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Materials · 2021 ·Vol. 14 ·期 16 ·4751 · IF 3.623

Electrochemically Inert Li2MnO3: The Key to Improving the Cycling Stability of Li-Rich Manganese Oxide Used in Lithium-Ion Batteries

Lian-Bang Wang,He-Shan Hu,Wei Lin,Qing-Hong Xu,Jia-Dong Gong,Wen-Kui Chai,Chao-Qi Shen

Lithium-rich manganese oxide is a promising candidate for the next-generation cathode material of lithium-ion batteries because of its low cost and high specific capacity. Herein, a series of xLi2MnO3·(1 − x)LiMnO2nanocomposites were designed via an ingenious one-step dynamic hydrothermal route. A high concentration of alkaline solution, intense hydrothermal conditions, and stirring were used to obtain nanoparticles with a large surface area and uniform dispersity. The experimental results demonstrate that 0.072Li2MnO3·0.928LiMnO2nanoparticles exhibit a desirable electrochemical performance and deliver a high capacity of 196.4 mAh g−1at 0.1 C. This capacity was maintained at 190.5 mAh g−1with a retention rate of 97.0% by the 50th cycle, which demonstrates the excellent cycling stability. Furthermore, XRD characterization of the cycled electrode indicates that the Li2MnO3phase of the composite is inert, even under a high potential (4.8 V), which is in contrast with most previous reports of lithium-rich materials. The inertness of Li2MnO3is attributed to its high crystallinity and few structural defects, which make it difficult to activate. Hence, the final products demonstrate a favorable electrochemical performance with appropriate proportions of two phases in the composite, as high contents of inert Li2MnO3lower the capacity, while a sufficient structural stability cannot be achieved with low contents. The findings indicate that controlling the composition through a dynamic hydrothermal route is an effective strategy for developing a Mn-based cathode material for lithium-ion batteries.Keywords:lithium-rich manganese oxide;nanocomposite;dynamic hydrothermal;inert Li2MnO3;cycling stability

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2021 ·Vol. 32 ·期 13 ·17105-17114 · IF 2.478

Effect of heat treatment on structural and magnetic properties of Li–Ni ferrite prepared via sol–gel auto-combustion method

Song Jiali,Wang Zhi,Gao Yu

Nanocrystalline Li 0 . 35 Ni 0.3 Fe 2.35 O 4 ferrites were prepared at different annealing temperatures by sol–gel auto-combustion method. The effects of the annealing temperature on the structure and magnetic properties of the synthesized Li–Ni ferrites were characterized by X-ray diffraction (XRD), scanning electron microscopy, Fourier transform infrared spectra and Vibrating Sample Magnetometer, and X-ray photoelectron spectrometer. Rietveld refinement of the XRD data confirmed the occurrence of phase transition from α-spinel to β-spinel, from which the ideal cation occupation and lattice parameter can be obtained. The grain size increased significantly with annealing temperature. The variation of saturation magnetization can be well explained in terms of the occupation of ions in tetrahedron and octahedron. The coercivity initially increased and later decreased significantly from 115 to 37 Oe with the increase of annealed temperature which could be attributed the fact that the 600 °C-annealed grain size is close to transition size from single- to multi-domain region.

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ACS Sustainable Chemistry & Engineering · 2020 · IF 7.632

Enabling Highly Stable Li–O2 Batteries with Full Discharge–Charge Capability: The Porous Binder- and Carbon-Free IrNi Nanosheet Cathode

Zhengyi Qian,Xudong Li,Liguang Wang,Tianpin Wu,Baoyu Sun,Lei Du,Yulin Ma,Chunyu Du,Pengjian Zuo,Geping Yin

Rechargeable aprotic Li–O2 batteries have drawn much attention in light of their ultrahigh theoretical energy density. However, the sluggish kinetics of oxygen cathode reactions lead to huge energy loss, while the unfavorable side reactions associated with the widely used carbon and binder account for fast battery decay during cycles. Herein, hierarchically holey IrNi alloy nanosheets are facilely designed on Ni foam substrate as a freestanding, binder- and carbon-free cathode to address these challenges. The IrNi nanosheets consist of numerous interconnected nanoparticles, forming abundant nanoholes, benefiting active-site exposure. Moreover, the meso-/macropores pave channels for the transfer of oxygen and lithium ions and provide enough accommodation for the insoluble Li2O2 product. The corresponding Li–O2 batteries demonstrate low polarization and excellent cycle stability with full discharge/charge capability (up to 292 cycles at a current density of 0.2 mA cm–2 within a voltage range from 2.3 to 4.3 V). The long-term cycling performance is principally attributed to the exclusive catalytic stability of the holey IrNi nanosheets and its good compatibility with dimethyl sulfoxide-based electrolyte. Our research provides novel insights into the design of robust and freestanding porous cathodes for high energy density Li–O2 batteries.

