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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

Retarding Li dendrites growth via introducing porous g-C3N4 into polymer electrolytes for solid-state lithium metal batteries

Jianghai Wei,Xuewen Zheng,Weiteng Lin,Yu Si,Kemeng Ji,Chengyang Wang,Mingming Chen

Solid polymer electrolytes (SPEs) based solid-state lithium metal batteries (SSLMBs) are widespreadly practiced as one of the main technical routes aiming for chemically essential safety with acceptable energy density . However, uncontrollable Li dendrites growth and sluggish Li + transport remain obstacles to the further development of SPEs-based SSLMBs. Herein, a porous g-C 3 N 4 (PCN) is designed and introduced into polyethylene oxide (PEO). Within the following synthesized PEO-based composite solid electrolyte (PEO/PCN/LiTFSI CSE), PCN is found to be an attractive multifunctional filler. For its porous morphology and high specific surface area, abundant Lewis basic active sites are exposed, which facilitates Li + to be uniformly distributed in PEO/PCN/LiTFSI CSE and thus more effectively mitigates the Li dendrites growth comparing to those with bulk g-C 3 N 4 filler, making PCN-involved Li symmetrical cell (Li|PEO/PCN/LiTFSI|Li) run steadily for 1400 h under the current density of 0.1 mA cm −2 at 60 °C. PCN also accelerates Li + transport in the manner of reducing PEO crystallinity and promoting LiTFSI dissociation. The Li + conductivity of PEO/PCN/LiTFSI CSE reaches 3.47 × 10 −4 S cm −1 at 60 °C. Therefore, long life span and high rate performances are together achieved in SSLMB assembled with PEO/PCN/LiTFSI CSE. This work reveals a feasible strategy to fabricate dendrite-free SSLMBs cycling within a fairly long time.

CAS / MDL: 75-05-8
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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Dynamic Disulfide Bonds Contained Covalent Organic Framework Modified Separator as Efficient Inhibit Polysulfide Shuttling in Li–S Batteries

Mengke Li,Gaojie Yan,Peng Zou,Haifeng Ji,Han Wang,Zongjie Hu,Zhipeng Yang,Yi Feng,Haijie Ben,Xiaojie Zhang

First, a new covalent organic framework (HUT9) with disulfide bonds have been synthesized, which can be grown in situ on carbon nanotubes (CNT) as separator modification material for Li–S batteries. Experiments and DFT showed that disulfide bond could effectively capture soluble polysulfides (LiPSs) during discharge process, while promoting the conversion of LiPSs to Li2S/Li2S2 and improve the utilization rate of sulfur. The polar groups of the covalent organic framework provide chemisorption, and an interwoven network of HUT9@CNT (physical constraints) cooperates to inhibit the transport of LiPSs. The modified battery has a capacity retention rate of 83% (decay rate of 0.032% per cycle) after 500 cycles at 1 C. Specifically, the battery with 2-HUT9@CNT modified separators (sulfur loading: 4 mg cm–2, sulfur content: 80%, electrolyte/sulfur ratio: 10 mL g–1) can reach 3.4 mAh cm–2 area capacity after 50 cycles. This work enriched the COF material system and provided guidance for the application of organic materials in an energy storage system.

CAS / MDL: 308068-56-6
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JOURNAL OF ELECTRONIC MATERIALS · 2022 ·Vol. 51 ·期 8 ·4115-4124 · IF 2.047

The Effect of Compaction Density of Sulfur/Carbon Cathodes on the Practical Application of Li-S Pouch Cells

Li Jiaojiao,Xiao Zhen,Zhou Xiaozheng,Zhang Wenkui,Zhang Jun,Gan Yongping,Huang Hui,He Xinping,Wang Guoguang,Xia Yang

Lithium-sulfur (Li-S) batteries are a promising electrochemical energy storage device due to their low cost, high energy density, and excellent sustainability, making them superior to many commercial lithium-ion batteries. Despite the great road to market, Li-S batteries still suffer from low practical energy density, which is intimately related to fundamental scientific and technological issues of sulfur cathodes. As a non-negligible parameter in sulfur cathodes, the compaction density plays a crucial role in the energy density of Li-S batteries. Herein, the effect of compaction density of sulfur/carbon cathodes on the electrochemical performance of Li-S batteries is investigated. It is demonstrated that sulfur/carbon cathodes with an optimized compaction density of 1.2 g cm −3 not only can guarantee the good contact of active materials, but can also ensure the rational dosage of electrolyte, thereby increasing the sulfur utilization as well as reducing the dissolution of polysulfide into the electrolyte. As a result, the pouch cells paired with the sulfur/carbon cathode and Li metal anode deliver superior specific capacity and remarkable cycling performance, which is attributable to the better contact between particles and the faster redox kinetics. This work reveals the contribution of the compaction density of the sulfur cathode to the electrochemical performance of the Li-S battery, providing an instructive paradigm for the rational design of an advanced sulfur cathode for large-scale commercialized Li-S pouch cells.

