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151.
The thermal variation of the first stage ternary compound Cs(THF)1.75C24 has been investigated by powder neutron diffraction. Two phase transitions have been observed. The first one occurs at 248 K and can be interpreted as a three-dimensional segregation within the graphitic host. The second one starts at about 180 K and is continuous down to 50 K. This corresponds to a decorrelation of the graphen planes at low temperature. The origin of this transition could be the elastic constraint due to the kinks of the planes. 相似文献
152.
Zemin Sun Mengwei Yuan Kefan Shi Yuhui Liu Di Wang Dr. Caiyun Nan Dr. Huifeng Li Prof. Genban Sun Prof. Xiaojing Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7244-7249
NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni2+ to the surroundings of Li+, resulting in electron-deficient properties of the Ni sites, which would function as “electron-hungry” sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li−NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm−2, which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO2. Reasonable intercalation adjustment effectively activates laminated Ni2+ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials. 相似文献
153.
Juan Li Shuang Hou Tiezhong Liu Liangke Wang Chen Mei Yayun Guo Prof. Lingzhi Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(9):2013-2024
Improving the performance of anode materials for lithium-ion batteries (LIBs) is a hotly debated topic. Herein, hollow Ni−Co skeleton@MoS2/MoO3 nanocubes (NCM-NCs), with an average size of about 193 nm, have been synthesized through a facile hydrothermal reaction. Specifically, MoO3/MoS2 composites are grown on Ni−Co skeletons derived from nickel–cobalt Prussian blue analogue nanocubes (Ni−Co PBAs). The Ni−Co PBAs were synthesized through a precipitation method and utilized as self-templates that provided a larger specific surface area for the adhesion of MoO3/MoS2 composites. According to Raman spectroscopy results, as-obtained defect-rich MoS2 is confirmed to be a metallic 1T-phase MoS2. Furthermore, the average particle size of Ni−Co PBAs (≈43 nm) is only about one-tenth of the previously reported particle size (≈400 nm). If assessed as anodes of LIBs, the hollow NCM-NC hybrids deliver an excellent rate performance and superior cycling performance (with an initial discharge capacity of 1526.3 mAh g−1 and up to 1720.6 mAh g−1 after 317 cycles under a current density of 0.2 A g−1). Meanwhile, ultralong cycling life is retained, even at high current densities (776.6 mAh g−1 at 2 A g−1 after 700 cycles and 584.8 mAh g−1 at 5 A g−1 after 800 cycles). Moreover, at a rate of 1 A g−1, the average specific capacity is maintained at 661 mAh g−1. Thus, the hierarchical hollow NCM-NC hybrids with excellent electrochemical performance are a promising anode material for LIBs. 相似文献
154.
Kenna L. Salvatore Diana M. Lutz Dr. Haoyue Guo Dr. Shiyu Yue Joceline Gan Dr. Xiao Tong Dr. Ping Liu Dr. Esther S. Takeuchi Dr. Kenneth J. Takeuchi Dr. Amy C. Marschilok Dr. Stanislaus S. Wong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(42):9389-9402
Solution-based, anionic doping represents a convenient strategy with which to improve upon the conductivity of candidate anode materials such as Li4Ti5O12 (LTO). As such, novel synthetic hydrothermally-inspired protocols have primarily been devised herein, aimed at the large-scale production of unique halogen-doped, micron-scale, three-dimensional, hierarchical LTO flower-like motifs. Although fluorine (F) doping has been explored, the use of chlorine (Cl) dopants is the primary focus here. Several experimental variables, such as dopant amount, lithium hydroxide concentration, and titanium butoxide purity, were probed and perfected. Furthermore, the Cl doping process did not damage the intrinsic LTO morphology. The analysis, based on interpreting a compilation of SEM, XRD, XPS, and TEM-EDS results, was used to determine an optimized dopant concentration of Cl. Electrochemical tests demonstrated an increased capacity via cycling of 12 % for a Cl-doped sample as compared with pristine LTO. Moreover, the Cl-doped LTO sample described in this study exhibited the highest discharge capacity yet reported at an observed rate of 2C for this material at 143mAh g−1. Overall, these data suggest that the Cl dopant likely enhances not only the ion transport capabilities, but also the overall electrical conductivity of our as-prepared structures. To help explain these favorable findings, theoretical DFT calculations were used to postulate that the electronic conductivity and Li diffusion were likely improved by the presence of increased Ti3+ ion concentration coupled with widening of the Li migration channel. 相似文献
155.
