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JOURNAL OF ENVIRONMENTAL MANAGEMENT · 2022 · IF 8.91

Novel study on catalytic pyrolysis of chitin biomass using waste cathode material recovered from spent Li-ion battery

Liang Chen,Yafei Shen

Waste cathode (BC) from spent lithium-ion battery (LIB) was preliminarily studied for the catalytic pyrolysis of chitin biomass using thermogravimetric and pyrolysis-gas chromatography/mass spectrometry analysis. Compared with the dry-mixing method (BC1), the wet-impregnation method (BC2) significantly increased the decomposition rate of chitin pyrolysis and decreased the apparent activation energy from 85 kJ/mol to 76 kJ/mol. BC2 had a superior catalytic effect on the conversion of heavy components into light fractions. In particular, the selectivities for acetamides and acetonitrile were improved. Furthermore, BC2 enhanced the cleavage of glucosidic, C–O, and C–C bonds, thereby improving the thermolysis of chitin to acetamido acetaldehyde. The production of acetamides, acetonitriles, and other light components (e.g., ketones) was further enhanced via deoxygenation and hydrogenation reactions. Additionally, the selectivity of N-heterocycles (pyridine and pyrrole) and their derivatives (tar-N surrogates) decreased, indicating that tar was significantly reduced during the catalytic pyrolysis and gasification of chitin biomass.

CAS / MDL: 1398-61-4 9012-76-4
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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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Materials Advances · 2022 ·Vol. 3 ·期 8 ·3631-3641 · IF 0

Multifunctional sandwich-structured double-carbon-layer modified SnS nanotubes with high capacity and stability for Li-ion batteries

Jia Luo,Huaiyu Li,Guo Yu,Wenyuan Xu,Hong Yin,Zhaohui Hou

Tin monosulfide (SnS) anodes have attracted much attention for lithium-ion batteries (LIBs) due to their excellent chemical stability, high theoretical specific capacity and outstanding reversibility. However, the slow kinetics and large volume expansion of intrinsic SnS electrodes in the conversion reaction process restrict their application to a certain extent. To address the poor conductivity and volume fluctuation, N-doped double-carbon-layer protective hierarchical structures decorating SnS nanotubes (N-DCSNs) are introduced by in situ polymerization directed using a g-C3N4 soft template. Particularly, N-doped double carbon layers provide fast transport channels for electrons and ions, affording decent conductivity and rapid ionic diffusion rate. Most importantly, the volume expansion of SnS during the charge–discharge cycles can be buffered owing to the confinement effect of the double carbon layer. Synergistic effects of N-DCSNs enhance the mechanical integrity and electrochemical kinetics during the charge–discharge process, leading to high-capacity retention and long-term stability properties. As a remarkable anode for LIBs, the N-DCSN electrode delivers high capacities of 911.5 and 511.3 mA h g−1 at 0.2 and 1.0 A g−1 after 270 and 1000 cycles, respectively. The feasible and versatile structure design can offer new ideas for the preparation and regulation of other transition metal sulfide anode materials, and provide a relevant experimental basis for the further development of lithium/sodium storage equipment.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

Carbon-coated Si/N-doped porous carbon nanofibre derived from metal–organic frameworks for Li-ion battery anodes

Yaru Li,Xiaoyan Liu,Jiwei Zhang,Haitao Yu,Jingwei Zhang

In order to more effectively alleviate the volume extension and shrinkage of the Si anode during Li intercalation/deintercalation processes, and also to improve the electron and ion transport dynamics, carbon coated Si-porous carbon composite fibres with a sandwich structure were prepared using a sacrificial template (ZIF-8) to construct mesoporous carbon, combined with electrospinning technology and subsequent hydrothermal carbon coating. The carbon fibre skeleton and carbon-coated sandwich structure provide support for the volume extension and shrinkage of Si, avoiding Si from directly contacting with the electrolyte, and forming a stable solid electrolyte interphase film. Furthermore, the polyvinylpyrrolidone spinning solution assists ZIF-8 to obtain a mesoporous structure inside the carbon fibre, which improves the specific surface area and pore volume of the composite material. In this case, the mesoporous structure also helps to alleviate the volume extension and shrinkage of Si during the charging /discharging processes and improves the transmission dynamics of lithium ions and electrons. Benefit from the unique structural features, this anode composite material exhibits enhanced electrochemical properties for Li-ion batteries, with a reversible specific capacity of 1114 mAh g −1 at 1 A g −1 , and demonstrates a capacity retention rate of 66% with a specific capacity of 740 mAh g −1 after 400 cycles.