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JOURNAL OF MEMBRANE SCIENCE · 2020 · IF 7.183

Fire-retardant sp3 boron-based single ion conducting polymer electrolyte for safe, high efficiency and dendrite-free Li-metal batteries

Yunfeng Zhang,Jiaying Wang,Chang Tan,Yang He,Yazhou Chen,Shikang Huo,Danli Zeng,Chen Li,Hansong Cheng

Single lithium ion conducting polymer electrolytes (SIPEs) are an emerging class of alternative polymer electrolytes for protecting lithium metal anode . This work explores a fully aromatic sp 3 boron based SIPE, lithium poly (4,4′-dihydroxydiphenyl sulfone borate), Li-PSB, via a one-step synthetic procedure. A series of highly porous SIPE membranes, defined as po -PBSBs, comprising of Li-PSB and a fully aromatic polybenzimidazole (PBI) binder are firstly prepared. As a polymer electrolyte, po -PBSB exhibits high lithium ion transference number of close to unity, high ionic conductivity , excellent thermal dimensional stability and promising flame-retardant. X-ray Photoelectron Spectroscopy (XPS) and Density Functional Theory (DFT) calculations depict multi-coordinated lithium ion transport channels in the po -PBSB membranes. By serving as polymer electrolyte in lithium metal batteries (LMBs), Li/LiFePO 4 (LFP) cell, the po -PBSB shows an effective suppression of lithium dendrite growth. As a consequence, po -PBSB based Li/LFP cell demonstrates superior cycling performance remaining 76.1% of its initial capacity with nearly 100% coulombic efficiency at 1.0C after 200 cycles. The excellent performance may be ascribed to the remarkable lithium ion transference number, high organic solvent absorption in pores and thermal and electrochemical stabilities of the po- PBSB. We believe that the novel SIPE materials have great potential for application in high-safety LMBs.

CAS / MDL: 127-19-5 872-50-4
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Nanoscale · 2020 ·Vol. 12 ·期 47 ·24196-24205 · IF 6.895

Ti3C2Tx nanosheet wrapped core–shell MnO2 nanorods @ hollow porous carbon as a multifunctional polysulfide mediator for improved Li–S batteries

Heng Zhang,Peigen Zhang,Long Pan,Wei He,Qi Qi,Zhuoheng Bao,Li Yang,Wei Zhang,Michel W. Barsoum,ZhengMing Sun

Lithium–sulfur (Li–S) batteries are regarded as potential next-generation energy storage systems due to their high theoretical energy densities. However, the dissolution of lithium polysulfides (LiPSs) upon cycling can result in severe capacity degradation. Achieving high rate capabilities with good cycling stability remains a huge obstacle for the practical implementation of Li–S batteries. Here we developed a novel, multifunctional, hierarchical structure by self-assembling core–shell MnO2 nanorods @ hollow porous carbon with 2D Ti3C2Tx nanosheets, labelled as MCT, as an efficient polysulfide mediator for Li–S cathodes. The integration of the polar MnO2 core and hollow porous carbon shell captures LiPSs two ways: physical confinement and chemisorption. The conductive Ti3C2Tx nanosheets construct a continuous and conductive network, which not only promotes charge transfer and ion diffusion but also boosts LiPS adsorption and conversion. Based on these merits, the MCT/S cathode delivers good rate capability (688 mA h g−1 at 2.0C) and outstanding long-term cyclability (0.044% capacity decay per cycle over 600 cycles at 2.0C).

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ACS Applied Energy Materials · 2020 · IF 4.473

Insight of Redox Shuttling Inhibition for a Polyethylene Oxide/TiO2/Polypropylene Separator of Li–O2 Battery with Enhanced Cycling Stability

Jia Liu,Ying Wang,Dan Zhou,Dan Li,Ziye Kang,Haiming Xie

Although a redox mediator (RM) strategy can lower the overpotential of Li–O2 batteries (LOBs), the redox shuttling results in an undesired RM consumption and a continued decomposition of lithium metal anode, leading to a poor cycling stability. In this work, a hybrid inorganic–organic composite separator based on polyethylene oxide/TiO2/polypropylene (PEO/TiO2/PE) in LOBs has been reported for the first time, which aims to suppress the RM shuttling. The influences of TiO2 nanoparticles and PEO on battery performance are systematically investigated. Benefiting from the synergistic advantages, a LOB with PEO/TiO2/PE separator displays stable cyclability, considerable rate performance, and good reversibility. Additionally, the mechanism of inhibiting shuttling effect by this composite separator is proposed. We hope that this work can give an insight into the development of multiple functional separators for Li anode protection in LOBs.

