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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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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 MEMBRANE SCIENCE · 2023 · IF 9.5

Based on high cross-linked structure design to fabricate PEI-based nanofiltration membranes for Mg2+/Li+ separation

Yifan Zhang,Yaru Fan,Guoli Zhou,Yijun Cao,Jingtao Wang,Xiaobin Jiang,Ning Zhang,Shaohua Yin

With the rapid development of Li-ion batteries (LiBs), the demand for lithium sharply increased. Salt lakes contribute to major extractable lithium in the world, however, the efficient separation of Mg 2+ and Li  +  remains a challenge. The PEI-based nanofiltration (NF) membrane shows great potential for Mg 2+ /Li + separation in recent studies, due to its positively charged surface and tunable pore size. In this work, ethylenediamine-terminated polyethyleneimine (EDA@PEI) was utilized as the aqueous monomer reacting with trimesoyl chloride (TMC) via interfacial polymerization (IP) to fabricate a new class of PEI-based NF membranes. This work explored critical membrane fabrication parameters and characterizations of EDA@PEI NF membranes. Additionally, this work compared EDA@PEI-TMC and PEI-TMC membranes on their physicochemical properties and NF performance. The results show that PEI containing EDA groups at ends provides the probability for connection of the backbone via TMC, thus enhancing the cross-linking degree (DNC) of EDA@PEI NF membranes. Meanwhile, the presence of EDA groups enhances the Zeta potential of membranes. The best-performing EDA@PEI-TMC membrane exhibits the highest rejection for Mg 2+ of 99.21 %, and excellent Mg 2+ /Li  +  separation that S Li/Mg reaches 69.20, 80.62 and 46.79 at Mg 2+ /Li + mass ratios of 40:1, 60:1, and 120:1, respectively. During a 48-h NF test, EDA@PEI-TFC membrane shows consistent performance and steady flux. This work demonstrates the great application potential of EDA@PEI NF membranes for Mg 2+ /Li + separation, and provides a candidate for fabricating PEI-based NF membranes.

CAS / MDL: 7631-90-5
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Potassium 2-thienyl tri-fluoroborate as a functional electrolyte additive enables stable interfaces for Li/LiFe0.3Mn0.7PO4 batteries

Shuai Li,Ruilin Tang,Chuan Hu,Xiaobin Niu,Liping Wang

As a promising cathode material for high-performance lithium-ion batteries, olivine LiFe 1-x Mn x PO 4 (0 < x < 1, LFMP) combines the high safety of LiFePO 4 and the high energy density of LiMnPO 4 . During the charge-discharge process, poor interface stability of active materials leads to capacity decay, which prevents its commercial application. Here, to stabilize the interface, a new electrolyte additive potassium 2-thienyl tri-fluoroborate (2-TFBP) is developed to boost the performance of LiFe 0.3 Mn 0.7 PO 4 at 4.5 V vs. Li/Li + . Specifically, after 200 cycles, the capacity retention remains at 83.78% in the electrolyte containing 0.2% 2-TFBP while the capacity retention without 2-TFBP addition is only 53.94%. Based on the comprehensive measurements results, the improved cyclic performance is attributed to that 2-TFBP has a higher highest occupied molecular orbit (HOMO) energy and its thiophene group can be electropolymerized above 4.4 V vs. Li/Li + for generating uniform cathode electrolyte interphase (CEI) with poly-thiophene, which can stable materials structure and suppress the decomposition of electrolytes. Meanwhile, 2-TFBP both promotes the deposition/exfoliation of Li + at anode-electrolyte interfaces and regulates Li deposition by K + cations through the electrostatic mechanism. This work presents that 2-TFBP has a great application prospect as a functional additive for high-voltage and high-energy-density lithium metal batteries .

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Nanomaterials · 2023 ·Vol. 13 ·期 9 ·1505 · IF 5.3

The Facile Synthesis of Hollow CuS Microspheres Assembled from Nanosheets for Li-Ion Storage and Photocatalytic Applications

Yiyang Zhao,Yonghui Shao,Hao Chen,Xinwen Luo,Xiaodi Liu

Herein, well-defined hollow CuS microspheres assembled from nanosheets were successfully synthesized through a facile solvothermal method. Hollow CuS microspheres have an average diameter of 1.5 μm; moreover, the primary CuS nanosheets have an ultrathin thickness of about 10 nm and are bound by {0001} polar facets. When used as anodes for lithium-ion batteries (LIBs), hollow CuS microspheres exhibit excellent electrochemical properties, including a large discharge capacity (610.1 mAh g−1at 0.5 C), an excellent rate capability (207.6 and 143.4 mAh g−1at 1 and 5 C), and a superior cyclic stability (196.3 mAh g−1at 1 C after 500 cycles). When used as photocatalysts for Rhodamine B (RhB), hollow CuS microspheres can degrade more than 99% of the initial RhB within 21 min. These excellent Li-ion storage properties and photocatalytical performances are attributed to their unique hierarchical hollow structure.Keywords:CuS;hollow microsphere;nanosheet;lithium-ion batteries;photocatalyst

