Phase evolution,structure, and electrochemical performance of Al-, Ga- and Ta- substituted Li7La3Zr2O12 ceramic electrolytes by a modified wet chemical route

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is one of the most promising solid-state electrolytes (SSEs) for advanced solid-state lithium batteries (SSLBs). In this work, Li_6.25Al_0.25La₃Zr₂O₁₂, Li_6.4Ga_0.2La₃Zr₂O₁₂, and Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramics are prepared by a modified wet chemical route. The composition of the black mixtures derived from the precursors is ascertained. The phase evolution and structural properties from the ceramic mother powders to the final ceramic electrolytes are discussed in detail. The characteristic of cubic LLZO with the space group I-43d arises in the Li_6.4Ga_0.2La₃Zr₂O₁₂ ceramic electrolyte pellet after the secondary higher-temperature (1200 °C) sintering. The Rietveld refinement reveals the roles of Al³⁺ substitution at the Li⁺ sites and Ta⁵⁺ substitution at the Zr⁴⁺ sites to adjust crystal structure. In addition, the electrochemical performance of the ceramic pellets is also investigated. Remarkably, the Li_6.4La₃Zr_1.4Ta_0.6O₁₂ ceramic electrolyte has the most outstanding electrochemical performance, showing the high ionic conductivity of 6.88 × 10^?4 S cm^?1 (25 °C), the low activation energy of 0.42 eV and an extremely low electronic conductivity of 1.77 × 10^?8 S cm^?1 (25 °C). Overall, it is supposed that this work may help to achieve high-quality modified LLZO ceramic electrolytes, especially using the wet chemical strategy.     

High lithium ionic conductivity in the garnet‐type oxide Li7−2xLa3Zr2−xMoxO12 (x=0‐0.3) ceramics by sol‐gel method

Lithium garnet‐type oxides Li_7?2xLa₃Zr_2?xMo_xO₁₂ (x=0, 0.1, 0.2, 0.3) ceramics were prepared by a sol‐gel method. The influence of molybdenum on the structure, microstructure and conductivity of Li₇La₃Zr₂O₁₂ were investigated by X‐ray diffraction, scanning electron microscopy, and impedance spectroscopy. The cubic phase Li₇La₃Zr₂O₁₂ has been stabilized by partial substitution of Mo for Zr at low temperature. The introduction of Mo (x≥0.1) can accelerate densification. Li_6.6La₃Zr_1.8Mo_0.2O₁₂ sintered at lower temperature 1100°C for 3 hours exhibits highest total ionic conductivity of 5.09 × 10^?4 S/cm. Results indicate that the Mo doping LLZO synthesized by sol‐gel method effectively lowers its sintering temperature and improves the ionic conductivity.     

Crystal structure of cubic Li7-3xGaxLa3Zr2O12 with space group of I-43d

Cubic Li_7-3xGa_xLa₃Zr₂O₁₂ is a cubic phase with a space group of I-43d instead of Ia-3d. This structure is more conducive to the migration of lithium ions. However, the effect of Ga on the size and environment of lithium ion transport channels has not been researched. In this work, Li_7-3xGa_xLa₃Zr₂O₁₂ (x = 0–0.25) was formulated, and the crystal structure was obtained by neutron diffraction. The results indicated that the minimum channel size to control Li⁺ migration in LLZO was the bottleneck size between the Li2 and Li3 sites (bottleneck size 2), and compared with lanthanum ions, the zirconium ions were closer to lithium ions. As the Ga content increased, bottleneck size 2 levelled off, while the lithium concentration and the distance between skeleton ions and lithium ions decreased. As a result, the lithium ionic conductivity primarily increased and then decreased. When doping 0.2 pfu of Ga, LLZO exhibited the highest lithium ionic conductivity of 1.45 mS/cm at 25 °C due to the coordinated regulation of Li⁺ concentration, bottleneck size, and the distance between skeleton ions and lithium ions.     

