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1.
氧化铝具有许多重要的工业用途,而制备高热稳定活性氧化铝的技术也在不断地发展[1,2],因此,研究其高温烧结下的相变过程很有意义.离子深法作为新型测试手段,已成功地用于生物大分子结构与功能研究方面[‘],而在固体材料测试中的应用尚未见报道.我们以EU’“作为荧光探针,并结合**D和*nR研究了川对。在不同烧结温度下的相变过程.1实验部分样品的制备采用复盐分解法.先将Elf刀s用高纯硝酸溶解定容.以占AlzO。重量1%的量加入到硫酸铝锭溶液中,进行超声处理,冷冻干燥.再依次登于900”C、1000C、1100C、1200C的高温炉…  相似文献   

2.
采用水热晶化反应,制备出传统需要高温固相反应合成的掺杂NASICON化合物Na(1-x)Zr(2-x)NbxP3O12(0<x<1),并应用XRD、IR方法对产物的晶体结构进行了研究,表明水热晶化产物是纯的物相并具有与NaZr2P3O12相同的结构.固体31PNMR研究证实Nb(5+)部分取代了Zr(4+)所在位置,参与骨架的组成,并统计分布于结构中.水热晶化产物与固相反应产物具有相同的离子电导性能.  相似文献   

3.
采用水热晶化反应,制备出传统需要高大相反合成的掺杂,NASICON化合物Na1-xZr2-xNbxP3O12(0<X<1),并应用XRD,IR方法对产物的晶体结构进行了研究。表明水热晶化产物是纯的物相并具有与NaZr2P3O12相同的结构,固体^31PNMR研究证实Nb^5+部分取代了Zr^4+所在位置,参与骨架的组成,并统计分布于结构中,水热晶化产物与固相反应产物具有相同的离子电导性能。  相似文献   

4.
以wag/P”-AI。O。为固体电解质的CO。、SO。、NO。等气体传感器的研究已有很多报道[‘-‘],多采用的是个AI。O。结构的电解质。AI刀。和p”-AI刃。的结构具有一定的相似性,但后者具有更高的迁移离子浓度和更开放的晶体结构,表现出更好的离子导电性‘’‘.由于卢”-AI。O。为介稳结构,需要加入如Li。O、MgO等作为稳定剂才能稳定存在.以Li对稳定的产”-al。O。烧结较容易,P”-AI。O。相转化率高,但以MsO为稳定剂制备的”-AI刃。其显微结构和抗吸湿性能更为优越.LJLi对和MgO共同稳定的产”-AI。O。可以…  相似文献   

5.
细胞内游离离子及离子通道的核磁共振研究   总被引:1,自引:0,他引:1  
生物细胞内游离离子及离:子通道(Ca^2 、Mg^2 、Na^ 、K^ 以及Na^ /Ca^2 和Na^ /Li^ 交换等)在生理病理过程中起着重要作用。用于这些方面研究的生物核磁共振方法主要包括有:^31PNMR、^19NMR、^7Li NMR及^23Na NMR等。^31P NMR主要用于对细胞内小分子代谢物、pH及游离Mg^2 的分析测定;^19F NMR是利用氟代指示剂间接地测定细胞内游离Mg^2 和Ca^2 的浓度,进而对钙镁离子通道进行分析研究;^7Li NMR、^23Na NMR等方法分别用于研究Li^ 、Na^ /Li^ 交换、Mg^2 /Li^ 交换、Na^ 及K^ 等。为了更好地理解和阐释细胞内离子的调控机制,本文对近几年核磁共振技术在这些方面的应用进行了综述。  相似文献   

6.
Li3Sc2(PO4)3因具有有利的离子传导通道、低的电子电导率和高的稳定性而成为全固态锂离子电池用固体电解质最具竞争力的材料之一,然而这一化合物只有在245℃以上的γ相才具有快离子传导特性。人们主要采用Zr4+、Ti4+等阳离子部分取代其中的Sc3+以改善材料的室温电导率,有关该化合物PO43-阴离子替代的报道还很少。本研究试图利用机械研磨技术,通过向Li3Sc2(PO4)3原料混合物中加入适量SiO2,以期能够实现对该化合物的部分阴离子替代。研究结果表明:所制备的Li3+xSc2(PO4)3-x(SiO4)x(x=0~0.6)系列化合物在x=0.15时电导率达到最大值,σ298=9.55×10-4 S.m-1,离子传导激活能达到最小值45.06 kJ.mol-1。29Si MAS-NMR测试结果证实所加入的SiO2主要以[SiO4]四面体形式存在替代Li3Sc2(PO4)3中部分[PO4]四面体。  相似文献   

