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ChemElectroChem · 2018 ·Vol. 5 ·期 13 ·1702-1707 · IF 4.446

Super P Carbon Modified Lithium Anode for High-Performance Li−O2 Batteries

Jiaqi Wang,Junxiang Liu,Yichao Cai,Fangyi Cheng,Zhiqiang Niu,Jun Chen

Graphical Right off the batt : A Li@Super P composite anode with a high specific surface area is fabricated through a low-cost brushing method, which effectively decreases the interface impedance and overpotential of Li depositing/stripping. The anode can also mitigate the detrimental shuttling effect of I 3 − generated from LiI during the charging process. The combination of the protected Li anode and LiI mediator delivers superior Li−O 2 battery performance. Rechargeable Li−O 2 batteries represent a highly attractive battery technology, owing to a high theoretical energy density of 3500 Wh kg −1 , but they suffer from large charging polarization and lithium anode degradation on cycling. Herein, we report a Li−O 2 battery system with reduced polarization and a long lifespan, which is realized by using a novel Li@Super P composite anode integrated with lithium iodide in ether-based electrolyte. Coating a Super P carbon layer, with an optimal thickness of approximately 30 μm, onto the lithium anode results in a lowered interface impedance and a decreased Li depositing/stripping overpotential (<15 mV) over 300 cycles at 0.3 mA cm −2 . The Li−O 2 batteries assembled with the Li@Super P anode and LiI additive could mitigate the detrimental shuttling effect of I 3 − and deliver a high reversible capacity of 1000 mAh g −1 with a median charge voltage lower than 3.3 V after 50 cycles. This study provides a simple yet effective way to protect the lithium anode and design high-performance Li−O 2 batteries.

CAS / MDL: 10377-51-2
研究领域: 材料科学 · 电化学 · 电池技术
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Cross-linked PVDF-b-PAA composite binder enhanced LiMn2O4/C film based electrode for selective extraction of lithium from brine with a high Mg/Li ratio

Zheng Zhang,Jinfeng Zhang,Zhihua Zhang,Xiao Du,Xiaogang Hao,Xiaowei An,Guoqing Guan,Jun Li,Zhong Liu

A novel physically blended polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA) composite binder enhanced LiMn 2 O 4 /C (carbon black) film based electrode was successfully fabricated, and applied in an electrochemically switched ion exchange (ESIX) process for selective extraction of Li + from high Mg/Li ratio brine. The multifunctional composite binder system enabled the obtained LiMn 2 O 4 /C/PVDF- b -PAA film coated electrode to exhibit superior mechanical, hydrophilic and electrochemical properties compared with the LiMn 2 O 4 /C/PVDF film coated electrode. Based on the density functional theory (DFT) calculations, the ion exchange interaction between H + of –COOH groups in PAA and Li + facilitated the transport of Li + at the electrode interface, which enhanced lithium extraction performance of the film coated electrode. For treating the simulated brine (Mg/Li: ∼500), the intercalation capacity of Li + was about 15.1 mg g −1 , and the total extraction efficiency of lithium reached up to 62.8% after two electrochemical intercalation tests. Moreover, the film coated electrode displayed excellent selectivity towards Li + ions even in pre-treated actual brine (Mg/Li: ∼292.2). The Mg/Li mass ratio in the recovery solution could decrease to 0.46, and the calculated Li + /Mg 2+ separation coefficient reached as high as 631.08. In particular, the highly stable and scalable electroactive film could be prepared effectively, thus increasing its applicability. It is expected that such a LiMn 2 O 4 /C/PVDF- b -PAA film coated electrode could be a promising candidate for the selective extraction of Li + from high Mg/Li mass ratio brines.