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IONICS · 2023 ·Vol. 29 ·期 8 ·3001-3012 · IF 2.8

Fast Li-ion conductor additive toward high-rate lithium storage capacity for Li2ZnTi3O8 in lithium-ion batteries

Tang Haoqing,Zhao Siying,Weng Qiang,Liu Tao,Tang Zhiyuan,Liu Xiaotong

A novel strategy to improve the ionic conductivity of the Li 2 ZnTi 3 O 8 (LZTO) anode is proposed by embedding exfoliation and exchange of Li + montmorillonite (MMT) in LZTO particles. Li 2 ZnTi 3 O 8 and montmorillonite (LZTO-MMT) composites are shown to induce not only a high concentration of Li + in the interlamellar channel of MMT but also a reduction in the distance for Li + migration to ensure fast and stable Li + diffusion kinetics. Furthermore, the thus obtained LZTO and 6 wt% MMT (LZTO-6MMT), composed of fast Li + conductor MMT, exhibits increased Li + conductivities, excellent high-rate Li + storage capacities, and significant improvement in cycle reversibility. The LZTO-6MMT electrode delivers 219.6 mAh g −1 at a current density of 1.0 A g −1 after 500 cycles and shows an excellent high-rate performance of 127.8 and 112.0 mAh g −1 over 2000 cycles at 5.0 and 10.0 A g −1 , respectively. X-ray photoelectron spectroscopy and ex situ Raman spectrum analyses suggest that the chemical bonds and crystal structure remain stable after multiple Li + intercalation/deintercalation processes. To the best of our knowledge, this is the first report on the introduction of fast-ion conductor MMT into LZTO and its application to lithium-ion batteries.

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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2023 · IF 3.8

Zeolitic imidazolate framework-8 modified poly(vinylidene fluoride-co-hexafluoropropylene)/polyacrylonitrile composite separators for Li-ion batteries

Yanhuai Ding,Cong Zhang,Hao Zheng,Yi Han

As one of the most stable metal-organtic framework (MOF), zeolitic imidazolate framework-8 (ZIF-8) has been widely studied for applications in the field of energy storage, catalysis, and environment protection. In this paper, ZIF-8 was employed to enhance the electrochemical properties and thermal stability of the electrospun poly(vinylidene fluoride- co -hexafluoropropylene)/polyacrylonitrile (PVDF-HFP/PAN) composite separator. The results indicate that the test cells assembled with the composite separators show improved rate capability, high discharge capacity, and stable cycling performances. The addition of ZIF-8 can improve the affinity of PVDF-HFP/PAN toward liquid electrolytes, and further enhance the ionic conductivity of the composite separators. In addition, the thermal stability of the PVDF-HFP/PAN separator has been improved by ZIF-8 nanoparticles . This work can provide insight into the application of MOF materials in Li-ion batteries.

CAS / MDL: 25014-41-9 9011-17-0
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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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Materials Today Energy · 2023 · IF 9.3

Separator modification by MoxC/N-doped graphene enabling polysulfide catalytic conversion for high-performance Li–S batteries

Xiyun Yang,Jiamin Liu,Fulu Chu,Jie Lei,Feixiang Wu

The shuttle effect and sluggish electrochemical conversion of polysulfides have been believed to strongly influence the performances of lithium-sulfur (Li–S) batteries. Herein, we propose the synthesis of nanosized Mo x C electrocatalysts embedded on N-doped graphene and develop its application for separator modification of Li–S batteries. The N-doped graphene provides a two-dimension conductive barrier layer to chemically adsorb polysulfides and inhibit polysulfides diffusion, while Mo x C nanoparticles could serve as the functional electrocatalyst to facilitate the redox kinetics of the multiphase conversion. The Li–S coin cells with Mo x C@N-rGO-modified separator can exhibit good long-term cycling stability with a capacity decay of 0.069% per cycle after 400 cycles at 0.5C and excellent rate performance with a discharge capacity of 653 mAh/g at 4C. An area capacity of 4.5 mAh/cm 2 is also achieved with a high sulfur loading of 5.2 mg/cm 2 and a low electrolyte/sulfur ratio of ∼5 μL/mg.