Xiao-Yi Song Yu-Hang Zhang Ping-Ping Sun Prof. Dr. Jun Gao Prof. Dr. Fa-Nian Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(25):5654-5661
Novel lithium–lanthanide (Ln: cerium and praseodymium) bimetallic coordination polymers with formulas C10H2LnLiO8 (Ln: Ce (CeLipma) and Pr (PrLipma)) and C10H3CeO8 (Cepma) were prepared through a simple hydrothermal method. The three compounds were characterized by means of FTIR spectroscopy, X-ray diffraction, single-crystal X-ray diffraction, SEM, TEM, and X-ray photoelectron spectroscopy. The results of structural refinement show that they belong to triclinic symmetry and P space group with cerium (or praseodymium) and lithium cations, forming coordination bonds to oxygen atoms from different pyromellitic acid molecules, and leading to the construction of 3D structures. It is interesting to note that the frameworks exclude any coordination water and lattice water. As an electrode material for lithium-ion batteries, CeLipma exhibits a maximum capacity of 800.5 mAh g−1 and a retention of 91.4 % after 50 cycles at a current density of 100 mA g−1. The favorable electrochemical properties of the lanthanide coordination polymers show potential application prospects in the field of electrode materials. 相似文献
156.
Dr. Marzia Dell'Aera Dr. Filippo Maria Perna Dr. Paola Vitale Dr. Angela Altomare Prof. Alessandro Palmieri Dr. Lewis C. H. Maddock Leonie J. Bole Dr. Alan R. Kennedy Prof. Eva Hevia Prof. Vito Capriati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8742-8748
We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R4ZnLi2) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R4ZnLi2 provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et4ZnLi2 into equimolar amounts of solvent-separated Et3ZnLi and EtLi. 相似文献
157.
为了解决锂电池负极表面锂枝晶生长带来的性能衰退和安全问题。 以沸石咪唑酯骨架-8(ZIF-8)为前驱体制得介孔碳材料(MCM),用于金属锂负极表面改性。 X射线粉末衍射(XRD)和拉曼光谱表明,退火制得的MCM具有一定的石墨化程度,N2气吸脱附测试(BET)证明MCM具有典型的介孔特征。 对比不同温度退火样品的XRD、拉曼光谱和BET测试结果,确定900 ℃为最佳退火温度。 优化的MCM作为表面改性剂对金属锂负极进行改性研究。 电池充放电循环后,负极样品的XRD和扫描电子显微镜(SEM)测试表明,MCM能够通过均衡锂负极表面的电荷分布抑制金属锂的取向沉积和锂枝晶的生长。 本研究为制备抑制锂电池负极枝晶生长表面改性剂提供了一种简便而有效的合成方法,有利于锂电池循环寿命的延长和安全性能的提高。 相似文献
158.
Dr. Hong Shang Yu Gu Prof. Yingbin Wang Dr. Zicheng Zuo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5434-5440
Nonuniform nucleation is one of the major reasons for the dendric growth of metallic lithium, which leads to intractable problems in the efficiency, reversibility, and safety in Li-based batteries. To improve the deposition of metallic Li on Cu substrates, herein, a freestanding current collector (NGDY@CuNW) is formed by coating pyridinic nitrogen-doped graphdiyne (NGDY) nanofilms on 3D Cu nanowires (CuNWs). Theoretical predictions reveal that the introduction of nitrogen atoms in the 2D GDY can enhance the binding energy between the Li atom and GDY, therefore improving the lithiophilicity on the surface for uniform lithium nucleation and deposition. Accordingly, the deposited metallic Li on the NGDY@CuNW electrode exhibits a dendrite-free morphology, resulting in significant improvements in terms of the reversibility with a high coulombic efficiency (CE) and a long lifespan at high current density. Our research provides an efficient method to control the surface property of Cu, which also will be instructive for other metal batteries. 相似文献
159.
One‐Pot Synthesis of Pomegranate‐Structured Fe3O4/Carbon Nanospheres‐Doped Graphene Aerogel for High‐Rate Lithium Ion Batteries
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Dr. Dafang He Lixian Li Fengjuan Bai Chenyang Zha Prof. Liming Shen Prof. Harold H. Kung Prof. Ningzhong Bao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4454-4459
A unique hierarchically nanostructured composite of iron oxide/carbon (Fe3O4/C) nanospheres‐doped three‐dimensional (3D) graphene aerogel has been fabricated by a one‐pot hydrothermal strategy. In this novel nanostructured composite aerogel, uniform Fe3O4 nanocrystals (5–10 nm) are individually embedded in carbon nanospheres (ca. 50 nm) forming a pomegranate‐like structure. The carbon matrix suppresses the aggregation of Fe3O4 nanocrystals, avoids direct exposure of the encapsulated Fe3O4 to the electrolyte, and buffers the volume expansion. Meanwhile, the interconnected 3D graphene aerogel further serves to reinforce the structure of the Fe3O4/C nanospheres and enhances the electrical conductivity of the overall electrode. Therefore, the carbon matrix and the interconnected graphene network entrap the Fe3O4 nanocrystals such that their electrochemical function is retained even after fracture. This novel hierarchical aerogel structure delivers a long‐term stability of 634 mA h g?1 over 1000 cycles at a high current density of 6 A g?1 (7 C), and an excellent rate capability of 413 mA h g?1 at 10 A g?1 (11 C), thus exhibiting great potential as an anode composite structure for durable high‐rate lithium‐ion batteries. 相似文献
160.