研究领域: 材料科学 · 电化学工程
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2024 · IF 11.2

Hybrid of bulk NbC and layered Nb4C3 MXene for tailoring hydrogen storage kinetics and reversibility of Li-Mg-B-H composite: an experimental and theoretical study

Haizhen Liu,Liwen Lu,Hui Luo,Jiayi Deng,Guangxu Li,Hua Ning,Yi Fan,Cunke Huang,Zhiqiang Lan,Wenzheng Zhou,Jin Guo,Xinhua Wang

The Li-Mg-B-H composite (2LiBH 4  + MgH 2 ) is acknowledged as a promising material for hydrogen storage due to its large hydrogen capacity (11.4 wt.%). However, the sluggish kinetics and poor reversibility make it difficult to be practically used. In this work, the hydrogen storage performances of 2LiBH 4  + MgH 2 have been significantly improved by a hybrid of bulk NbC and layered Nb 4 C 3 MXene (denoted as “Nb-C”). The 2LiBH 4  + MgH 2  + 6 wt.% Nb-C can release 8.5 wt.% H 2 within 30 min at 400°C and the dehydrogenated composite can absorb 9.3 wt.% H 2 within 30 min at 350°C and 7.5 MPa H 2 . The reversible dehydrogenation capacity maintains at 8.4 wt.% after 24 cycles, with a capacity retention ratio of 95.4%. By contrast, the undoped 2LiBH 4  + MgH 2 suffers from serious capacity degradation, with the capacity decreased dramatically to 3.5 wt.% after 3 cycles. Microstructural studies revealed that the doped composite has uniform particle and elemental distributions and possesses various multiphase interfaces of LiH/MgB 2 /NbC/Nb 4 C 3 , which is beneficial to hydrogen diffusion during the hydrogen uptake and release process. Theoretical studies by first principle calculation presented an extended bond length of the Mg-H and B-H bonds in the 2LiBH 4  + MgH 2  + NbC system, which may also explain the improved hydrogen storage properties of 2LiBH 4  + MgH 2 by addition of Nb-C. This work provides new insights into the role of transition metal carbides in regulating the Li-Mg-B-H hydrogen storage materials both experimentally and theoretically.

研究领域: 材料科学 · 理论计算
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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Highly-dispersed nano-TiB2 derived from the two-dimensional Ti3CN MXene for tailoring the kinetics and reversibility of the Li-Mg-B-H hydrogen storage material

Hui Luo,Yunshu Yang,Liwen Lu,Guangxu Li,Xinhua Wang,Xiantun Huang,Xiaoma Tao,Cunke Huang,Zhiqiang Lan,Wenzheng Zhou,Jin Guo,Haizhen Liu

Li–Mg–B–H composite (2LiBH 4  + MgH 2 ) possesses a very high hydrogen storage capacity of 11.4 wt%. However, it still suffers from high operating temperature, slow kinetics, and poor reversibility. In this work, the two-dimensional Ti 3 CN MXene was first synthesized and then introduced into the Li–Mg–B–H composite. The addition of 5 wt% Ti 3 CN reduces the onset dehydrogenation temperature of the 2LiBH 4  + MgH 2 composite by about 50 °C and shortens the induction period of the LiBH 4 decomposition at 400 °C from >90 min to <10 min. The reversible capacity maintains at 8.3 wt% after 20 cycles, with a capacity retention ratio of 93%. Microstructure studies show that Ti 3 CN will partially transform to a highly-dispersed nano-TiB 2 with particle size around 5 nm. Such nano-TiB 2 could serve as an active catalyst to significantly improve the kinetics and reversibility of the Li–Mg–B–H composite. This work offers a strategy to enhancing the hydrogen storage performance of the advanced metal borohydride-based composites by addition of the MXene material and provides some new insights in understanding the role of MXene in tailoring the hydrogen storage properties of the Li–Mg–B–H composite.

