Ultrafast high-temperature sintering of Li7La3Zr1.75Nb0.25Al0.15O12 (LLZO)

Rapid sintering of Li₇La₃Zr_1.75Nb_0.25Al_0.15O₁₂ (LLZO) is reported. The selection of heating elements, the effect of powder preparation and MgO additions in rapid sintered LLZO are described. Annealing LLZO powder at 750 ºC for 2 h in argon immediately before pressing helped to minimize porosity. A 15–20 s hold at 1372 ºC was sufficient to achieve densities >97%. The total sintering schedule time for rapid sintering represents a 99.7% decrease in sintering time compared to conventional sintering. At 70 °C under a pressure of 4.12 MPa cells had a critical current density of 1020 µA/cm².     

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.     

Improving the Li-ion conductivity and air stability of cubic Li7La3Zr2O12 by the co-doping of Nb,Y on the Zr site

The elements Nb and Y were simultaneously substituted to the Zr sites of an Li₇La₃Zr₂O₁₂ (LLZO) electrolyte to improve its Li-ion conductivity and air stability. Samples of Li₇La₃Zr_2-2xNb_xY_xO₁₂ were fabricated using a solid-state reaction method. The results show that the introduction of Nb and Y can stabilise cubic-phase LLZO. The total conductivity of Li₇La₃ZrNb_0.5Y_0.5O₁₂ electrolyte can reach 8.29 × 10^?4 S cm^?1 at 30 °C when sintered at 1230 °C for only 15 h. Surprisingly, the conductivity of Li₇La₃ZrNb_0.5Y_0.5O₁₂ can be maintained at 6.91 × 10^?4 S cm^?1 after exposure to air for 1.5 months, indicating excellent air stability. Furthermore, a LiFePO₄/Li₇La₃ZrNb_0.5Y_0.5O₁₂/Li cell displayed stable charge/discharge and cycling performance at ambient temperature, suggesting there is potential to use Li₇La₃ZrNb_0.5Y_0.5O₁₂ electrolyte in Li-ion batteries. Additionally, the effects of varying the co-doping amount and dwelling time on the Li-ion conductivity of Li₇La₃Zr_2-2xNb_xY_xO₁₂ were investigated.     

锂含量与烧结时间对固体电解质Li7La3Zr2O12电导率的影响

具有石榴石结构的固体电解质Li7La3Zr2O12在室温下即可呈现出较高的离子电导率。采用固相反应法,通过在原料中调控不同的锂源含量,以及经历不同的烧结时间,探索了上述制备工艺条件对样品室温离子电导率的影响规律。结果表明：采用不同的锂含量均可获得立方石榴石结构;当混合原料中的锂源采用–3%Li含量时,可以获得最高电导率(2.11×10–4 S/cm);对于不含锂过量的原料,当烧结时间为30 h时,可以获得最高电导率2.03×10–4 S/cm。这些结果表明Li7La3Zr2O12在全固态锂离子电池中具有广阔的应用前景。     

Ce incorporated pyrochlore Pr2Zr2O7 solid electrolytes for enhanced mild-temperature NO2 sensing

NO₂ sensor has attracted extensive attention due to its important application in environment monitor. Conventional NO₂ sensors based on the yttria-stabilized zirconia (YSZ) electrolyte possess fast response, high sensitivity and good stability, whereas its ionic conductivity decreases significantly at low- and intermediate-temperature, limiting the practical application in motor vehicles. In this work, a pyrochlore-phase A₂B₂O₇ solid electrolyte, Pr₂Zr_2−xCe_xO_7+δ (PZC), was applied for the first time to construct the amperometric-type NO₂ sensor. Ce incorporated significantly improved the sensing performance of the PZC NO₂ sensor with NiO as the sensing electrode. The effect of Ce-doped concentration and operating temperature on the sensitivity, selectivity, stability, response and recovery characteristics were investigated in detail. The results showed that the optimal sensor based on the Pr₂Zr_1.9Ce_0.1O_7+δ substrate gave high sensitivity, excellent selectivity and quick response-recovery behavior to NO₂ gas. The gas-sensing mechanism was also discussed. The PZC sensors are well established effective for sensing NO₂ at mild-temperature working window of 500–700 °C, and thus exhibit the promising application in motor vehicles.     

