes based on ionic liquids are used. The electrochemical performance of nanostructures and thin films is compared to evaluate the influence of the morphology. Characterization methods include X-Ray diffraction (XRD), cyclic voltammetry (CV), galvanostatic cycling and thin film calorimetry. The thin film and the nanostructured samples show a reversible capacity of 525 mAh/g and a maximum capacity 225 mAh/g, respectively.