CAS / MDL: 7664-39-3
研究领域: 材料科学 · 能源存储
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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Stabilization of Li–Se Batteries by Wearing PAN Protective Clothing

Zewen Yang,Kunjie Zhu,Zihao Dong,Dandan Jia,Lifang Jiao

Lithium–selenium (Li–Se) batteries have recently attracted more and more attentions as new secondary battery systems due to the similarity but better performances than lithium–sulfur (Li–S) batteries. However, the dissolution of selenium in electrolytes results in low selenium utilization, concentration polarization, inferior capacities, and unstable cycling performances. Herein, 46.58 wt% of selenium is loaded on carbon cloths through the calcination process, which were directly used as self-supporting cathodes. Carbonized polyacrylonitrile (PAN) nanofiber membranes produced by electrospinning are worn as the protective clothing between the cathode and separator to avoid the loss and dissolution of selenium. The stabilization of Li–Se batteries was enhanced by introducing two interlayers, as expected, they exhibit a stable reversible average capacity of 590 mA h g–1 during 1000 cycles at a current density of 0.5 C (1 C = 675 mA g–1). No polyselenide formation is found during charging/discharging, and the effects of the introduced PAN interlayers on improving the stability and reducing the polarization of the assembled Li–Se batteries are confirmed by mechanistic characterizations. These regulated Li–Se batteries present great application potential in the future, and the design idea can also be promoted to explore other energy storage systems.

研究领域: 材料科学 · 电化学 · 能源存储
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Energy Storage Materials · 2018 · IF 0

Highly synergetic catalytic mechanism of Ni@g-C3N4 on the superior hydrogen storage performance of Li-Mg-B-H system

Xu Huang,Xuezhang Xiao,Xuancheng Wang,Zhendong Yao,Chuntao Wang,Xiulin Fan,Lixin Chen

Li-Mg-B-H system with the composition of 2LiBH 4 -MgH 2 is one of the most promising reversible hydrogen storage materials because of the extremely high hydrogen storage capacity (11.5 wt%). Yet, sluggish kinetics with high desorption temperature (~ 400 °C) hindered its practical applications. Herein, a highly efficient catalyst of nanoNi@g-C 3 N 4 , comprised of transition metal nanocatalyst and carbon-based nonmetal material, was designed and fabricated to dramatically reduce its initial hydrogen desorption temperature to as low as ~105 °C, and eliminate induction period between the two dehydrogenation steps of 2LiBH 4 -MgH 2 by reducing the activation energy for the dehydrogenation of LiBH 4 from 200±6 to 126±7 kJ/mol. Multiple postmortem analyses revealed that the in situ formed MgNi 3 B 2 NPs and the H + defects on g-C 3 N 4 play the key role in synergically enhancing the hydrogen reversible desorption/absorption kinetics at low temperature: 1) in situ formed MgNi 3 B 2 acts as nucleation center of MgB 2 and leads to an excellent catalytic effect to accelerate the dehydrogenation kinetics of 2LiBH 4 -MgH 2 ; 2) the H + defects on g-C 3 N 4 , will interact with the H – in LiBH 4 to trigger the release of H 2 at low temperature and destabilize LiBH 4 and MgH 2 to form Li 3 N and Mg 3 N 2 respectively for the high electronegativity of N: 3) these in situ formed intermediates of Li 3 N and Mg 3 N 2 will be readily rehydrogenated as highly reversible Mg(NH 2 ) 2 and LiH. This novel transition metal and g-C 3 N 4 catalytic composites could provide alternative insights into designing nanosized catalytic hydrogen storage system with low desorption temperature and high capacity for hydrogen-fueled applications.