固态无机电解质Li7La3Zr2O12的改性研究进展

作为一种固态无机电解质材料,石榴石型立方相Li₇La₃Zr₂O₁₂具有较高的室温锂离子电导率、较宽的电化学窗口和优良的热稳定性等特点,是高安全性、高能量密度固态锂离子电池实现商业化应用的关键。阐述了Li₇La₃Zr₂O₁₂的晶体结构与锂传导机理,综述了元素掺杂、聚合物电解质复合、烧结助剂引入、表面包覆或修饰等方式对Li₇La₃Zr₂O₁₂的物相结构稳定性、界面阻抗与相容性、烧结活性、离子电导率等进行改性的最新研究进展。最后,针对Li₇La₃Zr₂O₁₂在产业化应用中所面临的障碍与挑战,提出了制备新工艺的开发、离子电导率的多重改性以及柔性复合电解质膜的结构设计与优化等应对策略,为推动高性能固态锂离子电池的发展提供依据。     

Phase transformation and grain-boundary segregation in Al-Doped Li7La3Zr2O12 ceramics

Cubic phase garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al₂O₃. The reported ionic conductivities were variable due to the complicated Al³⁺-Li⁺ substitution and Li_xAlO_y segregation in Al-LLZO ceramics. This work prepared Li_7?3xAl_xLa₃Zr₂O₁₂ (x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution, and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li⁺ ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO₂ and LaAlO₃ segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li⁺ ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li_6.04Al_0.32La₃Zr₂O₁₂ ceramic delivers the optimum Li⁺ ion conductivity of 1.7 × 10^?4 S cm^?1 at 25 °C.     

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.     

Dense freeze-cast Li7La3Zr2O12 solid electrolytes with oriented open porosity and contiguous ceramic scaffold

Freeze casting is used for the first time to prepare solid electrolyte scaffolds with oriented porosity and dense ceramic walls made of Li₇La₃Zr₂O₁₂ (LLZO), one of the most promising candidates for solid-state battery electrolytes. Processing parameters—such as solvent solidification rate, solvent type, and ceramic particle size—are investigated, focusing on their influence on porosity and ceramic wall density. Dendrite-like porosity is obtained when using cyclohexane and dioxane as solvents. Lamellar porosity is observed in aqueous slurries resulting in a structure with the highest apparent porosity and densest ceramic scaffold but weakest mechanical properties due to the lack of interlamellar support. The use of smaller LLZO particle size in the slurries resulted in lower porosity and denser ceramic walls. The intrinsic ionic conductivity of the oriented LLZ ceramic scaffold is unaffected by the freeze casting technique, providing a promising ceramic scaffold for polymer infill in view of designing new types of ceramic-polymer composites.     

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.     

Overcoming the abnormal grain growth in Ga-doped Li7La3Zr2O12 to enhance the electrochemical stability against Li metal

Li₇La₃Zr₂O₁₂ (LLZO) solid electrolyte is a promising candidate for next generation batteries. In the LLZO family with various doping elements, Ga-doped LLZO (Ga-LLZO) delivers the highest Li-ion conductivity of higher than 1 × 10⁻³ S cm⁻¹. However, Ga-LLZO ceramics always contain lots of overgrown huge grains after sintering, resulting in short-circuiting as applied with Li anode in batteries. Hence a simple two-step sintering strategy is developed to prepare fine-grained Ga-LLZO ceramics with good electrochemical properties. Pellets with the composition of Li_6.4Ga_0.2La₃Zr₂O₁₂ deliver pure garnet phase, uniform fine grains, high relative density of 97.3% and conductivity of 1.24 × 10⁻³ S cm⁻¹ at 27 °C after sintering at 1150 °C for 1 min and 1000 °C for 3 h. In addition, those fine-grained Ga-LLZO exhibit improved stability against molten Li. The Li/Ga-LLZO/Li symmetric cells show a critical current density of 0.7 mA cm⁻², and a stable cycling of over 600 h at 0.4 mA cm⁻² at 27 °C. The Li/Ga-LLZO/LiFePO₄ full cells deliver reversible capacity of 150 mAh g⁻¹, showing negligible decay after 50 cycles. These results bring the Ga-LLZO electrolytes one step closer to practical application in solid-state batteries.     

