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Nanoscale · 2023 ·Vol. 15 ·期 31 ·12961-12971 · IF 6.7

Squaraine-linked zwitterionic COF modified LLZTO nanoparticles for high performance polymer composite electrolytes in Li–S batteries

Shuo Wang,Mengke Li,Gaojie Yan,Zhipeng Yang,Yuchao Guo,Xi Sun,Yue Wang,Yi Feng,Huili Ding,Xiaojie Zhang

Lithium–sulfur (Li–S) batteries are severely restricted for practical application due to the polysulfide shuttle effect, Li dendrites and thermal runaway. The use of PEO-based polymer composite electrolytes (PCEs) as an alternative strategy suffers from limited lithium-ion conductivity with deficient long-range transfer route. Herein, Li6.4La3Zr1.4Ta0.6O12 (LLZTO) nanoparticles modified with an in situ-synthesized zwitterionic covalent organic framework layer (denoted as LLZTO@HUT4) were introduced into PEO-based PCEs. Zwitterionic HUT4 modified the lithiophobic LiOH/Li2CO3 layer on the surface of LLZTO nanoparticles, which could notably promote Li+ ion transport for superior electrochemical performance of PCEs. Additionally, the intermediate layer HUT4 located between LLZTO and PEO could further improve the mechanical properties of electrolytes due to the enhanced inorganic/organic interface compatibility and intermolecular interaction. As a result, the obtained LLZTO@HUT4-15%/PEO electrolyte exhibited a competent ionic conductivity of 0.73 mS cm−1 with a Li+ transference number of up to 0.74 at 60 °C. The assembled S@CNT|LLZTO@HUT4-15%/PEO|Li coin cell delivered a considerable initial discharge capacity of 1018 mA h g−1 at 0.2 C, with approximately 92.1% capacity retention after 100 cycles, elucidating an obviously suppressed shuttle effect.

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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2023 · IF 4.5

Co nanoparticles embedded into leaf-like porous carbon as a promising cathode catalyst for Li-O2 batteries

Chaoyang Sun,Fenglong Xiao,Di Wu,Gang Lian,Deliang Cui,Qilong Wang,Haohai Yu

Rechargeable Li-O 2 batteries show great potential due to their superior high energy density. However, the practical application is still limited by the sluggish kinetics, resulting in poor cycling performance and high overpotentials. Herein, highly dispersed Co nanoparticles embedded into porous N -doped carbon matrix (DCo-NC) with carbon nanotubes is explored through the pyrolysis of a bimetallic leaf-shaped ZnCo-ZIFs. The evaporation of Zn species and porous carbon matrix derived from ZIFs prevents the Co nanoparticles aggregation, exposes more Co-N active sites and provides abundant pores. They facilitate Li + and electron transfer, prevent Co nanoparticles from deactivation and provide enough space for Li 2 O 2 , thereby accelerating oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) kinetics. Accordingly, the Li-O 2 batteries with DCo-NC cathode exhibit reduced overpotential, high discharge capacity (10,490 mA h g −1 at 100 mA g −1 current density) and improved cycling performance (258 cycles at 500 mA g −1 with a limited capacity of 500 mA h g −1 , 103 cycles at 500 mA g −1 with a limited capacity of 1000 mA h g −1 ).

CAS / MDL: 10026-22-9 693-98-1
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CHEMISTRY OF MATERIALS · 2023 · IF 8.6

Reaction Pathway Analysis of B/Li2O in a Li–B–O System for Boron Nitride Nanotube Growth

Kai Zhang,Pan Xue,Jianghua Wu,Liyun Wu,Nanyang Wang,Tao Xu,Kaiping Zhu,Jun Pu,Qiulong Li,Yu Deng,Yagang Yao,Jin Zhang

