Nanoporous Anatase TiO<sub>2</sub> Mesocrystals: Additive-Free Synthesis, Remarkable Crystalline-Phase Stability, and Improved Lithium Insertion BehaviorJianfeng Ye, Wen Liu, Jinguang Cai et al.|Journal of the American Chemical Society|2010 Unique spindle-shaped nanoporous anatase TiO(2) mesocrystals with a single-crystal-like structure and tunable sizes were successfully fabricated on a large scale through mesoscale assembly in the tetrabutyl titanate-acetic acid system without any additives under solvothermal conditions. A complex mesoscale assembly process involving slow release of soluble species from metastable solid precursors for the continuous formation of nascent anatase nanocrystals, oriented aggregation of tiny anatase nanocrystals, and entrapment of in situ produced butyl acetate as a porogen was put forward for the formation of the anatase mesocrystals. It was revealed that the acetic acid molecules played multiple key roles during the nonhydrolytic processing of the [001]-oriented, single-crystal-like anatase mesocrystals. The obtained nanoporous anatase mesocrystals exhibited remarkable crystalline-phase stability (i.e., the pure phase of anatase can be retained after being annealed at 900 °C) and improved performance as anode materials for lithium ion batteries, which could be largely attributed to the intrinsic single-crystal-like nature as well as high porosity of the nanoporous mesocrystals.
Lithium Storage in Ordered Mesoporous Carbon (CMK‐3) with High Reversible Specific Energy Capacity and Good Cycling PerformanceCarbonaceous materials with high specific energy capacity are prime candidates for applications in rechargeable lithium batteries. The authors report the synthesis and characterization of ordered mesoporous carbon (CMK‐3), synthesized using ordered silica as a template, with high reversible specific capacity and good charge–discharge cycle characteristics. The performance of CMK‐3 is compared with that of carbon nanotubes, and its superiority is suggested to be related to the three‐dimensional ordered structure of CMK‐3.
Thiol‐Branched Solid Polymer Electrolyte Featuring High Strength, Toughness, and Lithium Ionic Conductivity for Lithium‐Metal BatteriesHangchao Wang, Qian Wang, Xin Cao et al.|Advanced Materials|2020 Abstract Lithium‐metal batteries (LMBs) with high energy densities are highly desirable for energy storage, but generally suffer from dendrite growth and side reactions in liquid electrolytes; thus the need for solid electrolytes with high mechanical strength, ionic conductivity, and compatible interface arises. Herein, a thiol‐branched solid polymer electrolyte (SPE) is introduced featuring high Li + conductivity (2.26 × 10 −4 S cm −1 at room temperature) and good mechanical strength (9.4 MPa)/toughness (≈500%), thus unblocking the tradeoff between ionic conductivity and mechanical robustness in polymer electrolytes. The SPE (denoted as M‐S‐PEGDA) is fabricated by covalently cross‐linking metal–organic frameworks (MOFs), tetrakis (3‐mercaptopropionic acid) pentaerythritol (PETMP), and poly(ethylene glycol) diacrylate (PEGDA) via multiple CSC bonds. The SPE also exhibits a high electrochemical window (>5.4 V), low interfacial impedance (<550 Ω), and impressive Li + transference number ( t Li+ = 0.44). As a result, Li||Li symmetrical cells with the thiol‐branched SPE displayed a high stability in a >1300 h cycling test. Moreover, a Li|M‐S‐PEGDA|LiFePO 4 full cell demonstrates discharge capacity of 143.7 mAh g −1 and maintains 85.6% after 500 cycles at 0.5 C, displaying one of the most outstanding performances for SPEs to date.
Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle lifeShuai Chen, Yuelong Xin, Yiyang Zhou et al.|Energy & Environmental Science|2013 Facile fabrication of well-aligned Li4Ti5O12 (LTO) nanosheet arrays grown directly on conductive Ti foil was achieved by hydrothermal growth in LiOH solution. The reaction between Ti foil and LiOH led to the growth of vertically aligned, rectangular lithium titanate oxide hydrate (H-LTO) nanosheet arrays, which could be converted into LTO nanosheet arrays through topotactic transformation via thermal decomposition. An appropriate LiOH concentration was essential for the formation of densely aligned H-LTO nanosheet arrays on the substrate. It was proposed that the formation of the H-LTO nanosheet arrays was through kinetics-controlled growth during the hydrothermal metal corrosion process. When used as a binder-free anode for LIBs, the self-supported LTO nanosheet arrays standing on Ti foil exhibited an excellent rate capability (a reversible capacity of 163 mA h g−1 and 78 mA h g−1 at 20 C and 200 C, respectively) and an outstanding cycling performance (a capacity retention of 124 mA h g−1 after 3000 cycles at 50 C). Furthermore, a flexible lithium ion battery, which could be fully recharged within 30 s and was able to light an LED, was assembled by using the LTO nanosheet arrays as the anode.
High sulfur loading composite wrapped by 3D nitrogen-doped graphene as a cathode material for lithium–sulfur batteriesChao Wang, Kai Su, Wang Wan et al.|Journal of Materials Chemistry A|2014 A sulfur composite cathode material based on 3D N-doped graphene has a high sulfur content of 87.6 wt% and shows an excellent rate capability and cyclability.