Effect of Li4SiO4 addition in Li6.22Al0.16La3Zr1.7Ta0.3O12 garnet type solid electrolyte for lithium ion battery application

Li_6.22Al_0.16La₃Zr_1.7Ta_0.3O₁₂ has been synthesized by solid state reaction method. With a view to reduce the sintering temperature and duration, the addition of Li₄SiO₄ has been done as sintering aid. The formation of desired phase was confirmed by XRD. The density of the ceramic samples was measured. The morphological study of ceramic samples was carried out from SEM. The elemental distribution has been studied using HRTEM analysis. IR spectra have been studied to know the structural groups present in the ceramic samples. The ionic conductivity of all samples has been measured using complex impedance analysis. The effect of Li₄SiO₄ addition on ionic conductivity of ceramic samples has been studied. The highest conductivity of 7.52 × 10⁻⁵ Scm⁻¹ at 25 °C was observed for 2 wt% Li₄SiO₄ added sample. This sample has a potential for being used as solid electrolyte for solid state lithium battery applications.     

湿化学法制备石榴石型固态电解质Li7La3Zr2O12

锂电池因能量密度高、循环寿命长、绿色清洁等特点被广泛应用,但其液态电解质易泄漏、挥发,且隔膜易被锂枝晶刺穿造成短路,引发危险。固态电解质大多是不具燃烧性的无机材料,室温下离子电导率较高、电化学窗口宽且适用温度范围广。因此,采用固态电解质替代液态电解质具有十分重要的意义。相对于其他类型固态电解质,石榴石型氧化物Li₇La₃Zr₂O₁₂（LLZO）具有离子电导率高、电化学窗口宽（>5V vs. Li/Li⁺）、对锂稳定性好和热稳定性高等特点,是非常具有发展潜力的无机固态电解质。本文采用溶胶-凝胶法和低温燃烧法两种湿化学法合成LLZO粉末,对应的电解质片在40℃时的离子电导率分别为1.22×10^-5S/cm和3.87×10^-6S/cm,活化能分别为0.34eV和0.32eV。从实验结果综合比较,溶胶-凝胶法为最佳制备方法。     

石榴石型固态电解质Li7La3Zr2O12的改性研究现状

固态电解质是高安全性、高能量密度的全固态锂电池的核心部件,其典型代表Li₇La₃Zr₂O₁₂(LLZO)具有高离子电导率、高机械强度、高电化学稳定性、低界面阻抗以及对锂金属负极良好的稳定性等优势,是科研人员重点关注的对象之一,但与液态电解质相比,目前LLZO仍存在低离子电导率和与电极固-固界面接触等问题。本文主要简介了LLZO的晶体结构、改性方式等对其离子电导率及界面阻抗的影响,同时对LLZO现存的问题进行了总结,对LLZO的未来发展方向进行了展望,为探索全固态锂电池的实际生产应用提供理论指导。     

Fracture toughness of single grains and polycrystalline Li7La3Zr2O12 electrolyte material based on a pillar splitting method

In the present study an advanced pillar splitting method is used to determine the fracture toughness of a garnet-type Li₇La₃Zr₂O₁₂ (LLZO) electrolyte. The obtained results are compared to data derived on the basis of conventional Vickers indentation. Furthermore, potential micro-pillar size effects are investigated. The estimated fracture toughness values for single grains and polycrystalline LLZO material obtained via both methods are in good agreement, yielding ∼ 1 MPa m^0.5, hence the data indicate that LLZO exhibits relatively low fracture toughness and has a brittle behavior.     

Li7La3Zr2O12 solid electrolyte sintered by the ultrafast high-temperature method

All-solid-state Li batteries (ASSLBs) are regarded as the systems of choice for future electrochemical energy storage. Particularly, the garnet Li₇La₃Zr₂O₁₂ (LLZO) is one of the most promising solid electrolytes due to its stability against Li metal. However, its integration into ASSLBs is challenging due to high temperature and long dwell time required for sintering. Advanced sintering techniques, such as Ultrafast High-temperature Sintering, have shown to significantly increase the sintering rate. Direct contact to graphite heaters allows sintering of LLZO within 10 s due to extremely high heating rates (up to 10⁴ K min^?1) and temperatures up to 1500 °C to a density around 80 %. The LLZO sintered in vacuum and Ar atmosphere has good mechanical stability and high phase purity, but kinetic de-mixing at the grain boundaries was observed. Nevertheless, the Li-ion conductivity of 1 mS cm^?1 at 80 °C was comparable to conventional sintering, but lower than for Field-Assisted Sintering Technique/Spark Plasma Sintering.     