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JOURNAL OF MEMBRANE SCIENCE · 2020 · IF 7.183

A novel nanofiltration membrane with [MimAP][Tf2N] ionic liquid for utilization of lithium from brines with high Mg2+/Li+ ratio

Huanhuan Wu,Yakai Lin,Wenyan Feng,Tianyin Liu,Lin Wang,Hong Yao,Xiaolin Wang

In order to utilize lithium from brines with high Mg 2+ /Li + ratio, a positively charged nanofiltration (NF) membrane was prepared by grafting amine-functionalized ionic liquid 1-(3-aminopropyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([MimAP][Tf 2 N]) onto the surface of polyamide (PA) membrane. The effects of [MimAP][Tf 2 N] contents on the chemical composition, surface morphology , surface charges and separation properties of the modified PA membranes were discussed. The results of chemical composition analyses indicated reaction of the amine group of [MimAP][Tf 2 N] with the residual acyl chloride groups, which was existed on the surface of the nascent PA membrane. The surfaces of all the modified PA membranes were positively charged at pH = 6.4 due to the quaternary ammonium group of [MimAP][Tf 2 N]. In the separation process, the resulting membrane presented high water permeance (37.8 L/(m 2 ⋅h)) and mono-/divalent cation selectivity (Li + and Mg 2+ ) with much higher MgCl 2 rejection (83.8%) than LiCl rejection (24.4%). For a simulative brine with a Mg 2+ /Li + ratio of 20, the rejections to Mg 2+ and Li + by the optimized membrane (NF-IL-2.0%) were around 81.9% and −45.2%, respectively, where the permeate with the Mg 2+ /Li + ratio of 3.5 was obtained and the selectivity ( S Li,Mg ) was 8.12. Additionally, the optimized membrane exhibited a stable performance for Mg 2+ /Li + separation. Therefore, there is a very possibility for utilization of lithium from brine with high Mg 2+ /Li + ratio by using the optimized NF membrane.

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Small · 2020 ·Vol. 16 ·期 13 ·1907163 · IF 11.459

A Polymer-Reinforced SEI Layer Induced by a Cyclic Carbonate-Based Polymer Electrolyte Boosting 4.45 V LiCoO2/Li Metal Batteries

Rongxiang Hu,Huayu Qiu,Huanrui Zhang,Peng Wang,Xiaofan Du,Jun Ma,Tianyuan Wu,Chenglong Lu,Xinhong Zhou,Guanglei Cui

Lithium (Li) metal batteries (LMBs) are enjoying a renaissance due to the high energy densities. However, they still suffer from the problem of uncontrollable Li dendrite and pulverization caused by continuous cracking of solid electrolyte interphase (SEI) layers. To address these issues, developing spontaneously built robust polymer-reinforced SEI layers during electrochemical conditioning can be a simple yet effective solution. Herein, a robust homopolymer of cyclic carbonate urethane methacrylate is presented as the polymer matrix through an in situ polymerization method, in which cyclic carbonate units can participate in building a stable polymer-integrated SEI layer during cycling. The as-investigated gel polymer electrolyte (GPE) assembled LiCoO 2 /Li metal batteries exhibit a fantastic cyclability with a capacity retention of 92% after 200 cycles at 0.5 C (1 C = 180 mAh g −1 ), evidently exceeding that of the counterpart using liquid electrolytes. It is noted that the anionic ring-opening polymerization of the cyclic carbonate units on the polymer close to the Li metal anodes enables a mechanically reinforced SEI layer, thus rendering excellent compatibility with Li anodes. The in situ formed polymer-reinforced SEI layers afford a splendid strategy for developing high voltage resistant GPEs compatible with Li metal anodes toward high energy LMBs.

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ACS Applied Materials & Interfaces · 2020 · IF 8.758

Toward Commercially Viable Li-S Batteries: Overall Performance Improvements Enabled by a Multipurpose Interlayer of Hyperbranched Polymer-Grafted Carbon Nanotubes

Shizhen Li,Honglei Zhang,Wanru Chen,Yulong Zou,Hangqi Yang,Jingbo Yang,Chuang Peng

Shuttle effect and the low utilization of dissolved lithium polysulfides (LiPSs) are two prevailing concerns in Li-S battery (LSB) research. Energy efficiency on the other hand is often overlooked but vital to the commercial deployment of battery technology. In this work, a composite of hyperbranched poly(amidoamine)-modified multiwalled carbon nanotubes (PAMAM-CNTs) is successfully prepared by chemical grafting and employed as an interlayer material in LSBs. The high content and highly dispersed polar functional groups of PAMAM can efficiently adsorb and enhance the redox reaction of LiPSs. The CNTs function as a scaffold and current collector that reduces the internal polarization. The assembled LSB displays a high energy efficiency of 86% and a low capacity fading rate of 0.037% per cycle over 1200 cycles at 2 C. The cell also shows excellent cycle performance, high sulfur utilization, and improved stability at a high areal capacity of 9 mAh cm–2 (achieved at a sulfur loading of 8.7 mg cm–2) and low electrolyte/sulfur ratio of 6.1 mL g–1. This thin (12 μm) and lightweight (0.34 mg cm–2) interlayer has a negligible impact on the overall cell energy density.

