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).     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Prompting structure stability of O3–NaNi0.5Mn0.5O2 via effective surface regulation based on atomic layer deposition

Layered O3 type oxides exhibit promising prospects as high-performance cathodes for sodium-ion batteries (SIBs) due to their low cost and high theoretical capacities. Nevertheless, the intrinsic surface composition and bulk structure degradation upon cycling presents a huge obstacle to stable sodium-ion storage/transportation. Besides, the effective surface decoration on layered O3 oxides is still challenging through conventional wet chemical route owing to their extraordinarily high surface sensitivities. Herein, a typical O3 type layered oxide of NaNi_0.5Mn_0.5O₂ (NNMO) was selected and successfully encapsulated by precisely controlled Al₂O₃ layers via atomic layer deposition (ALD) technology. With the optimally controlled Al₂O₃ thickness of 3 nm, the surface regulated NNMO delivers a highly reversible capacity of 73.6 mA h g^-1, with a significantly improved capacity retention of 68.0% after 300 cycles at 0.5 C, and a superior rate capability of 65.8 mA h g^-1 at 10 C. Further air sensitivity tests demonstrate that the protective layer could effectively mitigate the generation of sodium-based impurities on NNMO, and reduce the surface sensitivities. Both chemical and electrochemical aging tests confirm the contribution of Al₂O₃ coating layer in alleviating ion dissolution as well as stabilizing the structure and morphology of NNMO. Based on regulating the surface of O3 type layered oxides utilizing ALD technique, this work supplies an effective and facile strategy to overcome the challenges from fast structure degradation and electrochemical property decay, which not only highlights the significance and effectiveness of surface engineering in secondary batteries, but also sheds light on accurate interface construction and regulation for active electrode materials, particularly for those sensitive to ambient atmosphere.     

High-rate capability of carbon-coated micron-sized hexagonal TT-Nb2O5 composites for lithium-ion battery

With excellent specific capacity, superior cycle stability, safety and strong practical, Nb₂O₅ has been considered as one of the prospective anode materials for lithium-ion batteries (LIBs). However, current study suggests that Nb₂O₅ electrode materials for LIBs still face the vital issues of low electrical conductivity and poor rate performance. Therefore, carbon-coated TT-Nb₂O₅ materials are designed and synthesized through solid state method in this work, which present high specific capacity (228 mA h g^?1 at 0.2C), satisfactory rate properties (107 mA h g^?1 at 20 C). The outstanding electrochemical property can not only give the credit to the pseudocapacitance effect of TT-Nb₂O₅, but also attribute to introduction of carbon. The homogeneous carbon-coated materials enhance the electrical conductivity, increase the electron transmission speed and alleviate particle crushing. This research not only offers a new method for preparing excellent electrode materials, but also provides a kind of excellent anode material with prospective application for LIBs.     

Advances in multimetallic alloy-based anodes for alkali-ion and alkali-metal batteries

In order to meet the growing demand of portable electronic devices and electric vehicles, enhancements in battery performance metrics are required to provide higher energy/power densities and longer cycle lives, especially for anode materials. Alloying anodes, such as Group IVA elements-based materials, are attracting increasing interest as anodes for next-generation high-performance alkali-metal-ion batteries (AMIBs) owing to their extremely high specific capacities, low working voltages, and natural abundance. Nevertheless, alloying-type anodes usually display unsatisfactory cycle life due to their intrinsic violent volumetric and structural changes during the charge–discharge process, causing mechanical fracture and exacerbating side reactions. In order to overcome these challenges, efforts have been made in recent years to manufacture multimetallic anodes that can accommodate the induced strain, thus showing high Coulomb efficiency and long cycle life. Meanwhile, much work has been conducted to understand the details of structural changes and reaction mechanisms taking place by in-situ characterization methodologies. In this paper, we review the various recent developments in multimetallic anode materials for AMIBs and shed light on optimizing the anode materials. Finally, the perspectives and future challenges in achieving the practical applications of multimetallic alloy anodes in high-energy AMIB systems are proposed.     