Improving room-temperature electrochemical performance of solid-state lithium battery by using electrospun La2Zr2O7 fibers-filled composite solid electrolyte

Low ionic conductivity at room temperature and poor interfacial compatibility are the main obstacles to restrain the practical application of polymer solid electrolytes. In this work, lanthanum zirconate (LZO) fibers were prepared by electrospinning method and used for the first time as fillers in sandwich polypropylene carbonate (PPC)-based solid electrolyte. Meanwhile, a graphite coating was applied on one surface of the composite solid electrolyte (CSE) membrane. The results show that the LZO fibers significantly increases the room-temperature electrochemical performance of the CSE, and the graphite coating enhances the interfacial compatibility between electrolyte and lithium anode. Furthermore, an ultra-thin PPC-LZO CSE with a total thickness of 22 μm was prepared and used in NCM622/CSE/Li solid-state cell, which shows an initial discharge capacity of 165.6 mAh/g at the current density of 0.5C and a remaining capacity of 113.0 mAh/g after 250 cycles at room temperature. Rise to 1C, the cell shows an initial discharge capacity of 154.2 mAh/g with a remaining capacity of 95.6 mAh/g after 250 cycles. This ultra-thin CSE is expected to be widely applied in high energy-density solid-state battery with excellent room-temperature electrochemical performances.     

Preparation of Li6Zr2O7 Nanofibers with High Li‐Ion Conductivity by Electrospinning

Li₆Zr₂O₇ nanofibers were synthesized by a simple electrospinning technique. The thermal decomposition behavior, crystal structure, micromorphology, and electrical conductivity of the as‐prepared Li₆Zr₂O₇ nanofibers were characterized. The results show that Li₆Zr₂O₇ nanofibers were of pure phase after calcined at 750°C for 1 h. In addition, the as‐prepared Li₆Zr₂O₇ nanofibers reveal high conductivity in the measured temperature region, which can be attributed to the huge surface and nanosize effect of the nanofiber electrolyte. Moreover, we provide a general method to improve the conductivity of Li‐ion solid electrolyte.     

Ta、Ba共掺杂石榴石型Li7La3Zr2O12电解质的制备及性能研究

传统锂离子电池采用有机电解液体系,能量密度难以进一步提升,同时存在一定的安全隐患。采用无机固体电解质构建全固态锂电池,在提高电池能量密度同时可兼顾安全性问题。在众多无机固体电解质中,Li₇La₃Zr₂O₁₂(LLZO)石榴石电解质具有离子电导率高、与金属锂接触稳定等优势,成为受人关注的材料。为了进一步提高该材料的导电性,采用固相法合成Ta、Ba共掺杂LLZO(Li_7-x+yLa_3-yBa_yZr_2-xTa_xO₁₂)电解质,采用X射线衍射、扫描电子显微镜和电化学阻抗法分析样品的物相结构、微观形貌及离子电导率。结果表明,Ta⁵⁺掺杂能够稳定立方相结构,Ba²⁺作为掺杂剂和烧结剂,促进晶粒生长和陶瓷致密化,从而降低总电阻。其中,Li_6.45La_2.95Ba_0.05Zr_1.4Ta_0.6O₁₂样品在室温下的总电导率为1.07×10^-3 S·cm^-1,活化能为0.378 eV。Ta⁵⁺/Ba²⁺共掺杂有利于制备高致密度和高电导率的石榴石型电解质材料。     

Rapid synthesis of garnet-type Li7La3Zr2O12 solid electrolyte with superior electrochemical performance

Li₇La₃Zr₂O₁₂-based garnet-type solid electrolytes are promising candidates for use in all-solid-state lithium batteries (ASSLBs). However, their potential in large-scale commercial applications is largely hindered by the time/energy-consuming and lithium-wasting synthetic method which typically needs a long-duration high temperature solid state reaction process. Herein we invent a fast preparation route that involves a short-period thermal reaction (1100 °C for 10 min) in laboratory muffle furnaces following by conventional hot pressing technique to get almost fully dense (Al, Ga, Ta, Nb)-doped garnet-type electrolytes with high phase purity (>99.9 %). The large and compact grains, low porosity and high phase purities of garnet ceramic electrolytes synthesized in this study ensure superior electrochemical performance. Particularly, Ga-doped cubic Li₇La₃Zr₂O₁₂ shows extremely low E_a values (0.17?0.18 eV) and record-high lithium ionic conductivities (>2 × 10^?3 S cm^-1 at 25 °C).