Compared to other synthetic methods, the synthesis of boron nitride nanotubes (BNNTs) by the boron oxide chemical vapor deposition (BOCVD) method can balance the purity and quality of the product nanotubes. However, due to the solid reaction characteristics of boron monomers, the closed reaction system, and the synthesis temperature of over 1000 °C, growth studies of BNNTs have been in a dilemma. To this end, simultaneous thermal analysis combined with multi-atmosphere annealing experiments at corresponding temperatures is used to study the inorganic solid-state reaction of the classical BOCVD precursor B/Li2O in real time and confirmed by experimental results that lithium borate is the actual active component and catalyst. Further experiments reveal that the growth process of BNNTs and lithium borate not only consumes less of the precursor and ammonia but is also flexible in its configuration, showing exceptional efficiency and reactivity. Lastly, experiments have shown that the structure and activity of borate are equally applicable to alkali metals, alkaline earth metal, and transition metals.

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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

Ionic covalent organic frameworks triggered efficient synergy: Li+ de-solvation and the formation of LiF-rich interphase

Weifeng Zhang,Guoxing Jiang,Wenwu Zou,Longhai Zhang,Shulian Li,Shengguang Qi,Xiujun Wang,Zhiming Cui,Huiyu Song,Li Du,Zhenxing Liang

The parasitic side reaction between the electrolyte and the lithium metal (Li 0 ) forms an unstable heterogeneous interphase, causing the poor reversibility of Li plating/stripping. The rational design of protection layer on Li 0 anode is imperative to inhibit side reactions and achieve fast Li  +  transport on the Li 0 /electrolyte interface. Herein, by firstly coordinating the bis(fluorosulfonyl)imide anion (FSI − ) to the protection layer, a layer consisting of 2D ionic vinylene-linked covalent organic frameworks (ivCOF-FSI) is proposed to stabilize the Li 0 /electrolyte interface. As demonstrated theoretically and experimentally, the triazine group in the cationic framework is identified to promote Li + de-solvation process while partial FSI − prefers to form LiF-rich interphase. Attributed to these superiorities, the ivCOF-FSI layer endows the Li 0 /electrolyte interface with high reversibility in carbonate-based electrolytes by simultaneously suppressing the side effect and achieving rapid Li + transfer. Combined with the high stability of solid-liquid interface, the LiFePO 4 full cells with ivCOF-FSI/Li anode display enhanced cyclability under a high cathode loading of 9.4 mg cm −2 and a low negative/positive capacity ratio of 5. This work provides a novel route for stabilizing the interfacial chemistry of solid-liquid interface, aiming to pave the way for the next-generation high-energy-density batteries .

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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

PVDF-based electrolyte decorated by Li29Zr9Nb3O40 Li-ion conductor and electrochemical performance of related solid-state batteries

Jiahao Chen,Hong Zhang,Hongzhu Chen,Enjie Xia,Yanmei Wu,Zhicheng Li

Solid-state Li-ion batteries (LIBs) have recently attracted much attention for their high safety and energy density . Polyvinylidene fluoride (PVDF) is as a potential electrolyte for solid-state LIBs due to its high permittivity, wide voltage window and excellent thermal stability. Here, Y 3+ -doped Li 29 Zr 9 Nb 3 O 40 (LZNO) Li-ionic conductor with room temperature conductivity (σ 25 ) of 1.26 × 10 −4  S cm −1 is prepared. LZNO decorated PVDF-based composite solid electrolytes (CSEs) are fabricated. The PVDF-based CSE with 10% (mass ratio) of LZNO shows σ 25 of 2.34 × 10 −4  S cm −1 , and has thermal stability with melting temperature up to 332 °C and voltage window of 4.8 V. The assembled Li ( Ni 0.8 Co 0.1 Mn 0.1 ) O 2 |CSE|Li cells show initial specific discharge capacity of 216.7 mAh g −1 at 0.1 C, and exhibit high capacity and cycle performance. LiFePO 4 |CSE|Li cells display initial specific discharge capacity of 137.4 mAh g −1 at 0.5 C and high cycle performance. Addition of LZNO powder in CSEs can inhibit the dehydrofluorination of PVDF during the charge-discharge of cells, alleviate the deterioration of interface resistance, and greatly improve the specific discharge capacity of cells at high rates.