研究领域: 材料科学 · 能源化学
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ACS Sustainable Chemistry & Engineering · 2024 · IF 7.1

Heterostructured CuCo2S4-Co9S8 Nanosheets as Freestanding Cathodes for Flexible Fiber-Shaped Li-CO2 Batteries

Xiaoqi Zhu,Lin Chen,Qisheng Fang,Jianli Cheng,Yuefeng Su,Paula Ratajczak,Francois Beguin,Bin Wang

Li-CO2 batteries with attractive characteristics of high energy density power supply and carbon dioxide fixation have attracted widespread attention. However, the lack of suitable cathode catalysts and their unsatisfactory electrochemical performance have impeded their development as promising Li-CO2 batteries for energy storage. Constructing heterojunctions by interfacial engineering to improve performance is considered one of the effective strategies. Herein, heterostructured CuCo2S4-Co9S8 nanosheets are fabricated by a facile hydrothermal method and employed as efficient cathode catalysts for Li-CO2 batteries. The construction of heterojunctions by interfacial engineering has proved as an effective strategy to enhance the electrochemical performance of the Li-CO2 batteries. The delocalized electrons between CuCo2S4 and Co9S8 contribute to a low median charge potential (∼3.6 V), small polarization (0.62 V), high energy efficiency of up to 83%, and outstanding cycle life (480 h) of the CuCo2S4-Co9S8 cathodes. Meanwhile, as a proof of concept, flexible fiber-shaped Li-CO2 batteries based on these cathodes are fabricated and demonstrate boosted flexibility adaptability and provide a stable power supply at various bending conditions.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米技术
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ADVANCED MATERIALS · 2025 · IF 26.8

Subsurface Electron Trap Enabled Long-Cycling Oxalate-Based Li-CO2 Battery

Yuchun Liu,Tianqi Liu,Xinyun Wang,Jing Zhang,Xingwu Zhai,Tianchen Wei,Qianqi Shi,Chengjie Lu,Huan Yan,Yujian Xia,Weiren Cheng,Min Zhou

Li-CO₂ batteries promise ultrahigh theoretical energy densities but face efficiency limitations owing to the sluggish decomposition of stable Li 2 CO 3 . Redirecting the redox pathway toward Li 2 C 2 O 4 overcomes this challenge, but its metastability leads to facile conversion to Li 2 CO 3 during discharge. Herein, subsurface electronic confinement is engineered in Mo-based catalysts, leveraging electron-deficient boron (B) as electron traps in the subsurface atomic layers to tailor their interfacial electronic landscapes. This design elevates the Mo d-band and intensifies the hybridization between the Mo d-orbitals and O p-orbitals of oxalate. Strengthening the Mo-O interaction stabilizes Li 2 C 2 O 4 against decomposition. The highly reversible and stable redox chemistry enabled by MoB results in an exceptional cycling stability and energy efficiency across a wide temperature range, with an expanded practical viability. At 70 µA cm −2 , the MoB-based battery is cycled for >1400 h with a high energy efficiency of >85%. The energy efficiency even remains at >90% for ≈150 h at a high temperature (90 °C). This study pioneers a material design framework for use in stabilizing metastable products within Li-CO 2 batteries, advancing their applicabilities in extreme environments, such as deep-earth exploration, by revealing the role of subsurface charge redistribution in steering reaction pathways.

研究领域: 储能 · 材料科学 · 电化学 · 催化 · 纳米技术
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ACS Applied Materials & Interfaces · 2021 · IF 9.229

Surface LiMn1.4Ni0.5Mo0.1O4 Coating and Bulk Mo Doping of Li-Rich Mn-Based Li1.2Mn0.54Ni0.13Co0.13O2 Cathode with Enhanced Electrochemical Performance for Lithium-Ion Batteries

Xueqian Ji,Yuxing Xu,Hailan Feng,Pengfei Wang,Yuncheng Zhou,Jiechen Song,Qing Xia,Qiangqiang Tan