7.
化合物Na3Zr2Si2PO12。是由ZrO6八面体与SiO4或PO4四面体共角构成的开放三维骨架结构,Na 位于骨架间隙,称之为NASICON(NaSuperIoaicConductor),具有和Na-Al2O3相似的离子电导率(在300℃时,σ=0.2Ω-1·cm-1[1]但是由于该化合物在100-2000℃间存在单斜一、立方的可逆相变,使其应用受到限制.为了抑制这种相变,已进行了骨架掺杂的研究工作,制备出了多种化学掺杂的NASICON系统[2].在Na3Zr2Si2PO12化合物中,三个Na十分别位于结构中两个不同的位置,然而掺杂以后,骨架结构发生变化,这时Na十位置,将关系…  相似文献   

8.
高温固相反应合成了固体电解质Li_(9-nx)M~(n )_xN_2Cl_3(M=Na、Mg、Al)。利用粉末 X射线衍射测定样品结构。测定了离子电导率 ,分解电压和电子电导。得出掺杂可以提高快离子导体材料 Li_9N_2Cl_3的电导率。并讨论了掺杂阳离子的半径和价态与替代离子的关系和影响。使用 x=0.05mol的二价镁离子替代 Li_9N_2Cl_3中的 Li+离子可以很大程度的提高其电导率。  相似文献   

9.
ISSIe山和W6flSChllh山子1960年首次用pdCI。和二苯基磷合成出黄色的二聚络合物,后被H。yieY*确认为具有pRZ的桥式结构.此后一系列该类结构的化合物被合成并引起了广泛的兴趣.磷可以和两个甚至多个金属原子络合构成多核金属络合物,在催化反应中有重要应用.磷原子存在多种电子态,其3d空轨道也能参与成键.P乃1的NMR谱是研究含磷化合物立体结构的有力工具.P-31与其它核素之间的耦合常数以及P-31的化学位移对阐明化合物的立体构象以及电子结构具有重要作用.近年来,West饲用计算机神经网络技术预测P-:if的化学位移,但仅…  相似文献   

10.
设计合成了有机硒化合物1,4-二(2-苄硒基)乙氧基蒽,利用1H NMR、13C NMR、红外光谱和质谱对化合物进行了结构表征,采用荧光光谱技术研究了其对金属阳离子的识别。结果表明,其对汞离子有较强的识别能力,且对汞离子表现出开关性能。最后,初步讨论了其的识别机理和应用。  相似文献   

11.
(7)Li and (6)Li nuclear magnetic resonance (NMR) experiments are carried out on the perovskite Li(3x)La(1/3-x)NbO(3). The results are compared to those obtained on the titanate Li(3x)La(2/3-x)TiO3 (LLTO) in order to investigate the effect, on the lithium ion dynamics, of the total substitution of Nb(5+) for Ti(4+) in the B-site of the ABO(3) perovskites. The XRD patterns analysis reveals that this substitution leads to a change in the distribution of the La(3+) ions in the structure. La(3+) ions distribution is very important, in regard to ionic conductivity, because these immobile ions can be considered as obstacles for the long-range Li+ motion. If compared to the titanates, the compounds of the niobate solid solution have a bigger unit cell volume, a smaller number of La(3+) ions, and a higher number of vacancies. These should favor the motion of the mobile ions into the structure. This is not experimentally observed. Therefore, the interactions between the mobile species and their environment greatly influence their mobility. (7)Li and (6)Li NMR relaxation time experiments reveal that the Li relaxation mechanism is not dominated by quadrupolar interaction. (7)Li NMR spectra reveal the presence of different Li+ ion sites. Some Li+ ions reside in an isotropic environment with no distortion, some others reside in weakly distorted environments. T(1), T(1)(rho), and T(2) experiments allow us to evidence two motions of Li+. As in LLTO, T(1) probes a fast motion of the Li+ ions inside the A-cage of the perovskite structure and T(1)(rho) a slow motion of these ions from A-cage to A-cage. At variance with what has been observed in LLTO, these different Li+ ions can be differentiated through the spin-lattice relaxation times, T(1) and T(1)(rho), as well as through the transverse relaxation time, T(2).  相似文献   