CAS / MDL: 90076-65-6 7704-34-9
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DALTON TRANSACTIONS · 2022 ·Vol. 51 ·期 39 ·15067-15073 · IF 4.569

Wide band gap thiophosphates ASrPS4 (A = Li, Na, K, Rb, Cs): cation size effect induced successive structural transformation

Yi Huang,Junben Huang,Yong Zhang

Metal thiophosphates have aroused much research interest due to their structural chemistry and possible applications as infrared functional materials. In this study, five quaternary Sr-based alkali metal thiophosphates ASrPS4 (A = Li, Na, K, Rb, Cs) were obtained. Their structural comparison shows that their symmetry undergoes transformation from tetragonal (I41/acd) to monoclinic (P21/c) to orthorhombic (Pnma) system, which is induced by the cation size effects and coordination features of different alkali metal cations. The experimental and theoretical results demonstrate that the band gaps of all title compounds are large, namely 3.6–3.9 eV (experimental results) and 3.78–4.12 eV (HSE06). Theoretical analyses indicate that the [PS4] group could be regarded as a good unit for designing wide band gap compounds, and the birefringence of NaSrPS4 is 0.08 at the fundemental 1064 nm wavelength, which shows that it may be a potential infrared birefringent material.

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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Polyacrylonitrile Porous Membrane-Based Gel Polymer Electrolyte by In Situ Free-Radical Polymerization for Stable Li Metal Batteries

Zhichuan Shen,Jiawei Zhong,Shiyong Jiang,Wenhao Xie,Shiying Zhan,Kaiji Lin,Linyong Zeng,Hailing Hu,Guide Lin,Yuhan Lin,Shuhui Sun,Zhicong Shi

Because of their high ionic conductivity, utilizing gel polymer electrolytes (GPEs) is thought to be an effective way to accomplish high-energy-density batteries. Nevertheless, most GPEs have poor adaptability to Ni-rich cathodes to alleviate the problem of inevitable rapid capacity decay during cycling. Therefore, to match LiNi0.8Co0.1Mn0.1O2 (NCM811), we applied pentaerythritol tetraacrylate (PETEA) monomers to polymerize in situ in a polyacrylonitrile (PAN) membrane to obtain GPEs (PETEA-TCGG-PAN). The impedance variations and key groups during the in situ polymerization of PETEA-TCGG-PAN are investigated in detail. PETEA-TCGG-PAN with a high lithium-ion transference number (0.77) exhibits an electrochemical decomposition voltage of 5.15 V. Noticeably, the NCM811|PETEA-TCGG-PAN|Li battery can cycle at 2C for 120 cycles with a capacity retention rate of 89%. Even at 6C, the discharge specific capacity is able to reach 101.47 mAh g–1. The combination of LiF and Li2CO3 at the CEI interface is the reason for the improved rate performance. Moreover, when commercialized LFP is used as the cathode, the battery can also cycle stably for 150 cycles at 0.5C. PETEA and PAN can together foster the transportation of Li+ with the construction of a fast ion transport channel, making a contribution to stable charge–discharge of the above batteries. This study provides an innovative design philosophy for designing in situ GPEs in high-energy-density lithium metal batteries.

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HYDROMETALLURGY · 2022 · IF 4.217

Recovery of lithium from high Mg/Li ratio salt-lake brines using ion-exchange with NaNTf2 and TBP

Ruibing Bai,Junfeng Wang,Daoguang Wang,Junjie Cui,Yanqiang Zhang

In view of the complex problems for the ionic liquids (ILs) recovery with the system containing ILs and TBP, this work proposed a NaNTf 2 -based synergistic extraction system, NaNTf 2  + TBP, which could realize the effective reutilization of the extraction system without reducing the lithium separation ability. Under the optimal extraction parameters, the extraction efficiency of Li + exceeded 98%, while that of Mg 2+ was only ~1%. The results of mass spectrometry (ESI-MS) and slope analysis showed that two TBP molecules involved in the extraction process of Li + , and the Li + extraction mechanism obeyed the cation-exchange process. According to the red shift of the FT − IR peak of P O in TBP and the chemical shift changes of P in 31 P NMR, the interaction strength between TBP and different metal ion followed the sequence: E TBP−H  >>  E TBP−Li  >  E TBP−Mg  >  E TBP−K  >  E TBP−Na . It was also found that after a three−stage countercurrent extraction process, [Li + ] org was 0.42 g L −1 , and the total recovery efficiency of Li + was about 98%. The saturated extraction capacity for Li + could be as high as 5.4 g L −1 , and Li + could be stripped with the aqueous solution containing 0.2 mol L -1 HCl. In addition, the extraction efficiency of Li + was almost not attenuated after 6 extraction cycles. This new extraction system shows a certain industrial application prospect for Li + separation from the salt lake bine with high Mg/Li ratio.