Influence of sintering atmosphere on the phase,microstructure, and lithium-ion conductivity of the Al-doped Li7La3Zr2O12 solid electrolyte

Al-doped Li₇La₃Zr₂O₁₂ (Al–LLZO) solid electrolytes were sintered at 1150 ^°C for 8 h in atmosphere of oxygen, argon and air (named as Al–LLZO–O₂, Al–LLZO–Ar and Al–LLZO–Air, respectively). All the Al–LLZO samples exhibited a single cubic garnet-type structure. The sample of Al–LLZO–O₂ possessed the highest relative density (95.60%) and the largest average grain size among the three Al–LLZO samples. Furthermore, owing to its high relative density and small number of grain boundaries, Al–LLZO–O₂ demonstrated a higher lithium-ion conductivity than Al–LLZO–Ar and Al–LLZO–Air.     

The synergistic effect of dual substitution of Al and Sb on structure and ionic conductivity of Li7La3Zr2O12 ceramic

Li₇La₃Zr₂O₁₂ (LLZO) with cubic garnet type structure is a promising solid electrolyte. In this work, Li_6.925-3xAl_xLa₃Zr_1.925Sb_0.075O₁₂ (0 ≤ x ≤ 0.1) electrolytes were prepared by conventional solid-state reaction. The influence of Sb-Al cosubstitution on the structure, microstructure and conductivity of Li₇La₃Zr₂O₁₂ were investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and impedance spectroscopy. Single cubic phase has been achieved for Li_6.925-3xAl_xLa₃Zr_1.925Sb_0.075O₁₂ (x = 0–0.075). Suitable amount of Al-Sb cosubstitution accelerates densification and improves the ionic conductivity. Li_6.775Al_0.05La₃Zr_1.925Sb_0.075O₁₂ exhibits highest relative densities (96.7%) and total ionic conductivity (4.10 × 10^?4 S/cm at 30 °C).     

Synthesis of Ga-doped Li7La3Zr2O12 solid electrolyte with high Li+ ion conductivity

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) Li⁺ ion solid electrolyte is a promising candidate for next generation high-safety solid-state batteries. Ga-doped LLZO exhibits excellent Li⁺ ion conductivity, higher than 1 × 10^?3 S cm^?1. In this research, the doping amount of Ga, the calcination temperature of Ga-LLZO primary powders, the sintering conditions and the evolution of grains are explored to demonstrate the optimum parameters to obtain a highly conductive ceramics reproducibly via conventional solid-state reaction methods under ambient air sintering atmosphere. Cubic LLZO phase is obtained for Li_6.4Ga_0.2La₃Zr₂O₁₂ powder calcined at low temperature 850 °C. In addition, ceramic pellets sintered at 1100 °C for 320 min using this powder have relative densities higher than 94% and conductivities higher than 1.2 × 10^?3 S cm^?1 at 25 °C.     

High Li-ion conductivity of Al-doped Li7La3Zr2O12 synthesized by solid-state reaction

Li₇La₃Zr₂O₁₂ (LLZO) has cubic garnet type structure and is a promising solid electrolyte for next-generation Li-ion batteries. In this work, Al-doped LLZO was prepared via conventional solid-state reaction. The effects of sintering temperature and Al doping content on the structure and Li-ion conductivity of LLZO were investigated. The phase composition of the products was confirmed to be cubic LLZO via XRD. The morphology and chemical composition of calcined powders were investigated with SEM, EDS, and TEM. The Li-ion conductivity was measured by AC impedance. The results indicated the optimum sintering temperature range is 800–950 °C, the appropriate molar ratio of LiOH·H₂O, La(OH)₃, ZrO₂ and Al₂O₃ is 7.7:3:2:(0.2–0.4), and the Li-ion conductivity of LLZO sintered at 900 °C with 0.3 mol of Al-doped was 2.11×10⁻⁴ S cm⁻¹ at 25 °C.     

