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991.
Cyclopropyllithium, C3H5Li ( 1 ), was studied in the presence of one equivalent lithium bromide (LiBr) in diethylether (DEE)/tetrahydrofuran (THF) mixtures and in THF as solvents. Increasing the THF concentration in DEE/THF leads in the 6Li NMR spectrum to a main signal (S1) at δ0.85 (rel. to ext. LiBr/THF) and a second resonance (S2) at δ0.26 aside from a minor component at δ0.07. In pure THF, the ratio of these signals was 66: 28:6. 6Li and 13C NMR allowed to identify the main signal as belonging to a mixed dimer, 1 •LiBr, and the signal at 0.26 ppm to a fluxional mixed tetramer, 1 2•(LiBr)2. 1J(13C,6Li) coupling constants of 11.0 and 9.8 Hz were measured at 168 K for S1 and S2, respectively, and chemical exchange between both signals was detected by 2D 6Li,6Li exchange spectroscopy and analyzed by temperature-dependent 1D 6Li line-shape calculations. These yielded the equilibrium constants Keq for the chemical exchange Li4(C3H5)2Br2 ⇌ 2 Li2C3H5Br. Their temperature dependence leads to van't Hoff parameters of ΔH° = 4.6 kJ/mol, ΔS° = 41.4 J/mol K, and ΔG°298 = −7.8 kJ/mol. From the rate constants k, Eyring parameters of ΔH* = 42.0 kJ/mol, ΔS* = 33.0 J/mol K, and ΔG*298 = 32.2 kJ/mol were calculated for the forward reaction Li4(C3H5)2Br2 → 2 Li2C3H5Br and ΔH* = 37.5 kJ/mol, ΔS* = −8.4 J/mol K, and ΔG*238 = 40.0 kJ/mol for the reverse reaction 2Li2C3H5Br → Li4(C3H5)2Br2. 相似文献
992.
Florian Schmidt Andrea Pugliese Catherine C. Santini Franca Castiglione Monika Schönhoff 《Magnetic resonance in chemistry : MRC》2020,58(3):271-279
Electrophoretic nuclear magnetic resonance (eNMR) is a powerful tool in studies of nonaqueous electrolytes, such as ionic liquids. It delivers electrophoretic mobilities of the ionic constituents and thus sheds light on ion correlations. In applications of liquid electrolytes, uncharged additives are often employed, detectable via 1H NMR. Characterizing their mobility and coordination to charged entities is desirable; however, it is often hampered by small intensities and 1H signals overlapping with major constituents of the electrolyte. In this work, we evaluate methods of phase analysis of overlapping resonances to yield electrophoretic mobilities even for minor constituents. We use phase-sensitive spectral deconvolution via a set of Lorentz distributions for the investigation of the migration behavior of additives in two different ionic liquid-based lithium salt electrolytes. For vinylene carbonate as an additive, no field-induced drift is observed; thus, its coordination to the Li+ ion does not induce a correlated drift with Li+. On the other hand, in a solvate ionic liquid with tetraglyme (G4) as an additive, a correlated migration of tetraglyme with lithium as a complex solvate cation is directly proven by eNMR. The phase evaluation procedure of superimposed resonances thus broadens the applicability of eNMR to application-relevant complex electrolyte mixtures containing neutral additives with superimposed resonances. 相似文献
993.
以掺杂4 mol%Hf4+的LiNbO3:Fe:Hf系列晶体([Li]/[Nb]比变化)为研究对象,研究了系列晶体的可见吸收光谱,在632.8nm的写入光下晶体的衍射效率、灵敏度和抗光散射能力在不同[Li]/[Nb]下的变化规律.研究发现Hf4+的浓度达到阈值浓度后,随着[Li]/[Nb]比的增大,晶体的可见吸收边会发生红移,而且晶格中[Fe2+]/[Fe3+]也会增加,这就导致随着[Li]/[Nb]比的增加,样品的衍射效率逐渐减小,写入时间缩短,灵敏度增大.同时,在晶体中,随着[Li]/[Nb]的增大,陷阱中心Fe2+Li数量增大会使得晶体抗光散射能力减弱. 相似文献
994.
本文研究了一类具类p-Laplacian项Liénard微分方程.应用广义Borsuk定理,在系数c(t)为非常值函数的情况下,得到了该方程周期解存在性的一个新的结果.Abstract: In this article,we study a kind of p-Laplacian-like Liénard differential equation.By using the generalized Borsuk theorem in coincidence degree theory,a new result on the existence of its periodic solution is obtained in the case that the cofficient c(t)is not a constant function. 相似文献
995.
