全文获取类型
收费全文 | 2077篇 |
免费 | 37篇 |
国内免费 | 306篇 |
专业分类
化学 | 1939篇 |
晶体学 | 18篇 |
力学 | 17篇 |
综合类 | 4篇 |
数学 | 4篇 |
物理学 | 438篇 |
出版年
2024年 | 9篇 |
2023年 | 166篇 |
2022年 | 26篇 |
2021年 | 61篇 |
2020年 | 43篇 |
2019年 | 65篇 |
2018年 | 38篇 |
2017年 | 52篇 |
2016年 | 52篇 |
2015年 | 55篇 |
2014年 | 76篇 |
2013年 | 164篇 |
2012年 | 103篇 |
2011年 | 134篇 |
2010年 | 68篇 |
2009年 | 93篇 |
2008年 | 102篇 |
2007年 | 121篇 |
2006年 | 130篇 |
2005年 | 84篇 |
2004年 | 116篇 |
2003年 | 89篇 |
2002年 | 70篇 |
2001年 | 69篇 |
2000年 | 47篇 |
1999年 | 60篇 |
1998年 | 79篇 |
1997年 | 50篇 |
1996年 | 34篇 |
1995年 | 27篇 |
1994年 | 24篇 |
1993年 | 25篇 |
1992年 | 13篇 |
1991年 | 18篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 14篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1974年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2420条查询结果,搜索用时 343 毫秒
31.
Nanometric vanadium antimonate, VSbO4, was prepared by mechanical milling from Sb2O3 and V2O5 and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Mossbaüer spectroscopy (MS) and X-ray photoelectron spectroscopy (XPS) techniques. Its reactivity towards lithium was examined by testing Li/VSbO4 cells under galvanostatic and potentiostatic regimes. The amount of Li inserted was found to be consistent with a two-step process involving the reactions (i) VSbO4+8 Li→Sb+V+4 Li2O and (ii) Sb+3 Li→Li3Sb, the former being virtually irreversible and the latter reversible as suggested by the shape of the anodic and cathodic curves. Ex situ XPS measurements of the discharged and charged electrode provided direct evidence of the formation of alloyed Sb and confirmed the results of the potentiostatic curves regarding the irreversible or reversible character of the previous reactions. The Li/VSbO4 cell exhibited acceptable electrochemical performance, which surpassed that of other Sb-based compounds as the likely result of the formation of V and its associated enhanced electrode conductivity. 相似文献
32.
Ternary Lithium Rare Earth Nitrates with Lonesome Nitrate Ions: Li3[M(NO3)5](NO3) (M = Gd? Lu, Y). The Crystal Structure of Li3Er(NO3)6 Single crystals of the ternary nitrate Li3Er(NO3)6 are obtained from a solution of “Er(NO3)3” in the melt of LiNO3. In Li3Er(NO3)6 (monoclinic, P21/n, Z = 4; a = 776.0(1); b = 748.86(8); c = 2 396(1) pm; β = 90.76(3)°; R1 = 0.0490; wR2 = 0.0792), Er3+ is surrounded by five bidentate nitrate ligands yielding the anionic units [Er(NO3)5]2?. These are arranged in the direction of the 21 screw axis. Two lonesome NO3? ions are in the middle of such a “helix” and are connected by Li+ with the anions [Er(NO3)5]2?. The helices are moved against each other by about half of the lattice constant a and are connected by further Li+ ions. 相似文献
33.
Matthias Freytag Frank T. Edelmann Ludger Ernst Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》2004,630(3):377-383
The reaction of the symmetric diphosphene 2, 4, 6‐(CF3)3‐C6H2‐P=P‐C6H2‐2, 4, 6‐(CF3)3 4 with Ru3(CO)12 led to the 50‐electron Ru3P2 nido‐cluster Ru3(CO)9[μ‐P‐C6H2‐2, 4, 6‐(CF3)3]2 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru3P2 centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C6H2(CF3)3 groups is also appreciably distorted. Temperature‐dependent 19F NMR studies of the [A3M3X]2 spin system (A = M = CF3, X = 31P) of 5 indicated a rotational barrier ΔG≠ of 82.3 kJ mol‐1 at 141 °C. The same Ru3P2 core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru3(CO)12; hindered rotation about the C(aryl)—P bonds was also observed, in this case. 相似文献
34.
