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1.
以L iOH.H2O和Mn(CH3COO)2.2H2O作原料,应用微波-固相两段烧结法合成具有L i4Mn5O12结构特征,组成为L i3.22Na0.569Mn5.78O12.0的锂离子电池正极材料.XRD分析表明,在380℃的后处理温度下,微波烧结前处理有利于生成纯L i4Mn5O12尖晶石相.充放电实验表明,在4.5~2.5V电压区间,新制样品的初始放电容量为132 mAh.g-1,100循环的容量衰减率为6.8%;4个月存放样的初始放电容量为122 mAh.g-1,100循环的容量衰减率为17.4%.表现出较好的充放电性能和循环寿命.微波烧结使样品的Mn-O键被加强. 相似文献
2.
采用溶胶-凝胶法分别制备La0.95Sr0.05Ga0.9Mg0.1O3-δ(LSGM)和Ce0.8Nd0.2O1.9(NDC)电解质,并在NDC溶胶中加入0-15%(w,质量分数)的LSGM预烧粉体制得NDC-LSGM复合电解质,研究不同质量比复合电解质的结构和电性能.采用X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)和X能量色散谱仪(EDS)对样品进行结构表征,交流(AC)阻抗谱测试样品导电性能.结果表明:NDC-LSGM复合体系主要由立方萤石结构相、钙钛矿结构相和杂质相组成;LSGM的添加可促进晶粒的生长,产生大量相界面,清除或降低SiO2有害影响,明显提高晶界导电性;LSGM质量分数为10%的样品NL10具有最高晶界电导率和总电导率,400°C时NL10的晶界电导率σgb和总电导率σt分别为12.15×10-4和3.49×10-4S cm-1,与NDC的σgb(1.41×10-4S cm-1)和σt(1.20×10-4S cm-1)相比分别提高了7.62和1.91倍,总电导率的提高主要归因于晶界电导率的影响. 相似文献
3.
在Ar气保护下用悬浮熔炼制备La0.7Pr0.15Nd0.05Mg0.3N i3.3-xCo0.2A l0.1(Co0.75Mn0.25)x(x=0.0,0.2,0.4,0.6)合金,系统研究了Co和Mn对合金储氢性能和电化学性能的影响。XRD相分析表明,合金相主要由(La,Pr)(N i,Co)5,LaMg2N i9,(La,Nd)2N i7和LaN i3相组成;添加Co和Mn后合金中(La,Pr)(N i,Co)5,(La,Nd)2N i7和LaN i3相晶胞体积增加,LaMg2N i9相晶胞体积变小。合金放氢PCT曲线测试表明,随着合金中Co和Mn含量的增加,合金吸氢量先减小后增加,放氢平台压下降,合金氢化物稳定性增加。合金电极电化学性能测试表明,添加Co和Mn使合金电极放电容量减小,容量保持率S100从53.2%(x=0.0)增加到63.0%(x=0.6),合金电极的电循环稳定性增强,高倍率放电性能HRD1500先增加后减小。此外,合金电极的极化电阻先减小后增加,交换电流密度、循环伏安特性阳极峰电流密度和极限电流密度先增加后减小,合金内氢原子扩散系数先增加后减小,表明添加适量的Co和Mn可以提高合金电... 相似文献
4.
以高藜芦胺为起始原料,经N-磺酰化反应制得高藜芦磺酰胺(2);2分别与芳乙烯甲醚经对甲苯磺酸催化的Pictet-Spengler反应后用金属钠脱除Ts基团合成了(±)-norlaudanosine(5a)和(±)-O,O-dimethylcoclaurine(5b);使用半量拆分法,以N-乙酰-L-苯丙氨酸为拆分剂,制得(S)-(-)-5a和(S)-(-)-5b,其结构经1H NMR,13C NMR,IR,MS和HR-ESI-MS确证。 相似文献
5.