CAS / MDL: 25249-54-1 9003-39-8
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Nanotechnology Reviews · 2022 ·Vol. 11 ·期 1 ·824-833 · IF 6.739

Core–shell heterostructured composites of carbon nanotubes and imine-linked hyperbranched polymers as metal-free Li-ion anodes

Yu Dou,Jianye Zhang,Xiaoyan Han,Qiming He,Yingkui Yang

An in situ Schiff-base condensation between p -phthalaldehyde (PPD) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) or 1,3,5-tris(4-aminophenyl)triazine (TAPT) was actualized in the presence of carbon nanotubes (CNTs), producing imine-linked hyperbranched poly(PPD-TAPB) and poly(PPD-TAPT)-coated CNTs (abbreviated as CNT@HBP-1 and CNT@HBP-2, respectively). Such quasi-1D core–shell heterostructures are interleaved to build robust 3D networks with porous internal channels, which are favorable for efficient electron transport and ion diffusion, exposing active sites, fast redox kinetics, and high electrochemical utilization. When used as Li-ion anodes, both CNT@HBP-1 and CNT@HBP-2 exhibit larger specific capacity, better rate performance, and higher cycling stability compared to their pure polymers. Furthermore, CNT@HBP-2 delivers higher reversible capacities of 351 mA h g −1 at 0.05 A g −1 , and 81 mA h g −1 at 1.0 A g −1 , respectively, compared to CNT@HBP-1 (335 and 56 mA h g −1 ). Besides, CNT@HBP-2 retains 268 mA h g −1 over 100 cycles at 0.1 A g −1 , and 617 mA h g −1 in the 500th cycles at 0.5 A g −1 , respectively, outperforming CNT@HBP-1 (155 and 256 mA h g −1 ). Further improvements in the electrochemical performance for CNT@HBP-2 relative to CNT@HBP-1 are attributable to the incorporation of additional redox-active triazine units into HBP-2. This work would unlock insights into the rational development of metal-free polymer-based electrodes for rechargeable batteries.

CAS / MDL: 76-05-1 106-50-3
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Journal of Materials Chemistry A · 2022 ·Vol. 10 ·期 15 ·8424-8431 · IF 14.511

A dendrite-suppressed and utilization-improved metallic Li anode enabled by lithiophilic nano-Pb decoration on carbon cloth

Peng Du,Chenbo Yuan,Xiaoyu Cui,Kaifu Zhang,Yu Yu,Xiaodi Ren,Xiaowen Zhan,Shan Gao

The commercialization of Li metal anodes has been long hindered by uncontrolled dendrite growth, infinite volume expansion and poor Li metal utilization. Herein, we achieve a uniform nano-Pb decoration on carbon cloth (Pb@CC) by exploiting the thermal decomposition process of lead acetate trihydrate monitored by in situ Raman spectroscopy. 3D hosted Li anodes are fabricated via a record-fast infusion (1.0 s) of accurate weight-controlled molten Li into the highly lithiophilic Pb@CC host at a considerably low temperature of 250 °C. At an optimal Li loading of 10 mg, the Pb nanoparticles guide the uniform distribution of Li sites over the robust yet porous electron-conducting carbon network, which not only directs and confines Li nucleation and growth, but accommodates volume changes during repeated Li stripping/plating processes. The resulting Li electrodes afford an ultralong cycle life of 4648 h at low overpotentials of <50 mV under 1 mA cm−2/1 mA h cm−2 symmetric-cell cycling, which is among the best records ever reported in the literature. The corresponding LiFePO4 and LiNi0.8Co0.1Mn0.1O2 full cells deliver significantly higher cycling and rate performances than those with Li foils. Furthermore, the effect of Li utilization is explored in Li‖LiFePO4 full cells, with the best cyclability achieved at a low N/P ratio of 63.28. The present findings stretch the practical feasibility of wetting-assisted molten Li infusion in mitigating dendrite growth and improving Li utilization towards long-cycling high-energy-density Li metal batteries.

CAS / MDL: 6080-56-4
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JOURNAL OF ALLOYS AND COMPOUNDS · 2021 · IF 5.316

A Ti3C2Tx MXene - carbon nanocage - sulfur cathode with high conductivity for improving the performance of Li-S batteries

Xianwei Geng,Chenguang Liu,Yi Sun,Yingchao Zhao,Ruowei Yi,Pengfei Song,Chun Zhao,Ivona Mitrovic,Li Yang,Cezhou Zhao