To improve the initial Coulombic efficiency, cycling stability, and rate performance of the Li-rich Mn-based Li1.2Mn0.54Ni0.13Co0.13O2 cathode, the combination of LiMn1.4Ni0.5Mo0.1O4 coating with Mo doping has been successfully carried out by the sol–gel method and subsequent dip-dry process. This strategy buffers the electrodes from the corrosion of electrolyte and enhances the lattice parameter, which could inhibit the oxygen release and maintain the structural stability, thus improving the cycle stability and rate capability. After LiMn1.4Ni0.5Mo0.1O4 modification, the initial discharge capacity reaches 272.4 mAh g–1 with a corresponding initial Coulombic efficiency (ICE) of 84.2% at 0.1C (1C = 250 mAh g–1), far higher than those (221.5 mAh g–1 and 68.9%) of the pristine sample. Besides, the capacity retention of the coated sample is enhanced by up to 66.8% after 200 cycles at 0.1C. Especially, the rate capability of the coated sample is 95.2 mAh g–1 at 5C. XRD, SEM, TEM, XPS, and Raman spectroscopy are adopted to characterize the morphologies and structures of the samples. This coating strategy has been demonstrated to be an effective approach to construct high-performance energy storage devices.

研究领域: 材料科学 · 能源存储技术
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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
研究领域: 材料科学 · 医学 · 生物技术
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DESALINATION · 2024 · IF 8.3

Antibacterial polyamide nanofiltration membranes with intermediate layers of quaternized cellulose nanocrystal for Mg2+/Li+ separation

Jia-Min Jin,Hao Ye,Tian-Hao Li,Ming-Bang Wu,Lin Liu,Juming Yao

Positively charged and non-toxic intermediate layers are highly desirable for the construction of nanofiltration membranes in the field of Mg 2+ /Li + separation. Herein, we have prepared dual-electric layer nanofiltration membranes via introducing positively charged quaternized cellulose nanocrystals (Q-CNC) beyond the negatively charged polyamide skin layers. On the one hand, the strong interactions between Q-CNC and piperazine (PIP) could regulate the thickness, roughness, and residual groups of the polyamide (PA) layers, resulting in improved water flux. On the other hand, the Q-CNC has lots of positive charges which are beneficial for enhancing the rejections of negatively charged polyamide skin layers towards divalent cations since the Donnan and electrostatic effects are long-range forces. Moreover, this effect could be amplified by reducing the thickness of skin layers or decreasing the contents of residual carboxyl groups via adjusting the monomer concentrations. The obtained nanofiltration membranes possess high water flux of 51 L/m 2 /h/bar, and rejection for MgCl 2 of 86 %. The separation factor of Mg 2+ /Li + is 29 when the Mg 2+ /Li + mass ratio in the feed solution is 20:1. Moreover, the nanofiltration membrane with Q-CNC intermediate layers (QNFM) has good antibacterial properties, showing great potential in the fields of lithium extraction from salt lakes.

CAS / MDL: 25322-68-3
研究领域: 材料科学 · 环境工程 · 化学工程
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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

Enhanced red emission of upconversion nanoparticles via Li+ and Tm3+ codoping and active core-shell construction for sensitive detection of miRNAs

Yingchao Li,Canzhao Tu,Qianshun Chen,Yingying Lin,Baoming Li,Haixia Lyu

The overexpression of microRNA-222 (miRNA-222) is closely related to many human diseases, so the development of biosensors to detect this biomarker will contribute to the diagnosis of related diseases. Here, a simple, sensitive and specific fluorescence assay for the detection of miRNA-222 was developed using red-emitting upconversion nanoparticle (UCNP) as the donor and a DNA hairpin with black hole quencher-2 (BHQ-2) as the acceptor. Li + and Tm 3+ -doped UCNP with a strong emission peak at 654 nm was obtained by changing the doped ion ratio and constructing core-shell structures. Under optimal conditions, the linear range for detecting miRNA-222 is 0.5–2.5 nM and the limit of detection is as low as 0.077 nM without any complicated amplification strategy. Finally, the proposed assay was applied for the detection of miRNA-222 in serum samples. The results obtained were similar to those of the standard method, and the spiked recoveries were in the range of 97.62%–102.14 %, suggesting that the proposed method has practical value in a complex biological sample matrix.

研究领域: 生物医学 · 分子诊断 · 纳米技术 · 分析化学
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