The application of Li7La3Zr2O12 as a Li+ solid electrolyte is hampered by the lack of a reliable procedure to obtain and densify the fast-ion conducting cubic garnet polymorph. Dense cubic Li7La3Zr2O12-type phases are typically formed as a result of Al-incorporation in an unreliable reaction with the alumina crucible at elevated temperatures of up to 1230 °C. High Al3+-incorporation levels are also believed to hinder the three-dimensional movement of Li+ in these materials. Here, a new, facile hybrid sol–gel solid-state approach has been developed in order to accomplish reliable and controllable synthesis of these phases with low Al-incorporation levels. In this procedure, sol–gel processed solid precursors of Li7La3Zr2O12 and Al2O3 nanosheets are simply mixed using a pestle and mortar and allowed to react at 1100 °C for 3 h to produce dense cubic phases. Fast-ion conducting Al-doped Li7La3Zr2O12 phases with the lowest reported Al3+-content (∼0.12 mol per formula unit), total conductivities of ∼3 × 10−4 S cm−1, bulk conductivities up to 0.6 mS and ion conduction activation energies as low as 0.27 eV, have been successfully achieved. The ease of lithium diffusion in these materials is attributed to the formation of dense cubic phases with low Al3+ dopant ratios. This approach is applicable to Li7−xLa3Zr2−xTaxO12 phases and opens up a new synthetic avenue to Li7La3Zr2O12-type materials with greater control over resulting characteristics for energy storage applications.

Fast ion conducting garnet materials have been identified as promising electrolytes for all solid-state batteries. However, reliable synthetic routes to materials with fully elucidated cation site occupancies where an enhancement in lithium conductivity is observed remains a challenge. Ca-Incorporation is developed here as a promising approach to enhance the ionic conductivity of garnet-type Li7−xLa3Zr2−xTaxO12 phases. Here we present a new sol–gel synthetic strategy as a facile route to the preparation of materials of a desired stoichiometry optimized for Li+ conductivity. We have found that the ionic conductivity of Li6.4La3Zr1.4Ta0.6O12 is increased by a factor of four by the addition of 0.2 mol of Ca per formula unit. Ca is incorporated in the garnet lattice where it has no effect on the sinterability of the material and is predominately located at the La sites. We anticipate that the ease of our synthetic route and the phases presented here represents a starting point for the further realization of solid state electrolyte compositions with similarly high Li+ conductivities using this methodology.

Lithium-stuffed garnets attract huge attention due to their outstanding potential as solid-state electrolytes for lithium batteries. However, there exists a persistent challenge in the reliable synthesis of these complex functional oxides together with a lack of complete understanding of the lithium-ion diffusion mechanisms in these important materials. Addressing these issues is critical to realizing the application of garnet materials as electrolytes in all solid-state lithium-ion batteries. In this work, a cubic phase garnet of nominal composition Li6.5Al0.25La2.92Zr2O12 is synthesized through a microwave-assisted solid-state route for the first time, reducing considerably the reaction times and heating temperatures. Lithium-ion diffusion behavior is investigated by electrochemical impedance spectroscopy (EIS) and state-of-art muon spin relaxation (μSR) spectroscopy, displaying activation energies of 0.55 ± 0.03 eV and 0.19 ± 0.01 eV respectively. This difference arises from the high inter-grain resistance, which contributes to the total resistance in EIS measurements. In contrast, μSR acts as a local probe providing insights on the order of the lattice, giving an estimated value of 4.62 × 10−11 cm2 s−1 for the lithium diffusion coefficient. These results demonstrate the potential of this lithium-stuffed garnet as a solid-state electrolyte for all-solid state lithium-ion batteries, an area of growing interest in the energy storage community.

Microwave or ultrasonic treatment of metal alkoxides presents a fast, low cost route to both anode and cathode nanomaterials for Li-ion battery applications. Here, we demonstrate the formation of LiMPO4 (M = Fe, Mn) and Mn3O4 nanostructures via this simple route which exhibit excellent electrochemical performances. This approach opens up a new avenue for the targeted design of nanostructured materials, where co-location of the desired metals in a single starting material shortens reaction times and temperatures since there is a decrease in diffusional energy requirements usually needed for these reactions to proceed.

The lithium diffusion in nanostructured olivine LiFePO4 has been investigated for the first time using muon spectroscopy (μSR). A microwave-assisted approach has been employed for nanoparticle preparation, where the choice of solvent is shown to play an important role in determining particle morphology and crystal chemistry. Two phases have been obtained: Pnma LiFePO4 and the high pressure Cmcm phase. The Li+ diffusion behaviour is strikingly different in both phases, with DLi of 6.25 × 10−10 cm2 s−1 obtained for Pnma LiFePO4 in good agreement with measurements of bulk materials. In contrast, Li+ diffusion is impeded with the addition of the high pressure Cmcm phase, with a lower DLi of 3.96 × 10−10 cm2 s−1 noted. We have demonstrated an efficient microwave route to nanoparticle synthesis of positive electrode materials and we have also shown μSR measurements to be a powerful probe of Li+ diffusion behaviour in nanoparticles.