Lithium-sulfur (Li-S) batteries hold their promise in renewable next-generation energy storage technologies due to low cost and high theoretical energy. Herein, a Ti 3 C 2 T x MXene-carbon nanocage-sulfur (MXene/CNC/S) cathode is synthesized by a simple process with high conductivity and outstanding performance in Li-S batteries. The cathode with an unusually high sulfur content of 80% demonstrates an eminent initial specific capacity of 1275.5 mAh·g −1 at 0.1 C and retains 823.8 mAh·g −1 after 100 cycles, showing a high retention rate of 64.6%. Besides, it exhibits a great conductive feature for rate performance, delivering 630.5 mAh·g −1 capacity when the current rises to 4 C. In this composition electrode, the excellent electrochemical performance indicates that MXene can effectively adsorb polysulfides to help batteries achieve long-term cyclic performance. On the other hand, the introduction of CNC strongly improves the specific surface area of the cathode and constructs a high conductive network to reduce the stacking of MXene, thus exhibiting better rate performance and increasing utilization of sulfur. Our work holds future technological significance as it could accelerate progress towards lithium-sulfur batteries with high sulfur content and less pricy conductive materials.

CAS / MDL: 7789-24-4 68-04-2
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ELECTROCHIMICA ACTA · 2021 · IF 6.901

Elucidating the effect of Nb doping on the electrochemical performance of Fe–Mn based Li-rich cathode materials

Chen Hou,Yi-Ran Xing,Le-Le Yu,Yong-Heng Si,Han Lu,Yu-Juan Zhao

Fe–Mn based Li-rich cathode materials are regarded as one of the most promising cathode materials for their low cost and high energy density but possess drawbacks such as high oxygen release, low conductivity, and slow kinetics for lithium-ion transport. To address these issues, herein, we proposed a high-valance cations Nb 5+ doping strategy and synthesized a series of Li 1.26 [Fe 0.22 Mn 0.52 ] 1−x Nb 0.74x O 2 ( x  = 0, 0.02, 0.03, 0.04) cathode materials. Using a combination of experimental approaches and density functional theory (DFT) calculations, we found that the doped samples presented expanded interlayer spacing for Li-ion migration and better structural stability due to the large ionic radius of Nb 5+ and the strengthened Nb–O bond. Moreover, Nb doping could not only decrease the band gap and the density of states of the O 2p band but also contribute extra electrons to surrounding O atoms, thereby enhancing electronic conductivity and stabilizing lattice oxygen. Benefit from the underlying mechanisms mentioned above, the Nb 0.022 sample possessed a higher Coulombic efficiency (71.1 vs 65.0%) at 0.2 C, showing more stable cycling performance (90.4 vs 67.7 mAh g −1 ) at 0.5 C and rate capability. These favorable results can assist in the development of Fe–Mn based Li-rich cathode materials with excellent electrochemical properties.

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SOLID STATE IONICS · 2021 · IF 3.785

PVP-grafted synthesis for uniform electrospinning silica@carbon nanofibers as flexible free-standing anode for Li-ion batteries

Na Sun,Xuhui Wang,Xufeng Dong,Hao Huang,Min Qi

The application of the SiO 2 anodes for flexible and free-standing lithium-ion batteries (LIBs) is restricted by the weaknesses of SiO 2 nanoparticles , such as agglomeration, huge volume expansion and rapid capacity fading during charge/discharge cycles. Herein, the PVP-grafted-silica@carbon nanofibers (PVP-g-SiO 2 @CNF) flexible free-standing anode with high capacity and long cycle stability is successfully fabricated by PVP-grafted-SiO 2 , electrospinning and subsequent heat treatment . PVP modifies the interface between SiO 2 nanoparticles and electrospinning solution to prevent the nanoparticles from aggregation, which makes them are uniformly encapsulated in nanofibers. The uniform structure is beneficial to enhance the interface contact between SiO 2 and Li + , and alleviate volume expansion during lithiation . Furthermore, PVP introduces mesoporous into carbon nanofibers , facilitating the transports of ions and electrons to attain high-rate performance. As a flexible free-standing anode material for LIBs, PVP-g-SiO 2 @CNF achieves high reversible capacity, high-rate capacity and superior cycle stability (440 mAh g −1 at 0.1 A g −1 after 200 cycles), especially 89% capacity retention after 180° bending deformation . Consequently, enhanced capacity and cycle stability for flexible free-standing anode are available through PVP-grafted interface modification and electrospinning.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Efficient separation of Li and Mn from spent LiMn2O4 cathode materials by NH4HSO4 reduction roasting-selective ammonia leaching