12.
聚合物-锂改性蒙脱石复合材料离子迁移   总被引:1,自引:0,他引:1  
以聚合物(PEO,PEO-PMMA)和锂改性蒙脱石作为主要原料,采用聚合物粉末直接熔融嵌入的方法,制备聚合物-蒙脱石复合材料.利用NMR、AC阻抗等分析方法探讨了复合材料中聚合物链对 Li+离子迁移的影响.结果表明,聚合物(PEO)嵌入蒙脱石层间,层间聚合物链的无序度增大,有利于Li+离子迁移.PMMA引入对PEO链的改性,进一步加大聚合物链的无序度,更易于层间Li+离子迁移;复合材料的常温离子电导率接近10-2S·cm-1,且具有良好的温度稳定性.  相似文献   

13.
A series of Li1-zNi1+zO2 materials have been synthesised by the coprecipitation route. An X-ray diffraction study was carried out on these materials using the Rietveld method to determine the departure from the ideal stoichiometry z, which ranges from 0 to 0.138. The actual Li/Ni ratio was also checked by chemical analyses using inductively coupled plasma (ICP) for each sample. The stoichiometric sample (z approximately 0) was obtained using a 15% Li excess. (6/7)Li NMR results from LiNiO2 (z approximately 0) show that the asymmetric shape of the NMR signal is due to anisotropy. Calculations give evidence that the paramagnetic dipolar interaction from the electron spins carried by Ni is anisotropic but does not completely explain the experimental anisotropy. (6)Li MAS NMR (magic angle spinning NMR) experiments and temperature standardisation NMR measurements unambiguously assign the isotropic position at +726 ppm. The static-echo NMR spectra of the non-stoichiometric Li1-zNi1+zO2 phases also exhibit an asymmetric shape whose width increases with the departure from the ideal stoichiometry z. (6/7)Li static and MAS NMR show that the 2zNi(2+) ions thus formed modify the dipolar interaction within the materials and also affect the Fermi contact interaction, since a distribution of Li environments is observed using (6)Li NMR for non-stoichiometric samples.  相似文献   

14.
Deintercalated "Li(x)NiO2" materials (x = 0.25, 0.33, 0.50, 0.58, and 0.65) were obtained using the electrochemical route from the Li0.985Ni1.015O2 and Li0.993Ni1.007O2 compounds. Refinements of X-ray diffraction data using the Rietveld method show a good agreement with the phase diagram of the Li(x)NiO2 system studied earlier in this laboratory. Electronic conductivity measurements show a thermally activated electron-hopping process for the deintercalated Li0.5NiO2 phase. In the Li(x)NiO2 materials investigated (x = 0.25, 0.33, 0.50, and 0.58), 7Li NMR shows mobility effects leading to an exchanged signal at room temperature. A clear tendency for Li to be surrounded mainly by Ni3+ ions with the 180 degree configuration is observed, particularly, for strongly deintercalated materials with smaller Li+ and Ni3+ contents, even upon heating, when this mobility becomes very fast in the NMR time scale. This suggests that Li/vacancy hopping does occur on the NMR time scale but that Ni3+/Ni4+ hopping does not occur independently. The position of Li seems to govern the oxidation state of the Ni around it at any time; the electrons follow the Li ions to satisfy local electroneutrality and minimal energy configuration. The observed NMR shifts are compatible with the Li/vacancy and Ni3+/Ni4+ ordering patterns calculated by Arroyo y de Dompablo et al. for x = 0.25 and x = 0.50, but not for x = 0.33 and x = 0.58.  相似文献   

15.
Within a temperature range of 120–330 K, 7Li NMR spectra in Li0.6CoO2 are obtained. It is shown that as the temperature increases, both smooth and stepwise variation of 7Li NMR contact shifts occurs. The observed effects are explained by the occupation of the excited levels of cobalt ions. The stepwise change of the resonance line width depending on the temperature is revealed. It is driven by the features of the diffusive motion of lithium ions. The calculation of the 1H NMR line shape provides the determination of the ratio of one-, two-, and three-spin proton clusters in Li0.6CoO2·xH2O.  相似文献   

16.
Cation-cation interactions are thought to play a significant role in shaping the nonlinear compositional dependence of ionic conductivity, known as the mixed-alkali effect (MAE) in glassy solid electrolytes. For providing a structural rationale of this effect, the discrimination of various cation sites in mixed-alkali glasses is of interest. In the present study, cross-polarization (CP) experiments have been applied to glasses in the system [(Li(2)O)x(Na(2)O)(1-x)](0.3)[B(2)O(3)]0.7 to discriminate between alkali ions by virtue of different heteronuclear (7)Li-(23)Na dipole-dipole coupling strengths. Cross-polarization studies involving two types of quadrupolar nuclei (both (7)Li and (23)Na have a spin-quantum number I = 3/2) are complicated by spin state mixing under radio frequency irradiation and magic-angle spinning (MAS). Therefore careful validation and optimization protocols are reported for the model compound LiNaSO(4) prior to conducting the measurements on the glassy samples. (23)Na -->( 7)Li CP/MAS NMR spectra have been obtained on glasses containing the Na(+) ions as the dilute species. They reveal that those lithium species interacting particularly strongly with sodium ions have the same average (7)Li chemical shift as the entire lithium population; the symmetrical situation applies to the (23)Na nuclei at the sodium rich end of the composition range. On the other hand, a clear site discrimination is afforded by temperature-dependent static (23)Na -->( 7)Li CP experiments, indicating that the Li ions that are most strongly interacting with sodium ions are strongly immobilized. This finding provides the first direct experimental evidence for the proposed secondary mismatch concept invoked for explaining the strong MAE in the dilute foreign ion limit.  相似文献   