Unveiling the presence of mixed oxidation states of Europium in Li7+δEuxLa3−δZr2−δO12−δ garnet and its impact on the Li-ion conductivity

Recently, lanthanides have been employed by researchers to examine their impact on the structure and properties of Li₇La₃Zr₂O₁₂ (LLZO) garnets. In this regard, we developed Europium oxide (Eu₂O₃) doped LLZO (Li_7+δEu_xLa_3−δZr_2−δO_12−δ) solid electrolyte which demonstrates a cubic phase with the symmetry of Iad (No.230) at room temperature. In this investigation, different concentrations of Eu ranging from 0.1 to 0.6 atoms per formula unit (pfu) were doped into Li₇La₃Zr₂O₁₂ to evaluate the impact of Eu on the stability of the cubic phase and thereby the ionic conductivity. The results unveiled that upon doping Eu³⁺ ions, the Eu²⁺ state is also formed and is then self-doped into the structure in which Rietveld refinement coupled with XPS, EPR, and solid-state NMR suggests that Eu³⁺ ions most probably partially occupy Zr⁴⁺ (16a) site, the Eu²⁺ ions occupy La³⁺ (24d) site, and the Li⁺ ions occupy two different sites (24d and 96h). It was further found that such a site preference induces distortion at LaO₈ polyhedrons opening up the neck for Li-ions diffusion, thereby enhancing the ionic conductivity. Moreover, it was revealed that Li-ions probably hop from 96h to 24d and then to 96h site to generate the Li-ion movement. Overall, by introducing Eu ions into the LLZO structure, an enhanced bulk ionic conductivity of 0.30 × 10⁻³ S/cm at 298 K with a minimum electronic conductivity of 2.547 × 10⁻⁹ S/cm at 298 K was achieved.     

Reaction mechanisms of lithium garnet pellets in ambient air: The effect of humidity and CO2

Li₇La₃Zr₂O₁₂ (LLZO) has been reported to react in humid air to form Li₂CO₃ on the surface, which decreases ionic conductivity. To study the reaction mechanism, 0.5‐mol Ta‐doped LLZO (0.5Ta–LLZO) pellets are exposed in dry (humidity ~5%) and humid air (humidity ~80%) for 6 weeks, respectively. After exposure in humid air, the formation of Li₂CO₃ on the pellet surface is confirmed experimentally and the room‐temperature ionic conductivity is found to drop from 6.45×10^?4 S cm^?1 to 3.61×10^?4 S cm^?1. Whereas for the 0.5Ta–LLZO samples exposed in dry air, the amount of formed Li₂CO₃ is much less and the ionic conductivity barely decreases. To further clarify the reaction mechanism of 0.5Ta–LLZO pellets with moisture, we decouple the reactions between 0.5Ta–LLZO with water and CO₂ by immersing 0.5Ta–LLZO pellets in deionized water for 1 week and then exposing them to ambient air for another week. After immersion in deionized water, Li⁺/H⁺ exchange occurs and LiOH H₂O forms on the surface, which is a necessary intermediate step for the Li₂CO₃ formation. Based on these observations, a reaction model is proposed and discussed.     

Sintering analysis of garnet-type ceramic as oxide solid electrolytes for rapid Li+ migration

Metallic doping can stabilize cubic phase Li₇La₃Zr₂O₁₂ (LLZO) solid electrolyte for high conductivity, due to the enhanced vacancies and disordered Li-site. However, the understanding of metallic doping in the crystal lattice during the high-temperature sintering process is still not clear. In present study, a gradient series of Fe doped LLZO are formulated via solid-phase reaction, and then investigated through crystal analysis and morphological characterization. Pair distribution function essay implies that doped Fe³⁺ promotes random distribution of Li⁺ over the available sites in the located crystal. Additionally, the ceramic morphology confirms that the particles sizes in LLZO pellets suddenly grow above 1000 ℃, and Fe doping can obviously suppress Li loss above 600 ℃. As a result, the LLZF0.15 exhibits the relatively high ionic conductivity of 1.99 × 10^–5 S cm^–1 at 45 ℃.     