Ao Zhou,Zhihong Liu,Zhiyong Liu

With the imminent peak in the retirement of rechargeable lithium-ion batteries worldwide, the development of efficient methods for recycling valuable elements from LIBs has attracted considerable attention. In this work, a novel method of NH 4 HSO 4 reduction roasting-selective ammonia leaching was proposed to thoroughly separate Li and Mn from the spent LiMn 2 O 4 cathode materials . Using the TG-DSC-FTIR, XRD, SEM-EDS and ICP methods, the detailed mechanism of reduction roasting process was revealed, showing that the Mn 4+ and Mn 3+ in the spinel structure of LiMn 2 O 4 were reduced by the NH 4 + from the molten ammonium salt, and transformed into water-soluble MnSO 4 and Li 2 Mn 2 (SO 4 ) 3 . According to the water-leaching performance of the roasting products, the sulfation conversion rate of Mn reaches 98.1 %, while Li is almost completely transformed under the optimal roasting conditions (475 ℃, 60 min). Using the NH 3 ·H 2 O-air leaching-system, complete separation of Li and Mn can be achieved. It was shown that the introduction of air into the ammonia solution at a rate of 0.2 L/min under the optimal leaching condition leads to Mn precipitation in the form of nanoscale Mn 3 O 4 particles with a precipitation rate of over 99.99 %, while Li still remains completely leached. Based on the in situ detection of the oxidation reduction potential and pH during the selective leaching, the key mechanism of efficient Mn precipitation was revealed. that is, the increasing potential accelerates the oxidation of Mn(OH) 2 , and the rapid consumption of Mn(OH) 2 promotes the hydrolysis of Mn 2+ , thereby achieving a significant improvement in the separation efficiency of Li and Mn.

CAS / MDL: 1336-21-6 7803-63-6
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Journal of Sustainable Metallurgy · 2023 ·Vol. 9 ·期 4 ·1456-1465 · IF 2.4

Extraction of Lithium From Salt Lake Brine with High Mg/Li Mass Ratio by N523-DIBK Extraction System

Li Hui-Fang,Li Li-Juan,Ji Lian-Min,Shi Dong

To develop a more stable and more efficient extraction system, a novel amide extraction system, containing extractant N , N -bis(2-ethylhexyl) acetamide (N523) and diluent diisobutyl ketone (DIBK), was proposed in this work. A series of operation conditions, such as the concentration of initial lithium in aqueous phase, the volume ratio of N523 and DIBK, phase ratio of O / A , the molar ratio of Fe/Li, were carried out. The lithium extraction rate reached up to 92% under the optimal extraction conditions. Considering the mass transfer of two phases and consumption of extractant, the three-stage counter-current extraction experiment was conducted. After 6 cycles experiment of the three stage counter-current extraction, the lithium extraction rate reached 99.89% and the separation factor of Li/Mg, Li/Na, Li/K, and Li/Ca were 103,300, 5288, 5233, and 760.4, respectively. The stoichiometry of the complex was LiFeCl 4 ·N523 by the slope method. The results indicated that N523-DIBK extraction system was effective to recovery of lithium from salt lake brine with high mass ratio of Mg/Li. Furthermore, the extraction thermodynamics study revealed lithium extraction was an exothermic process, which meant lower temperature promoted lithium extraction. Graphical Abstract

CAS / MDL: 108-83-8
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Nanofiltration membrane based on a dual-reinforcement strategy of support and selective layers for efficient Mg2+/Li+ separation

Hongshan Wang,Guangyong Zeng,Zhaomei Yang,Xi Chen,Ludan Wang,Yuan Xiang,Xiangdong Zeng,Zhenhua Feng,Binbin Tang,Xudong Yu,Ying Zeng

With the consumption of lithium resources increasing year by year, the investigation of high-performance salt lake lithium extraction technology is extremely important. In order to effectively separate Mg 2+ and Li + from brine, a novel charge-positive nanofiltration (NF) membrane with high permeability and excellent Mg 2+ /Li + separation factor was designed by interfacial polymerization (IP) in this work. A B15C5-MX-NF membrane was fabricated by blending hydrophilic two-dimensional (2D) MXene nanosheets into a PES membrane substrate to enhance the permeability, followed by the modification of polyamide (PA) layer with a crown ether molecule (Benzo-15-crown-5) to optimize the surface properties of membrane. The PA layer thickness was effectively reduced (58 nm) due to the enhancement in the interaction between the substrate membrane and PEI by the incorporation of MXene, while the addition of B15C5 provided additional Li + permeation channels. The B15C5-MX-NF membrane exhibited excellent permeability (16.1 L·m −2 ·h −1 ·bar −1 ) and superior selectivity for Mg 2+ /Li + ( S Li, Mg of 15.8) under the dual optimization of membrane substrate and PA layer. In addition, it was demonstrated by molecular dynamics (MD) simulations that the B15C5 molecules in the B15C5-MX-NF membranes had a specific recognition ability of Li + to allow its preferential permeation, thereby enhancing the Mg 2+ /Li + selectivity of the membranes. This study provides a new idea for the preparation of NF membranes for efficient Mg 2+ /Li + separation.

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