采用高温固相法制备了BaCe0.8Lu0.2O3-α质子导体。运用X射线衍射仪(XRD)、扫描电镜(SEM)对该材料的物相结构、微观形貌进行了表征。在500~900℃温度范围内,应用交流阻抗谱和气体浓差电池方法研究了材料在不同气体气氛中的离子导电性和氢-空气燃料电池性能。结果表明,BaCe0.8Lu0.2O3-α材料为单一斜方晶结构,具有良好的致密性。在500~900℃温度范围内,干燥或湿润的氮气、空气和氧气中,材料的电导率随着氧分压增大稍有增大。在湿润的氢气中,材料表现为纯的质子导电性。在以该材料为固体电解质的氢-空气燃料电池条件下,材料表现为质子、氧离子和电子的混合导电性,其中离子导电性始终占主导;氢-空气燃料电池在900℃下的最大输出功率密度为92.2mW·cm-2,高于我们以前报道的BaCe0.8RE0.2O3-α(RE=Pr,Eu,Ho,Er,等)材料。 相似文献
6.
采用密度泛函理论(DFT)研究了C_(3)H_(8)和CO_(2)在Ni_(x)Cu_(y)-B_(24)N_(28)(x+y=4,x=1、2、3、4)表面吸附及速控步骤反应机理.计算了C_(3)H_(8)、CO_(2)和相应中间体在Ni_(x)Cu_(y)-B_(24)N_(28)表面的吸附能以及6条可能路径下的反应热和活化能.计算结果表明,C_(3)H_(8)和CO_(2)在Ni_(x)Cu_(y)-B_(24)N_(28)表面是物理吸附,C_(3)H_(8)+CO_(2)→CH_(3)CHCH_(3)+OCOH是最有利的路径,其在不同催化剂表面的活化能顺序是NiCu_(3)-B_(24)N_(28)(1.42 eV)、Ni_(2)Cu_(2)-B_(24)N_(28)(1.57 eV)、Ni_(3)Cu-B_(24)N_(28)(1.62 eV)、Ni_(4)-B_(24)N_(28)(1.75 eV).由此可知,在Ni_(x)Cu_(y)-B_(24)N_(28)催化CO_(2)氧化C_(3)H_(8)的体系中,Cu含量直接影响其催化活性,即NiCu_(3)-B_(24)N_(28)用于催化CO_(2)氧化C_(3)H_(8)有一定优势. 相似文献
7.
贮氢电极合金ZrCr_(0.4)Mn_(0.2)V_(0.1)Co_(0.1)Ni_(1.2)高温电化学性能的研究 总被引:1,自引:0,他引:1
研究了AB2型Laves相贮氢电极合金ZrCr0.4Mn0.2V0.1Co0.1Ni1.2在不同温度下的放电容量、活化、高倍率和自放电等电化学性能.实验表明:25℃下,合金电极经13次循环后其最大放电容量为336mAh/g,在70℃下,仅需4次循环就达到298mAh/g;该合金在70℃,300mA/g电流下的高倍率放电性能比25℃时提高了约16%,但自放电性能却从3%/d下降到17%/d,虽然温度升高,合金的循环性能有所下降,但还是相当稳定的.这主要是因为循环过程中合金表面形成的氧化膜阻碍了合金元素进一步溶解造成的. 相似文献
8.
研究了在聚乙二醇2000(PEG)-硫酸钠(Na2SO4)-邻苯二酚紫(PV)体系中铍(Ⅱ)、铁(Ⅲ)、铁(Ⅱ)、铝(Ⅲ)、铬(Ⅲ)、锰(Ⅱ)的萃取行为。试验结果表明,铍(Ⅱ)在pH 3.5-7.0及铁(Ⅲ)在pH 4.0-7.0范围内可以被PEG相几乎完全萃取,而铝(Ⅲ)、铬(Ⅲ)在pH 1.0-7.0、锰(Ⅱ)在pH 1.0-4.5、铁(Ⅱ)在pH 1.0-4.5则不被萃取。从而实现了将铍(Ⅱ)(pH 3.5)、铁(Ⅲ)(pH 5.0)与铝(Ⅲ)、铬(Ⅲ)、锰(Ⅱ)、铁(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。 相似文献
9.