Effect of sintering process on the microstructure and ionic conductivity of Li7–xLa3Zr2–xTaxO12 ceramics

Li_7–xLa₃Zr_2–xTa_xO₁₂ (0 ≤ x ≤ 1) ceramics were prepared by pressureless sintering at 1230 °C in air. XRD, SEM and Impedance test were used to characterize the crystal structure, microstructure and electrical performance of Li_7–xLa₃Zr_2–xTa_xO₁₂ ceramics. According to XRD data, the specimens with x ≥ 0.2 sintered at 1230 °C for 1 h exhibit a cubic garnet structure without impurities. The Ta-doped specimens sintered at 1230°C for 1 h show high relative density of 91.6%–93.9%. Ta doping has a certain effect on the Li vacancy concentration, lithium arrangement, movable Li⁺ concentration and microstructure of the LLZO ceramic. The Li_6.6La₃Zr_1.6Ta_0.4O₁₂ ceramic sintered at 1230°C for 1 h has the highest total conductivity of 6.01 × 10^–4 S·cm^–1 at room temperature and the lowest activation energy of 0.27 eV.     

Optimization of Lithium Content and Sintering Aid for Maximized Li+ Conductivity and Density in Ta‐Doped Li7La3Zr2O12

Ta‐doped cubic phase Li₇La₃Zr₂O₁₂ (LLZ) lithium garnet received considerable attention in recent times as prospective electrolyte for all‐solid‐state lithium battery. Although the conductivity has been improved by stabilizing the cubic phase with the Ta⁵⁺ doping for Zr⁴⁺ in LLZ, the density of the pellet was found to be relatively poor with large amount of pores. In addition to the high Li⁺ conductivity, density is also an essential parameter for the successful application of LLZ as solid electrolyte membrane in all‐solid‐state lithium battery. Systematic investigations carried out through this work indicated that the optimal Li concentration of 6.4 (i.e., Li_6.4La₃Zr_1.4Ta_0.6O₁₂) is required to obtain phase pure, relatively dense and high Li⁺ conductive cubic phase in Li_7?xLa₃Zr_2?xTa_xO₁₂ solid solutions. Effort has been also made in this work to enhance the density and Li⁺ conductivity of Li_6.4La₃Zr_1.4Ta_0.6O₁₂ further through the Li₄SiO₄ addition. A maximized room‐temperature (33°C) total (bulk + grain boundary) Li⁺ conductivity of 3.7 × 10^?4 S/cm and maximized relative density of 94% was observed for Li_6.4La₃Zr_1.4Ta_0.6O₁₂ added with 1 wt% of Li₄SiO₄.     

Phase evolution during reactive flash sintering of Li6.25Al0.25La3Zr2O12 starting from a chemically prepared powder

Reactive flash sintering (RFS) of a chemically prepared multiphase precursor powder was performed to fabricate Li_6.25Al_0.25La₃Zr₂O₁₂ (Al-LLZO) ceramics. This approach allowed for obtaining single-phase dense samples in a remarkably short processing time of 30 s, at a furnace temperature of 600 °C, with an electric field of 50 V cm^?1 and a current limit of 150 mA mm^-2. The ceramics display high bulk conductivity of 0.18 mS cm^?1 at room temperature. Furthermore, phase evolution is studied by in-situ X-ray diffraction during: i) conventional heating and ii) RFS under current rate mode. As expected, the intermediate phases progressively dissolved into the Al-LLZO matrix by conventional heating. On the other hand, RFS promoted the growth of the intermediate La₂Zr₂O₇, an effect that was overcome by the thermally driven formation of Al-LLZO at higher temperatures. The observed different reaction pathway suggests that RFS can be used for stabilizing phases that are not thermodynamically favored upon conventional heating.     

Effect of Li2O excess in Li6.4Ga0.2La3Zr2O12 electrolyte for all-solid-state Li-ion batteries

Li₇La₃Zr₂O₁₂ is a promising material used as solid electrolyte in all-solid-state lithium batteries. However, the lithium ionic conductivity of LLZO is limited, and the cycling stability of lithium symmetric battery based on LLZO is not good. In this research, different Ga-doped LLZO samples were prepared by adding different excess amounts of Li₂O, and the effect of excess amount of Li₂O on the structure and performance of LLZO have been researched. The results show that with the rise of the amount of Li₂O, the lithium ionic concentration increases gradually, and the lithium ionic conductivity and the ratio of grain resistance to total resistance rise first and then drop. When the excess amount of Li₂O is 10 wt.%, the sample exhibits the highest lithium ionic conductivity of 1.36 mS/cm, and the lithium symmetric battery exhibits the most stable operation.     