CAS / MDL: 90076-65-6 7585-20-8
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ACS Applied Energy Materials · 2022 · IF 6.959

Interfacial Regulation and Hydrogen Fluoride Capture Enabled by Allyltrimethylsilane as Multifunctional Electrolyte Additive for Li/LiNi0.8Co0.1Mn0.1O2 Batteries

Sen Jiang,Xin Xu,Junying Yin,Yue Lei,Xiaolan Wu,Yunfang Gao

Lithium metal batteries (LMBs) coupled with Ni-rich cathodes are promising next-generation solutions for high-energy-density energy storage devices. Nevertheless, many challenges concerning structural evolution of electrode materials as well as electrolyte decomposition, which mainly stem from a defect of the electrode–electrolyte interface (EEI) toward aggressive chemistries: Li metal anode (LMA), high nickel cathode materials, and LiPF6-based carbonate electrolytes, need to be addressed. In this work, the EEI layers on the LMA and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode are tailored, and the hydrogen fluoride (HF) attack is eliminated by applying a multifunctional electrolyte additive allyltrimethylsilane (ATMS). Theoretical calculations and physicochemical characterizations reveal that the C═C and Si–C groups of ATMS can fulfill the bielectrode–electrolyte interphase regulation and HF capture, respectively. Consequently, by being incorporated with the ATMS additive, the Li/NCM811 battery delivers remarkably enhanced capacity retention of 82.9% with regard to the reference cell with the baseline electrolyte (46.4%) after 200 cycles, and the Li/Li cell exhibits a prolonged lifespan beyond 1000 h at 0.5 mA cm–2.

CAS / MDL: 872-50-4 24937-79-9
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Journal of Materiomics · 2022 · IF 8.589

In-situ construction of hybrid artificial SEI with fluorinated siloxane to enable dendrite-free Li metal anodes

Lei Wei,Zhaoqing Jin,Jianhao Lu,Yang Guo,Zilong Wang,Gaoping Cao,Jingyi Qiu,Anbang Wang,Weikun Wang

Lithium (Li) metal anode holds great promise for high-energy-density rechargeable batteries. However, it suffers from the Li dendrites growth and uncontrollable side reactions with electrolyte due to the unstable solid electrolyte interphase (SEI) layer. Herein, we propose a facile strategy for the in-situ fabricate of organic-inorganic composite artificial SEI layers on Li surfaces, which consist of organic fluorinated siloxane and inorganic LiF-rich phases. The hybrid artificial SEI endows high mechanical strength (13.1 GPa) and Li + transfer number (0.62). Such robust SEI protective layers can not only guide uniform nucleation and deposition of Li metal by facilitating uniform Li-ion distribution, but also prevent unfavourable side reactions. Accordingly, the protected metallic lithium anode (PMTFPS-Li) anode enables stable Li plating/stripping performance in symmetric cells for more than 300 h at 4 mA ·h/cm 2 under a high areal capacity of 4 mA/cm 2 . Moreover, the PMTFPS-Li/S cells could maintain more than 300 stable cycles at 0.5C and the PMTFPS-Li/LFP cells present excellent cycling performance (400 cycles at 1C) and enhanced rate capability (110.4 mA·h/g at 3 C). This work will inspire the design of artificial SEI on Li anodes for advanced Li metal batteries.