996.
Development of dispersive XAFS system for analysis of time‐resolved spatial distribution of electrode reaction 下载免费PDF全文
Misaki Katayama Ryota Miyahara Toshiki Watanabe Hirona Yamagishi Shohei Yamashita Terue Kizaki Yoshimi Sugawara Yasuhiro Inada 《Journal of synchrotron radiation》2015,22(5):1227-1232
Apparatus for a technique based on the dispersive optics of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐5 of the Synchrotron Radiation Center of Ritsumeikan University. The vertical axis of the cross section of the synchrotron light is used to disperse the X‐ray energy using a cylindrical polychromator and the horizontal axis is used for the spatially resolved analysis with a pixel array detector. The vertically dispersive XAFS (VDXAFS) instrument was designed to analyze the dynamic changeover of the inhomogeneous electrode reaction of secondary batteries. The line‐shaped X‐ray beam is transmitted through the electrode sample, and then the dispersed transmitted X‐rays are detected by a two‐dimensional detector. An array of XAFS spectra in the linear footprint of the transmitted X‐ray on the sample is obtained with the time resolution of the repetition frequency of the detector. Sequential measurements of the space‐resolved XAFS data are possible with the VDXAFS instrument. The time and spatial resolutions of the VDXAFS instrument depend on the flux density of the available X‐ray beam and the size of the light source, and they were estimated as 1 s and 100 µm, respectively. The electrode reaction of the LiFePO4 lithium ion battery was analyzed during the constant current charging process and during the charging process after potential jumping. 相似文献
997.
Julia Langer Dominik Wohlmuth Adriana Kovalcik Viktor Epp Franz Stelzer Martin Wilkening 《Annalen der Physik》2015,527(7-8):523-530
Single crystalline LiAlO is known as a very poor ion conductor. Thus, in its crystalline form it unequivocally disqualifies itself from being a powerful solid electrolyte in modern energy storage systems. On the other hand, its interesting crystal structure proves beneficial to sharpen our understanding of Li ion dynamics in solids which in return might influence application‐oriented research. LiAlO allows us to apply and test techniques that are sensitive to extremely slow Li ion dynamics. This helps us clarifying their diffusion behaviour from a fundamental point of view. Here, we combined two techniques to follow Li ion translational hopping in LiAlO that can be described by the same physical formalism: dynamic mechanical relaxation and electrical relaxation, i.e., ionic conductivity measurements. Via both methods we were able to track the same transport mechanism in LiAlO. Moreover, this enabled us to directly probe extremely slow Li exchange rates at temperatures slightly above 430 K. The results were compared with recent insights from nuclear magnetic resonance spectroscopy. Altogether, an Arrhenius‐type Li diffusion process with an activation energy of ca. 1.12 eV was revealed over a large dynamic range covering 10 orders of magnitude, i.e., spanning a dynamic range from the nano‐second time scale down to the second time scale.
998.
999.
采用溶剂热法,以乙二醇为溶剂,P123为软模板剂,制备了锂离子电池正极材料磷酸铁锂(LiFePO4),其振实密度约为1.2g·cm-3。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)和BET对样品的成分、晶型,形貌和孔结构进行了表征。结果表明:鸟巢状LiFePO4由单晶纳米片组成,具有开放的三维多孔分级结构。通过时间单因素实验探讨鸟巢状分级结构LiFePO4的生长机理,其生长过程可以概括为:成核定向生长团聚定向生长。电化学性能测试结果表明材料在0.1C倍率下充放电时,其首次放电比容量达132.5mAh·g-1。 相似文献
1000.
Dr. Ya‐Xia Yin Sen Xin Prof. Yu‐Guo Guo Prof. Li‐Jun Wan 《Angewandte Chemie (International ed. in English)》2013,52(50):13186-13200
With the increasing demand for efficient and economic energy storage, Li‐S batteries have become attractive candidates for the next‐generation high‐energy rechargeable Li batteries because of their high theoretical energy density and cost effectiveness. Starting from a brief history of Li‐S batteries, this Review introduces the electrochemistry of Li‐S batteries, and discusses issues resulting from the electrochemistry, such as the electroactivity and the polysulfide dissolution. To address these critical issues, recent advances in Li‐S batteries are summarized, including the S cathode, Li anode, electrolyte, and new designs of Li‐S batteries with a metallic Li‐free anode. Constructing S molecules confined in the conductive microporous carbon materials to improve the cyclability of Li‐S batteries serves as a prospective strategy for the industry in the future. 相似文献