Dual regulation of Li+ migration of Li6.4La3Zr1.4M0.6O12 (M = Sb,Ta, Nb) by bottleneck size and bond length of M−O

Bottleneck size is the minimum Li⁺ migration channel of Li₇La₃Zr₂O₁₂ (LLZO) and it greatly influences the Li⁺ conductivity. Doping different elements on the Zr site of LLZO can adjust the bottleneck size and improve the Li⁺ conductivity. However, the regulation mechanism is not clear. In this work, Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) has been prepared and the bottleneck size has been adjusted by doping different pentavalent ions. The results manifest that the cell parameter and bottleneck size decrease with the rise of the radius of doped pentavalent ions. This is because larger pentavalent ion leads to larger bond length of M–O, and weaker covalent component between M⁵⁺ and O^2-, corresponding, the formal charge on the M⁵⁺ become larger, and the bond length of La–O slightly decreases due to the coulomb repulsion between La³⁺ and M⁵⁺ increase. While, the activation energy drop firstly and then rise with the rise of bottleneck size because of the migration of Li⁺ not only relate to the size of the migration channel but also to the strength of M–O covalent bonding. The bottleneck size and bond length of M–O synergistically affect the migration of Li⁺.     

Achieving enhanced densification and superior ionic conductivity of garnet electrolytes via a co-doping strategy coupled with pressureless sintering

Lithium garnet oxides with 6.5 mol Li, such as Li_6.5La₃Zr_1.5(Ta/Nb)_0.5O₁₂, typically crystallise in cubic structure and exhibit excellent room-temperature ionic conductivity close to 1 mS cm^?1. However, it is challenging to densify garnet oxides. In this work, we investigated how the co-doping of tantalum (Ta) and niobium (Nb) affects the densification of pressureless sintered garnet electrolytes with compositions of Li_6.5La₃Zr_1.5Ta_(0.5?x)Nb_xO₁₂, where x = 0–0.5. The highest densification (94.5% of relative density) was achieved in Li_6.5La₃Zr_1.5Ta_0.1Nb_0.4O₁₂ (TN-LLZO) when it was sintered at 1150 °C for 6 h. This TN-LLZO garnet electrolyte delivers an ionic conductivity of 1.04 × 10^?3 S cm^?1 (at 22 °C) with a low activation energy of 0.41 eV. Our findings demonstrate that the content of dopants (Ta and Nb) plays a critical role in enhancing the sintering performance of garnet ceramics at ambient pressure.     

Dopant effect on Li+ ion transport in NASICON-type solid electrolyte: Insights from molecular dynamics simulations and experiments

The performance of sodium superionic conductor (NASICON)-type LiZr₂(PO₄)₃ (LZP) solid electrolytes for Li-ion batteries is dependent on their ion transportation properties. Therefore, to achieve high stability, ionic conductivity, and good compatibility with Li, the LZP solid electrolyte has chosen and doped with Al to improve aforesaid properties. Also, the effect of the dopant on various parameters has been investigated via MD simulations and experimentally. In this study, molecular dynamics (MD) simulations were used to investigate the effect of Al doping on the ion transport properties of Li_1+xAl_xZr_2?x(PO₄)₃ (LAZP, x = 0.0–1.0) solid electrolytes. A facile solid-state reaction was used to synthesize both pristine and Al-doped solid electrolytes and to estimate the effect of doping on the ionic conductivity and ion diffusion in LZP. Computational and experimental results provided strong evidence of improved ion conductivity and diffusion in LZP owing to the presence of the Al dopant. Furthermore, the computational results agreed well with the experimental results, thereby validating the computational model. A maximum ionic conductivity of σ_Li = 2.77 × 10^?5 S cm ^?1 (for x = 0.2) was obtained. Enhanced ionic conductivity was observed with Al dopants owing to the creation of interstitial Li ions through a reduction in grain boundary resistance. However, a further increase in the amount of dopant reduced the ionic conductivity of LZP owing to Li-ion trapping at the most stable and metastable sites around the Al insertions. Doped LZP solid electrolytes are suitable for use in energy storage devices because of their enhanced ionic conductivity compared to that of pristine LZP.     