CAS / MDL: 109-99-9
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JOURNAL OF LUMINESCENCE · 2022 · IF 4.171

Insight into luminescence properties of Li+ co-doped Sr2SnO4:Eu3+ phosphors by co-precipitation assisted hydrothermal synthesis

Qingling Zeng,Wenxiang He,Ning Zhang,Dongcai Guo

Sr 2 SnO 4 :Eu 3+ phosphors were prepared by a co-precipitation combined with hydrothermal method for the first time, and Li + was introduced to improve its luminescence performance. X-ray diffraction analysis determined that Sr 2 SnO 4 :Eu 3+ , Li + phosphors were successfully synthesized. The effects and mechanisms of Li + doping on the luminescence properties of Sr 2 SnO 4 :Eu 3+ were specifically discussed. At 260 nm excitation, the fluorescence spectra of the products were dominated by the 5 D 0 - 7 F 1 characteristic emission peak of Eu 3+ at 598 nm, with the electric dipole transition 5 D 0 - 7 F 2 being distinctly lower than the magnetic dipole transition 5 D 0 - 7 F 1 , indicating that Eu 3+ selectively replaced the highly symmetrical defective sites of Sn 4+ . The luminous intensity and decay lifetime were significantly enhanced through co-doping Li + , which played an essential role as a charge compensator. The optimum doping concentration of Li + was 7%. Finally, the color purity of Sr 2 SnO 4 :Eu 3+ , Li + reached 99.9%, suggesting that it could be developed as a potential orange-emitting material for solid-state lighting.

CAS / MDL: 7790-69-4
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2022 ·Vol. 33 ·期 20 ·16383-16395 · IF 2.779

Construction of high-performance Li-rich Mn-based cathodes assisted by a novel water-soluble LiPAA binder

Zhao Taolin,Chang Liyao,Ji Rixin,Chen Shaokang,Jin Xiaoyu,Zheng Yingdi,Huang Xiyun,Shen Jiangang,Zhang Yuxia

Recently, all types of electrical equipment put forward increasing requirements on the energy density of secondary rechargeable batteries. The low specific capacity of cathode material is the primary factor that restricts the energy density of Li-ion batteries. Li-rich Mn-based cathode materials have the advantages of high specific capacity, high operating voltage, low cost, and environmental friendliness. However, they have the limitations of low first Coulombic efficiency and serious capacity/voltage attenuation. In this work, lithium polyacrylate (LiPAA) has been employed as a water-soluble binder in the electrode to develop a high-performance Li-rich Mn-based cathode. The effect of the LiPAA binder on voltage drop and electrochemical performance of Li[Li 0.2 Co 0.13 Ni 0.13 Mn 0.54 ]O 2 cathode has been examined to reveal the modification mechanism. The results show that carboxyl group (–COOH) in the LiPAA structure can form strong hydrogen bonds with the oxygen atoms in the active material, making the electrode components firmly bonded and thus maintaining the structural stability of the cathode upon cycling. Moreover, the LiPAA binder can effectively inhibit voltage drop of Li[Li 0.2 Co 0.13 Ni 0.13 Mn 0.54 ]O 2 . The discharge voltage of the electrode decreases by only 117 mV after 50 cycles. Green water-soluble LiPAA has broad prospective applications as a binder of electrode materials of secondary batteries.

CAS / MDL: 9003-01-4 9003-04-7
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ELECTROCHIMICA ACTA · 2022 · IF 7.336

Hydrophobic RuO2/Graphene/N-doped porous carbon hybrid catalyst for Li-air batteries operating in ambient air

Nan Wang,Jialin Fu,Xuecheng Cao,Lingling Tang,Xiankai Meng,Zhenyi Han,Linhao Sun,Shuo Qi,Dangsheng Xiong

Li–air batteries have received significant attention for their ultrahigh theoretical energy density. However, the byproducts induced by attacking air hinder the conversion of Li–O 2 batteries to Li–air batteries. Humidity is one of the main obstacles, not only causing side reactions with the discharge products but also leading to rapid corrosion of the lithium anode. Here, we fabricated a novel composite hydrophobic catalyst by loading RuO 2 and graphene on N-doped porous carbon. The catalyst was endowed with hydrophobicity and showed superior catalytic performance and low affinity to water in the air. A Li–air battery equipped with this novel composite catalyst exhibited eminent cycling performance in pure oxygen (over 470 h), humid oxygen [∼40% relative humidity (RH), over 310 h], and ambient air (∼42% RH, over 330 h) at a current density of 500 mA g −1 , and the discharge specific capacity increased from 13122.1 to 19358.6 mAh g −1 .