CAS / MDL: 107-06-2 126-73-8
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ELECTROCHIMICA ACTA · 2022 · IF 7.336

Usefulness of uselessness: Teamwork of wide temperature electrolyte enables LFP/Li cells from -40 °C to 140 °C

Bingying Zhu,Xiaotang Shi,Tianle Zheng,Jianwei Xiong,Ya-Jun Cheng,Yonggao Xia

Lithium secondary battery with a wide working temperature range is crucial to boost its increasing applications in harsh circumstances. Suppressing excessive electrolyte decomposition at high temperatures while maintaining reasonable electrochemical kinetics at low temperatures is critical for wide-temperature electrochemical performance. Construction of high temperature stable electrode-electrolyte interface layer by electrolyte formulation is an effective strategy to prevent electrolyte from uncontrollable decomposition. On the contrary to conventional thinking, propylene carbonate (PC) bearing poor filming ability to suppress electrolyte decomposition is used in this work to promote decomposition of the single lithium difluoro(oxalate)borate (LiODFB) salt in the electrolyte, producing inorganic-rich interface layer with good structure stability over a wide temperature range. Glutaronitrile (GLN) is further utilized to minimize the decomposition of PC by expelling PC out of the solvation sheath of lithium-ion. The teamwork of LiODFB, PC, and GLN makes a synergistic contribution to building a high-temperature stable electrode-electrolyte interface layer at both LFP and MCMB electrodes. Based on the approach developed in this work, the temperature window is successfully expanded to the range of from -40 °C to 140 °C. Excellent electrochemical performance is exhibited by both LFP/Li and MCMB/Li cells from -20 °C to 100 °C in terms of reversible capacity and cyclic stability.

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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Oxygen-deficient Nb2O5-x decorated MCMB anode with much enhanced rate and cycle performances for Li-ion batteries

Jiamei Lai,Chunhai Jiang,Zhimin Zou

Nanosized oxygen-deficient orthorhombic niobium pentoxide (Nb 2 O 5-x ) that possess high electronic conductivity and stable cycle performance for Li storage are uniformly deposited on the surface of mesophase carbon microspheres (MCMB), which as a whole exhibits very encouraging electrochemical Li ion storage performance, including a high specific capacity of 107 mAh g −1 at 10C (1C = 372 mA g −1 ) and a high capacity retention of 85.4 % after 300 cycles at 3C in the optimized case. The Li + diffusion coefficient of the composite anode as determined by the potentiostatic intermittent titration technique (PITT) is obviously improved as compared to that of pristine MCMB. Ex situ X-ray diffraction characterizations confirm the phase transformation from orthorhombic Nb 2 O 5-x to amorphous Li y Nb 2 O 5-x accompanied by the formation of NbO through a conversion reaction in the first lithiation process. The ultrafast Li + diffusion within the amorphous Li y Nb 2 O 5-x as well as the current-sharing effect of the secondary particles can explain the much enhanced Li ion storage property. The results of this work convincingly demonstrate that designing MCMB/Nb 2 O 5-x composite can be a more practical way to improve the energy and powder densities of Li-ion batteries rather than seeking alternative anode materials with higher capacities.

CAS / MDL: 10026-12-7
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Advanced Energy Materials · 2022 ·Vol. 12 ·期 37 ·2201734 · IF 29.698

Unraveling the Key Atomic Interactions in Determining the Varying Li/Na/K Storage Mechanism of Hard Carbon Anodes

Qi Li,Jun Zhang,Lixiang Zhong,Fushan Geng,Ying Tao,Chuannan Geng,Shuzhou Li,Bingwen Hu,Quan-Hong Yang

Hard carbons have been identified as competitive anodes for Li/Na/K-ion batteries but their Li/Na/K-ion storage mechanisms significantly vary in different batteries. It is fundamental to understand the basic science behind the difference. Herein, it is theoretically revealed that defects on the carbon layers generally have an influential impact on the atomic interactions including the metal–metal (M–M) and metal–carbon (M–C) interactions, thereby determining whether the stored alkali-metal atoms are in ionic or quasi-metallic states. Upon increasing the number of metal atoms on a carbon layer composed of only hexatomic rings, K tends to be stored in an ionic state similar to Li due to the dominant M–C interaction, while on a carbon layer with defects, K tends to be stored in a quasi-metallic state similar to Na due to the dominant M–M interaction. For experimental verification, a glassy carbon, the extreme form of hard carbon with dominant sp 2 hybridization and only Stone–Wales defects, is selected as a model anode, and its Li/Na/K-ion storage mechanisms are exactly consistent with the theoretical prediction. More profoundly, for the first time, the quasi-metallic K cluster information is captured by ex situ electron paramagnetic resonance.