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APPLIED SURFACE SCIENCE · 2020 · IF 6.182

H2O2 assisted hydrothermal oxidation of partially etched vanadium carbides (MXene) and their electrochemical properties as anode for Li-ion batteries

Wei Luo,Yi Liu,Fan Li,Jinghao Huo,Dan Zhao,Jianfeng Zhu,Shouwu Guo

The novel V 2 CT x MXenes have gained increasing attention as anode materials in lithium-ion batteries, but to boost their practical to the theoretical values is still challenging. Herein, the partially etched V 2 CT x was oxidized in the presence of H 2 O 2 through a hydrothermal reaction and the electrochemical properties of as-obtained oxidized V 2 CT x were assessed. It is illustrated that the oxidized V 2 CT x possesses a large surface interlayer spacing, and enriched with VO 2 (A) and O-terminate groups. Once used as anode materials for Li-ion batteries, the oxidized V 2 CT x shows enhanced specific lithium ion storage capacities of 318 mAh·g −1 at 100 mA·g −1 after 100 cycles, and 125 mAh·g −1 at 1000 mA·g −1 after 1000 cycles, and better cycling stability and excellent rate performance over the V 2 CT x .

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SOLAR ENERGY · 2020 · IF 4.608

Enhanced performance of carbon-based perovskite solar cells with a Li+-doped SnO2 electron transport layer and Al2O3 scaffold layer

Yue Qiang,Yahong Xie,Ying Qi,Peng Wei,Haokun Shi,Cong Geng,Haichao Liu

SnO 2 (Tin oxide) is one of the most successful electron transport layer (ETL) materials in perovskite solar cells (PSCs) because of its low sintering temperature and simple preparation process. Similarly, carbon-based hole transport material-free PSCs (C-PSCs) have been widely studied because of their excellent stability and low price. Therefore, C-PSCs having SnO 2 as ETL can be envisaged as a promising PSCs system for commercial flexible equipment. However, studies on this system are still scarce because of its low power conversion efficiency (PCE). In this paper, the electron lifetime and current (J sc ) of a PSC containing a Li-SnO 2 /Al 2 O 3  + CH 3 NH 3 PbI 3 /carbon structure are greatly improved by doping lithium into SnO 2 (Li-SnO 2 ) and sandwiching an Al 2 O 3 interlayer into the Li-SnO 2 ETL and CH 3 NH 3 PbI 3 . A PCE of 10.01% is obtained, which is 42.3% higher than a PSC having a SnO 2 /CH 3 NH 3 PbI 3 /carbon structure. The entire preparation process is very simple and is carried out in an air atmosphere below 200 °C (20–40% humidity).

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SOLID STATE IONICS · 2020 · IF 3.107

Preparation of Li (tri-(4-carboxyphenyl) amine) doped polypyrrole as cathode material of lithium ion batteries and its electrochemical performances

Chang Su,Pengju Guo,Lihuan Xu

The Li (tri-(4-carboxyphenyl) amine) (Li-TCPA 2 ) doped polypyrrole (PPy-Li-TCPA 2 ) composites were successfully prepared by in-situ chemical oxidation using pyrrole and Li-TCPA 2 as raw materials. The structure, morphology, electrochemical properties of prepared materials were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), specific surface area test (BET), scanning electron microscopy (SEM), cyclic voltammogram (CV) and electrochemical impedance spectra (EIS), respectively. Also, the charge-discharge properties of the prepared composites were studied by galvanostatic charge-discharge testing. The results demonstrated that as-prepared composite material exhibited a reversible redox process at 2.0–4.0 V. And the discharge specific capacity for PPy-Li-TCPA 2 (2:1) and PPy-Li-TCPA 2 (6:1) are 50.4 mAh·g −1 and 63.7 mAh·g −1 as measured at 30 mA·g −1 between 2.0 and 4.0 V, while PPy-Li-TCPA 2 (4:1) exhibited the discharge specific capacity of 91.1 mAh·g −1 , which were remarkably higher than that of the pure PPy (29.5 mAh·g −1 ) under the same experimental conditions. At the same time, PPy-Li-TCPA 2 (4:1) has improved rate performance and stable cycleability. The excellent electrochemical properties are attributed to the introduction of Li-TCPA 2 as dopant , which improved the electrical conductivity and the redox activity of PPy. Furthermore, the resulted well-dispersed particle structure of the composite as well as its improved specific surface area for doped PPy facilitated to the contact of the electrolyte with the active material, leading to the increased utilization ratio of active material and the enhanced electrochemical performances .

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