Masafumi Kobayashi Tetsuya Inoguchi Takashi Iida Takashi Tanioka Hiroshi Kumase Yasushi Fukai 《Journal of fluorine chemistry》2003,120(2):2838-110
Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride. 相似文献
35.
锂离子二次电池碳负极材料的改性 总被引:5,自引:1,他引:5
作为锂离子二次电池的碳负极材料,其改性方面的研究内容主要有:引入非金属元素,引入金属元素,处理表面及其它方面。纺入的非金属元素有硼,硅,氮,磷和硫。引入的金属元素有钾,铝,镓和钒,镍,钴,铜,铁等过渡金属元素。表面处理的方法包括氧化,形成表面层等。 相似文献
36.
37.
Natural graphite samples with average particle sizes of 5, 10 and 15 μm (NG5 μm, NG10 μm and NG15 μm, respectively) were fluorinated by ClF3 (3 × 104 Pa) at 200 and 300 °C for 2 min. X-ray photoelectron spectra of surface-fluorinated samples showed that surface fluorine concentration increased with increase in the particle size of graphite and reaction temperature. Small amounts of chlorine were also detected in all the fluorinated samples. Raman spectra of original and surface-fluorinated samples indicated that the surface disordering was increased for NG10 μm and NG15 μm. Surface areas were decreased by the fluorination for NG5 μm and NG10 μm but unchanged for NG15 μm. The mesopores with diameter of 1.5-2 nm increased while those of 2-3 nm decreased for all the samples. First coulombic efficiencies for NG10 μm and NG15 μm were highly increased by surface fluorination in 1 mol/dm3 LiClO4-EC/DEC/PC (EC: ethylene carbonate, DEC: diethyl carbonate, PC: propylene carbonate) solution. 相似文献
38.
19F and 31P NMR spectroscopy were used to study the kinetics of the hydrolysis of LiPF6 in the homogenous solvent system propylene carbonate (PC)—dimethyl carbonate (DMC)—H2O. It was found that the main products of the hydrolysis are HF, LiPO2F2 and Li2PO3F. The content of POF3 and PF5 was negligibly low. We set up a hypothesis that the main factor determining the rate of the process is the so-called ‘secondary’ catalytic effect, caused by solvated H+ ions. 相似文献
39.
Graphitic anode materials for lithium ion batteries processed under high humidity conditions show severe performance losses. The sensitivity of these materials towards humidity can be significantly reduced by adsorbing metal ions like silver or copper ions, with subsequent heat treatment of these composites. Results of X-ray photoelectron spectroscopy, high-resolution electron microscopy, thermogravimetry, and differential thermal analysis indicate that the deposited metals exist in metallic and carbide, MxC (M=Cu or Ag), forms. They remove or cover (i.e. deactivate) active hydrophilic sites at the surface of the graphite. These composites absorb less water during processing. The electrochemical performance, including reversible capacity, coulombic efficiency in the first cycle, and cycling behavior, is markedly improved. This approach provides a potentially powerful method to manufacture lithium ion batteries under less demanding conditions.Presented at the 3rd International Meeting on Advanced Batteries and Accumulators, 16–20 June 2002, Brno, Czech Republic 相似文献
40.
Natalia N. Sergeeva 《Tetrahedron letters》2006,47(35):6169-6172
The palladium-catalyzed reaction of RLi with various 5,10,15,20-tetrasubstituted porphyrins offers a convenient synthetic route to chlorins and porphodimethenes (calixphyrins). The reactions utilized various Pd catalysts and CuI and yielded either 2,3-substituted chlorins or 5,10-disubstituted porphodimethenes in yields ranging from 20-40%. The reaction of octaethylporphyrin with t-BuLi in the presence of a Pd-catalyst generated the corresponding 5,10-porphodimethene in 72% yield. 相似文献