17.
本文报道1^H、7^Li、23^Na、133^Cs NMR测定N, N'-二羧甲基大环醚双内酯(1-4)和大环胺双内酰胺(5), N-对甲苯磺酰基大环醚双内酯(6, 7), 4'-丹磺酰氨基苯并-18-冠-6(8)与Li^+、Na^+、K^+、Cs^+、Cd^2+和Pb^2+金属离子的配位作用, 并以非线性最小二乘法拟合计算了配合物的形成常数; 同时, 发展了一种用133^Cs NMR测量冠醚和碘离子竞争配合Cs^+的配合物形成常数的新技术。  相似文献   

18.
Electrochemical studies provide broad, but not cation- or anion-specific information on the migration of charged ions. However, individual ion diffusion (as a weighted average of charged and neutral ions) can be measured using pulsed-gradient spin-echo (PGSE) NMR. In this paper, the lithium transport in an electrolyte including a lithium salt was measured using electrophoretic NMR (ENMR) with non-blocking electrodes. A propylene carbonate (PC) solution doped with LiN(SO(2)CF(3))(2) (LiTFSI) was inserted in a homemade NMR cell equipped with Li/Li electrodes. The drift migrations of lithium cation ((7)Li), anion ((19)F), and solvent ((1)H) were measured independently under potentials of up to 3.0 V. Greatly enhanced dynamic lithium transport was observed for the first time in the bulk electrolyte under an electric field closely related to real conditions in a rechargeable lithium battery.  相似文献   

19.
A comparative analysis of 6,7Li NMR spectra is performed for the samples of monoclinic lithium titanate obtained at different synthesis temperatures. In the 7Li NMR spectra three lines are found, which differ in quadrupole splitting frequencies v Q and according to ab initio EFG calculations are assigned to three crystallographic sites of lithium: Li1 (v Q ~ 27 kHz); Li2 (v Q ~ 59 kHz); Li3 (v Q ~ 6 kHz). The dynamics of lithium ions is studied in a wide temperature range from 300 K to 900 K. It is found that the narrowing of 7Li NMR spectra as a result of thermally activated diffusion of lithium ions in the low-temperature Li2TiO3 sample is observed at a higher temperature in comparison with a sample of high-temperature lithium titanate. Based on the analysis of 6Li NMR spectra it is assumed that there is mixed occupancy of lithium and titanium sites in the corresponding layers of the crystal structure of low-temperature lithium titanate, which hinders lithium ion transfer over regular crystallographic sites.  相似文献   

20.
Li+ ions can interplay with other cations intrinsically present in the intra- and extra-cellular space (i.e. Na+, K+, Mg2+ and Ca2+) have therapeutic effects (e.g. in the treatment of bipolar disorder) or toxic effects (at higher doses), likely because Li+ interferes with the intra-/extra-cellular concentration gradients of the mentioned physiologically relevant cations. The cellular transmembrane transport can be modelled by molybdenum-oxide-based Keplerates, i.e. nano-sized porous capsules containing 132 Mo centres, monitored through 6/7Li as well as 23Na NMR spectroscopy. The effects on the transport of Li+ cations through the 'ion channels' of these model cells, caused by variations in water amount, temperature, and by the addition of organic cationic 'plugs' and the shift reagent [Dy(PPP)2](7-) are reported. In the investigated solvent systems, water acts as a transport mediator for Li+. Likewise, the counter-transport (Li+/Na+, Li+/K+, Li+/Cs+ and Li+/Ca2+) has been investigated by 7Li NMR and, in the case of Li+/Na+ exchange, by 23Na NMR, and it has been shown that most (in the case of Na+ and K+, all (Ca2+) or almost none (Cs+) of the Li cations is extruded from the internal sites of the artificial cell to the extra-cellular medium, while Na+, K+ and Ca2+ are partially incorporated.  相似文献   

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