Lithium-stuffed garnets attract huge attention due to their outstanding potential as solid-state electrolytes for lithium batteries. However, there exists a persistent challenge in the reliable synthesis of these complex functional oxides together with a lack of complete understanding of the lithium-ion diffusion mechanisms in these important materials. Addressing these issues is critical to realizing the application of garnet materials as electrolytes in all solid-state lithium-ion batteries. In this work, a cubic phase garnet of nominal composition Li6.5Al0.25La2.92Zr2O12 is synthesized through a microwave-assisted solid-state route for the first time, reducing considerably the reaction times and heating temperatures. Lithium-ion diffusion behavior is investigated by electrochemical impedance spectroscopy (EIS) and state-of-art muon spin relaxation (μSR) spectroscopy, displaying activation energies of 0.55 ± 0.03 eV and 0.19 ± 0.01 eV respectively. This difference arises from the high inter-grain resistance, which contributes to the total resistance in EIS measurements. In contrast, μSR acts as a local probe providing insights on the order of the lattice, giving an estimated value of 4.62 × 10−11 cm2 s−1 for the lithium diffusion coefficient. These results demonstrate the potential of this lithium-stuffed garnet as a solid-state electrolyte for all-solid state lithium-ion batteries, an area of growing interest in the energy storage community.

The lithium diffusion in nanostructured olivine LiFePO4 has been investigated for the first time using muon spectroscopy (μSR). A microwave-assisted approach has been employed for nanoparticle preparation, where the choice of solvent is shown to play an important role in determining particle morphology and crystal chemistry. Two phases have been obtained: Pnma LiFePO4 and the high pressure Cmcm phase. The Li+ diffusion behaviour is strikingly different in both phases, with DLi of 6.25 × 10−10 cm2 s−1 obtained for Pnma LiFePO4 in good agreement with measurements of bulk materials. In contrast, Li+ diffusion is impeded with the addition of the high pressure Cmcm phase, with a lower DLi of 3.96 × 10−10 cm2 s−1 noted. We have demonstrated an efficient microwave route to nanoparticle synthesis of positive electrode materials and we have also shown μSR measurements to be a powerful probe of Li+ diffusion behaviour in nanoparticles.

Fast ion conducting garnet materials have been identified as promising electrolytes for all solid-state batteries. However, reliable synthetic routes to materials with fully elucidated cation site occupancies where an enhancement in lithium conductivity is observed remains a challenge. Ca-Incorporation is developed here as a promising approach to enhance the ionic conductivity of garnet-type Li7−xLa3Zr2−xTaxO12 phases. Here we present a new sol–gel synthetic strategy as a facile route to the preparation of materials of a desired stoichiometry optimized for Li+ conductivity. We have found that the ionic conductivity of Li6.4La3Zr1.4Ta0.6O12 is increased by a factor of four by the addition of 0.2 mol of Ca per formula unit. Ca is incorporated in the garnet lattice where it has no effect on the sinterability of the material and is predominately located at the La sites. We anticipate that the ease of our synthetic route and the phases presented here represents a starting point for the further realization of solid state electrolyte compositions with similarly high Li+ conductivities using this methodology.

The application of Li7La3Zr2O12 as a Li+ solid electrolyte is hampered by the lack of a reliable procedure to obtain and densify the fast-ion conducting cubic garnet polymorph. Dense cubic Li7La3Zr2O12-type phases are typically formed as a result of Al-incorporation in an unreliable reaction with the alumina crucible at elevated temperatures of up to 1230 °C. High Al3+-incorporation levels are also believed to hinder the three-dimensional movement of Li+ in these materials. Here, a new, facile hybrid sol–gel solid-state approach has been developed in order to accomplish reliable and controllable synthesis of these phases with low Al-incorporation levels. In this procedure, sol–gel processed solid precursors of Li7La3Zr2O12 and Al2O3 nanosheets are simply mixed using a pestle and mortar and allowed to react at 1100 °C for 3 h to produce dense cubic phases. Fast-ion conducting Al-doped Li7La3Zr2O12 phases with the lowest reported Al3+-content (∼0.12 mol per formula unit), total conductivities of ∼3 × 10−4 S cm−1, bulk conductivities up to 0.6 mS and ion conduction activation energies as low as 0.27 eV, have been successfully achieved. The ease of lithium diffusion in these materials is attributed to the formation of dense cubic phases with low Al3+ dopant ratios. This approach is applicable to Li7−xLa3Zr2−xTaxO12 phases and opens up a new synthetic avenue to Li7La3Zr2O12-type materials with greater control over resulting characteristics for energy storage applications.

Microwave or ultrasonic treatment of metal alkoxides presents a fast, low cost route to both anode and cathode nanomaterials for Li-ion battery applications. Here, we demonstrate the formation of LiMPO4 (M = Fe, Mn) and Mn3O4 nanostructures via this simple route which exhibit excellent electrochemical performances. This approach opens up a new avenue for the targeted design of nanostructured materials, where co-location of the desired metals in a single starting material shortens reaction times and temperatures since there is a decrease in diffusional energy requirements usually needed for these reactions to proceed.