Polymer electrolytes and interfaces in solid-state lithium metal batteries

The polymer electrolyte based solid-state lithium metal batteries are the promising candidate for the high-energy electrochemical energy storage with high safety and stability. Moreover, the intrinsic properties of polymer electrolytes and interface contact between electrolyte and electrodes have played critical roles for determining the comprehensive performances of solid-state lithium metal batteries. In this review, the development of polymer electrolytes with the design strategies by functional units adjustments are firstly discussed. Then the interfaces between polymer electrolyte and cathode/anode, including the interface issues, remedy strategies for stabilizing the interface contact and reducing resistances, and the in-situ polymerization method for enhancing the compatibilities and assembling the batteries with favorable performances, have been introduced. Lastly, the perspectives on developing polymer electrolytes by functional units adjustment, and improving interface contact and stability by effective strategies for solid-state lithium metal batteries have been provided.     

Single-Crystalline TiO2(B) Nanobelts with Unusual Large Exposed {100} Facets and Enhanced Li-Storage Capacity

The {100} facet of single-crystalline TiO₂(B) is an ideal platform for inserting Li ions, but it is hard to be obtained due to its high surface energy. Here, the single-crystalline TiO₂(B) nanobelts from H₂Ti₃O₇ with nearly 70% {100} facets exposed are synthesized, which significantly enhances Li-storage capacity. The first-principle calculations demonstrate an ab in-plane 2D diffusion through the exposed {100} facets. As a consequence, the nanobelts can significantly accommodate Li ions in LiTiO₂ formula with specific capacity up to 335 mAh g⁻¹, which is in good agreement with the electrochemical characterizations. Coating with conductive and protective poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), the cut-off discharge voltage is as low as 0.5 V, leading to a capacity of 160.7 mAh g⁻¹ after 1500 cycles with a retention rate of 66% at 1C. This work provides a practical strategy to increase the Li-ion capacity and cycle stability by tailoring the crystal orientation and nanostructures.     

Structural,magnetic and magnetostrictive properties of Co1-xLixFe2O4 synthesized by cathode materials of spent Li-ion batteries

In this study, we investigated the effects of substituting Li⁺ for Co²⁺ at the B sites of the spinel lattice on the structural, magnetic and magnetostrictive properties of cobalt ferrites. The Li⁺ substituted cobalt ferrites, Co_1-xLi_xFe₂O₄, with x varying from 0 to 0.7 in 0.1 increments, were synthesized with a sol-gel auto-combustion method using the cathode materials of spent Li-ion batteries. X-ray diffraction analysis revealed that all the Co_1-xLi_xFe₂O₄ nanopowders had a single-phase spinel structure and the lattice parameters decreased with increasing Li⁺ content, which can be proved by slight shifts towards higher diffraction angle values of the (311) peak. Field emission scanning electron microscopy was used to observe the fractured inner surface of the sintered cylindrical rods and the increased porosity resulted in a decreased magnetostriction. The oxidation states of Co and Fe in the cobalt ferrite samples were examined by X-ray photoelectron spectroscopy. High resolution transmission electron microscopy micrographs showed that most particles were roughly spherical and with sizes of 25–35?nm. Li⁺ substitution had a strong effect on the saturation magnetization and coercivity, which were characterized with a vibrating sample magnetometer. The Curie temperature was reduced due to the decrease in magnetic cations and the weakening of the exchange interactions. The magnetostrictive properties were influenced by the incorporation of Li⁺ at the B sites of the spinel structure and correlated with the changes in porosity, magnetocrystalline anisotropy and the cation distribution.     

锂离子电池用聚合物电解质的最新进展II.含液聚合物电解质

由于干态聚合物电解质目前还不能满足聚合物锂离子电池的应用要求,人们致力于开发含液体增塑剂的聚合物电解质,包括凝胶型和微孔型两类体系。本文综述了含液聚合物电解质的最新进展,重点论述了各种新体系和新方法。     

Quantum chemical studies of Li cation binding to polyalkyloxides

A quantum chemical study of the binding of Li⁺ cation to polyalkyloxides has been carried out. The lithium cation interaction with three polyalkyloxides (polyethylene oxide (PEO), polytrimethylene oxide (PTMO), and polypropylene oxide (PPO)) has been investigated using ab initio molecular orbital theory at the HF/6-31G^* level with molecular models for the polymers. Coordination by one to six oxygens was considered. In addition, higher level calculations were carried out using G3(MP2) theory for coordination of Li⁺ by one oxygen. For coordination of lithium by one oxygen, the binding energy ordering is PTMO>PPO>PEO, with PTMO having the largest lithium cation affinity. The same ordering is found for larger coordination numbers with the exception of coordination by six oxygens, where the ordering changes due to the steric interactions.