CAS / MDL: 57-50-1
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Sustainable Energy & Fuels · 2022 ·Vol. 6 ·期 15 ·3658-3668 · IF 6.813

A novel mixed ether-based electrolyte for lithium–sulfur batteries with Li anode protection by dual salts

Xirui Kong,Yichen Kong,Xiaobin Liao,Sheng Liu,Yan Zhao

Lithium–sulfur batteries (LSB) are regarded as one of the next-generation energy storage systems with a high energy density. However, the shuttle effect of lithium polysulfides (LiPSs) and irreversible consumption of the Li anode prevent the practical application of Li–S batteries. In this work, a mixed tetrahydrofuran (THF) and dipropyl ether (DPE) based electrolyte has been optimized for Li–S batteries. Due to the common-ion effect, the LiPS solubility has been significantly inhibited when the sulfur cathode is operating in a concentrated electrolyte containing an optimized solvent system with weak dissolving power. And no self-discharge effect occurred in the cells with these electrolytes during a 10 day storage. Besides, the coulombic efficiency (CE) for Li deposition/stripping has been improved by optimizing the ratio of dual lithium salts. Impressively, Li‖Cu half-cells can run stably for more than 500 cycles with a high CE (>99.3%). For these reasons, a Li–SeSPAN cell with a L1L2TE-1382 electrolyte demonstrates an excellent capacity retention (>94% after 500 cycles) with an ultrathin (50 μm) Li metal anode. With a good compatibility of the optimized electrolyte for both the Li metal anode and sulfur cathode, this work provides a new design strategy for the electrolyte for lithium–sulfur batteries.

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ACS Applied Energy Materials · 2022 · IF 6.959

Tailoring Electrolytes to Enable Low-Temperature Cycling of Ni-Rich NCM Cathode Materials for Li-Ion Batteries

Bin Liang,Fangyuan Cheng,Xiaoyu Ge,Xuejun Tan,Chun Fang,Jiantao Han

The Ni-rich LiNixMnyCozO2 (x + y + z = 1, x > 0.5, Ni-rich NMC) materials are one of the most potential cathodes for high energy density lithium-ion batteries (LIBs) due to their high specific capacity and relatively low cost. However, performances of LIBs with the Ni-rich NCM cathode below 0 °C are restricted by low ion conductivity of the electrolyte and a slow ion diffusion rate at the electrode–electrolyte interphase. Here, γ-butyrolactone (GBL) with a low melting point and high ion conductivity is used to partially replace ethylene carbonate, which is conducive to lower the freezing point and increase the low-temperature ionic conductivity of the electrolyte, and the addition of GBL improves the dissolution of lithium difluoro(oxalato)borate (LiDFOB) in a traditional carbonate solvent. Instead of lithium hexafluorophosphate (LiPF6), LiDFOB can form a F-, B-, and O-rich interfacial phase at the Ni-rich NCM cathode, suppressing the fatal interface reaction and reducing the interface impedance. As a result, the electrolyte using GBL as the cosolvent and LiDFOB as the lithium salt can significantly improve the specific discharge capacity and cycling stability of LiNi0.8Co0.1Mn0.1O2/Li cells at 0 °C and −30 °C. At 0 °C, the LiNi0.8Co0.1Mn0.1O2/Li cells have a discharge specific capacity of 160 mA h g–1 and a capacity retention rate of 99% over 100 cycles. They deliver a decent capacity at −30 °C. This rational design of an electrolyte via optimizing the combination of a solvent and a lithium salt has been confirmed to be a low cost but rather an effective method to improve the low-temperature performances of LIBs.

CAS / MDL: 96-48-0
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