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ACS Applied Materials & Interfaces · 2023 · IF 9.5

CO2-Activation Nanofiber Carbon Paper as a High-Performance Interlayer for Trapping Polysulfides in Li–S Batteries

Ling Meng,Chenying Song,Qixuan Lin,Guanghang Sun,Jin Long,Xiting Zhang,Hailong Li,Jian Hu,Siyu Ye

Lithium–sulfur (Li–S) batteries have high theoretical energy density but low sulfur utilization due to the inherent insulating nature of sulfur and the shuttle effect of polysulfides. Herein, the CO2-activation carbon paper was prepared by poly(p-phenylenebenzobisoxazole) (PBO) nanofiber and was first applied as an interlayer for efficiently alleviating the shuttle effect of polysulfides in Li–S batteries. This interlayer exhibits good flexibility and strength with rich −C═O and −COOH functional groups on the three-dimensional porous structure, which improves chemical adsorption on Li2Sx species and ion rapid diffusion via interconnected diffusion channels and thus enhances the electrochemical kinetics. The initial specific capacity is 1367.4 mAh g–1 and remains 999.8 mAh g–1 after 200 cycles at 0.2C and 780.1 mAh g–1 at 5C, and the Coulombic efficiency is high, up to 99.8%, which is much better than that for the carbon paper without CO2 activation. The highly conductive flexible PBO carbon paper may bring breakthroughs in performance and thus lead to more practical applications of Li–S batteries.

CAS / MDL: 68-12-2 7704-34-9
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MOLECULES · 2023 ·Vol. 28 ·期 7 ·3191 · IF 4.6

Synthesis of High Specific Surface Lithium-Ion Sieve Templated by Bacterial Cellulose for Selective Adsorption of Li+

Xi Zhang,Xudong Zheng,Tongtong Xu,Yuzhe Zhang,Guomeng Li,Zhongyu Li

In recent years, with the development of batteries, ceramics, glass and other industries, the demand for lithium has increased rapidly. Due to the rich lithium resources in seawater and salt-lake brine, the question of how to selectively adsorb and separate lithium ions from such brine has attracted the attention and research of many scholars. The Li-ion sieve stands out from other methods thanks to its excellent special adsorption and separation performance. In this paper, mesoporous titanium dioxide and lithium hydroxide were prepared by hydrothermal reaction using bacterial cellulose as a biological template. After calcination at 600 °C, spinel lithium titanium oxide Li2TiO3was formed. The precursor was eluted with HCl eluent to obtain H2TiO3. The lithium titanate were characterized by IR, SEM and X-ray diffraction. The adsorption properties of H2TiO3were studied by adsorption pH, adsorption kinetics, adsorption isotherm and competitive adsorption. The results show that H2TiO3has a single-layer chemical adsorption process, and has a good adsorption effect on lithium ions at pH 11.0, with a maximum adsorption capacity of 35.45 mg g−1. The lithium-ion sieve can selectively adsorb Li+, and its partition coefficient is 2242.548 mL g−1. It can be predicted that the lithium-ion sieve prepared by biological template will have broad application prospects.Keywords:lithium ion sieve;bacterial cellulose;hydrothermal method;titanium;selective adsorption

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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Electrochemical conversion of natural graphite minerals into carbon nanostructures incorporated with Fe3Si for Li-ion storage application

Ali Reza Kamali,Haoyu Zhao

Natural graphite mineral (NGM) is an abundant and low-cost carbon source with the potential of being employed as the precursor for producing high-quality carbon nanostructures for energy storage applications. In this article, one-pot electrochemical conversion of NGM into graphitic carbon nanostructures incorporated with Fe 3 Si nanocrystals with enhanced bulk electrical conductivity and Li-ion storage performance is reported. To this end, electrodes made of NGM are negatively polarized in molten LiCl-NaCl at 740 °C under various cathode current densities. At 1 A cm −2 , the high-yield conversion of the mineral into carbon nanotubes (CNTs), nanofibers and onion-like carbon nanoparticles is realized. The product exhibits a specific electrical conductivity of 9.83 S m 2 g −1 , and the Li + transfer resistance of 24 Ω. The Li-ion storage capacity of the material is evaluated to be high at 382 mAh g −1 after 220 Li-ion insertion and extraction cycles under the current density of 200 mA g −1 , making the material an attractive low-cost candidate for the anode of lithium ion batteries . The ferromagnetic behavior of the nanostructured Fe 3 Si incorporated carbon is characterized by the saturation magnetization of 11.1 emu g −1 , potentially promoting the recyclability of spent anode material . This article reports on the green and low-cost conversion of NGMs into nanostructured carbon materials with enhanced Li-ion storage performance.

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