Enhanced Li-ion conductivity of strontium doped Li-excess garnet-type Li7+xLa3-xSrxZr2O12

The mechanism underlying the enhancement of the conductivity of Li₇La₃Zr₂O₁₂ (LLZO), an oxide-based solid electrolyte that contains excess Li, was experimentally investigated through subvalent cation substitution. We prepared Sr-substituted Li-rich LLZO with high conductivity of the order of 10⁻⁴ S/cm by using a solid-state method. We investigated the mechanism underlying the conductivity enhancement via detailed structural analysis through Sr K-edge X-ray absorption near edge spectroscopy and X-ray diffraction and neutron powder diffraction analyses. The results suggested that the conductivity enhancement is due to the change in Li⁺ arrangement caused by the incorporation of excess Li into the LLZO lattice.     

High densification and Li-ion conductivity of Al-free Li7-xLa3Zr2-xTaxO12 garnet solid electrolyte prepared by using ultrafine powders

Ta-doped Li₇La₃Zr₂O₁₂ (Ta-LLZO) is considered as a promising solid electrolyte due to high Li-ion conductivity and good chemical stability against electrode materials. In this work, Ta-LLZO was prepared by a conventional solid-state reaction. Ultrafine powders were obtained by ball-milling to improve the surface activity. Ta-LLZO is sintered in ZrO₂ crucibles to avoid introducing Al into the samples. The particle size distribution, phase structure, morphology, ionic conductivity, electronic conductivity, density and electrochemical performance of semi-solid battery were characterized by laser diffraction particle size analyzer, X-ray diffraction, scanning electron microscope, AC-impedance, DC polarization, Archimedes method and a battery testing system, respectively. The results show that the ball milling to reduce the particle size is an effective way to solve the problem of relatively low density and Li-ion conductivity for Al-free Li_7-xLa₃Zr_2-xTa_xO₁₂. For Al-free Li_7-xLa₃Zr_2-xTa_xO₁₂, the increase of x (0.2?≤?x?≤?0.4) promotes the grain growth and sintering densification, but the increase of x (0.4?<?x?≤?0.6) has an adverse effect. Li_6.7La₃Zr_1.7Ta_0.3O₁₂ sintered at 1180?°C for 12?h shows the relative density of 92% and the highest Li-ion conductivity of 1.03?×?10^?3 S/cm at ³0?°C with the activation energy of about 0.37?eV, while Li_6.6La₃Zr_1.6Ta_0.4O₁₂ sintered at 1180?°C for 12?h shows the highest relative density of 96% and the Li-ion conductivity of 6.68?×?10^?4 S/cm at 30?°C with the activation energy of about 0.46?eV. The electronic conductivity of Al-free Li_7-xLa₃Zr_2-xTa_xO₁₂ is 10^?9 S/cm orders of magnitude. The semi-solid battery shows the first discharge capacity of 104.6 mAh/g and 92.5% capacity retention after 20 cycles.     

Microstructure and Li‐Ion Conductivity of Hot‐Pressed Cubic Li7La3Zr2O12

The effect of hot‐pressing temperature on the microstructure and Li‐ion transport of Al‐doped, cubic Li₇La₃Zr₂O₁₂ (LLZO) was investigated. At fixed pressure (62 MPa), the relative density was 86%, 97%, and 99% when hot‐pressing at 900°C, 1000°C, and 1100°C, respectively. Electrochemical impedance spectroscopy showed that the percent grain‐boundary resistance decreased with increasing hot‐pressing temperature. Hot pressing at 1100°C resulted in a total conductivity of 0.37 mS/cm at room temperature where the grain boundaries contributed to 8% of the total resistance; one of the lowest grain‐boundary resistances reported. We believe hot pressing is an appealing technique to minimize grain‐boundary resistance and enable correlations between LLZO composition and bulk ionic conductivity.