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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Nanofibrous Cathode Catalysts with MoC Nanoparticles Embedded in N-Rich Carbon Shells for Low-Overpotential Li–CO2 Batteries

Qian-Cheng Zhu,Zi-Rui He,De-Yu Mao,Wan-Ni Lu,Sheng-Long Yi,Kai-Xue Wang

Li–CO2 batteries with high theoretical energy densities are recognized as next-generation energy storage devices for addressing the range anxiety and environmental issues encountered in the field of electric transportation. However, cathode catalysts with unsatisfactory activity toward CO2 absorption and reduction/evolution reactions hinder the development of Li–CO2 batteries with desired specific capacities and sufficient cycle numbers. In this work, a multifunctional nanofibrous cathode catalyst that integrates N-rich carbon shells embedded with molybdenum carbide nanoparticles and multiwalled carbon nanotube cores was designed and prepared. The N-rich carbon shell could strengthen the absorption capacity of CO2 and Li2CO3. The molybdenum carbide nanoparticles would improve the catalytic activity of both CO2 reduction and evolution reactions. The carbon nanotube cores would provide an efficient network for electron transportation. The synergistic effect of the cathode catalysts enhances the electrochemical performance of Li–CO2 batteries. A high cycling stability of more than 150 cycles at a current density of 250 mA g–1 with a cutoff capacity of 1000 mAh g–1 and a charge/discharge overpotential of less than 1.5 V is achieved. This work provides a feasible strategy for the design of a high-performance cathode catalyst for lithium–air batteries.

CAS / MDL: 10241-05-1 108-78-1
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JOURNAL OF RARE EARTHS · 2022 · IF 4.632

Li+ doping induced zero-thermal quenching in Cs3Zn6–x–yB9O21:xEu3+,yLi+ (0 ≤ x ≤ 0.10, 0.06 ≤ y ≤ 0.16)

Yuxing Bai,Liwei Wu,Qilin Cheng,Li Wu,Yongfa Kong,Yi Zhang,Jingjun Xu

Thermal stability is a crucial index to assess application value of high-power LEDs, which is related to lattice defects. Herein, an effective structure - engineering strategy is proposed to achieve excellent properties. Under the 394 nm excitation, Cs 3 Zn 5.94 B 9 O 21 :0.06Eu 3+ possesses two characteristic emissions peaked at 591 and 612 nm with limited thermal stability. By introducing Li +  ions into the lattice, the sample exhibits high color purity and excellent zero-thermal quenching because the defect contents of the phosphor can be effectively modulated via charge-compensation effect. Then, under the stimulus of high temperature, the corresponding trap levels with a suitable depth ( E  = 1.27 eV) will release electrons to recombine with the luminescent centers, compensating for the energy loss. The study provides a meaningful guide for optimizing and designing novel functional photoluminescent materials.

CAS / MDL: 534-17-8 1308-96-9
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JOURNAL OF LUMINESCENCE · 2022 · IF 4.171

Enhanced X-ray-induced luminescence and persistent luminescence of NaLuF4:Tb3+ nanoparticles with Li+ and Gd3+ co-doped

Yangqing Wu,Mei Wang,Shaolian Sun,Shan Shao,Ziyu Pan,Jinkai Li,Haoming Wei,Bingqiang Cao

X-ray excitation photodynamic therapy is a new photodynamic therapy mode that induces tumor cell apoptosis by indirectly stimulating photosensitizer on nanoparticles with X-ray as excitation light source and generating singlet oxygen. It solves the problem of light penetration in traditional photodynamic therapy and realizes the treatment of deep tumors. At present, the weak X-ray-induced luminescence restricts further development of X-ray photodynamic therapy. NaLuF 4 :Li + /Gd 3+ /Tb 3+ rare-earth nanoparticles with uniform size and regular morphology were synthesized by solvothermal method . The X-ray-induced luminescence intensity of NaLuF 4 :Li + /Gd 3+ /Tb 3+ NPs was improved by Li + and Gd 3+ ions co-doping. The light yield of NaLuF 4 :Li + /Gd 3+ /Tb 3+ NPs with 5% Li + ions doping was 1.4 times than that of reference sample due to the change of crystal field symmetry. Furthermore, the effective lifetime of persistent luminescence increased from 221.5 s to 251.9 s after 15% Li + ions doping. The thermoluminescence curves confirmed that the trap concentration was increased after Li + ions doping, which was responsible for enhancing persistent luminescence lifetime . Long persistent luminescence emission laid a foundation for further application in photodynamic therapy.

CAS / MDL: 112-80-1 112-88-9
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