在pH值为9.5~9.9的氨-氯化铵的缓冲溶液中,镍(Ⅱ)、铜(Ⅱ)、镉(Ⅱ)、钴(Ⅱ)、锌(Ⅱ)形成氨合络合物,而银(Ⅰ)、铋(Ⅲ)、铁(Ⅲ)、铁(Ⅱ)、汞(Ⅱ)、汞(Ⅰ)、锰(Ⅱ)、铅(Ⅱ)、锡(Ⅳ)、锡(Ⅱ)、钒(Ⅴ)、铝(Ⅲ)、钛(Ⅳ)等生成各种形式的沉淀。用甲醇-乙醇-氯化铵-氨-水体系(pH9.0~9.1),在硅胶H薄层板上,可以实现镍(Ⅱ)、铜(Ⅱ)、镉(Ⅱ)、钴(Ⅱ)、锌(Ⅱ)的分离。双硫腙显色后,用CS-930双波长薄层扫描仪测定含量。线性范围:锌0.01~0.20微克,铜0.01~0.25微克,镍、镉、钴0.01~0.30微克。 相似文献
10.
用微波辐射法合成了(Ce0.67Tb0.33)MgAl11O19(PG)和BaMgAl10O17(PB)两种荧光体,经X射线粉末衍射分析,其d值和I/I0值与JCPDF3673和26163基本一致。计算得到PG的晶胞参数a=05582nm,c=21884nm;P-B的晶胞参数α=05616nm,c=22614nm。测定了两种荧光体的激发光谱和发射光谱。P-G的色坐标x=0316,y=0565;P-B的色坐标x=0156,y=0106。与市售同类荧光粉相比,P-G的相对发光强度为88%,P-B的相对发光强度为80%。 相似文献
11.
12.
以四氯化碳作为惰性参考溶剂, 研究了N-甲基-2-吡咯烷酮(NMP)、环丁砜、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMA)和γ-丁内酯(γ-BL)等五种萃取剂在几种芳烃溶剂中的~1H NMR谱。观察到萃取剂分子的化学位移在芳烃溶剂中均大幅度移向高场, 且NMP、γ-BL的共振谱线在芳烃中发生分裂或重叠。在不同的芳烃溶剂中, 以在苯乙烯中NMP、DMF、DMA、环丁砜共振谱线的移动幅度为最大。各萃取剂谱线位移的幅度随着苯环上甲基数目的增多而递减。结合溶液热力学的结果, 推断出NMP等萃取剂和芳烃分子之间存在着弱化学作用。 相似文献
13.
Howle CR Arrowsmith AN Chikan V Leone SR 《The journal of physical chemistry. A》2007,111(29):6637-6648
Fourier transform visible spectroscopy, in conjunction with VUV photons produced by a synchrotron, is employed to investigate the photodissociation of CH3CN. Emission is observed from both the CN(B2Sigma+-X2Sigma+) and CH(A2Delta-X2Pi) transitions; only the former is observed in spectra recorded at 10.2 and 11.5 eV, whereas both are detected in the 16 eV spectrum. The rotational and vibrational temperatures of both the CN(B2Sigma+) and CH(A2Delta) radical products are derived using a combination of spectral simulations and Boltzmann plots. The CN(B2Sigma+) fragment displays a bimodal rotational distribution in all cases. Trot(CN(B2Sigma+)) ranges from 375 to 600 K at lower K' and from 1840 to 7700 K at higher K' depending on the photon energy used. Surprisal analyses indicate clear bimodal rotational distributions, suggesting CN(B2Sigma+) is formed via either linear or bent transition states, respectively, depending on the extent of rotational excitation in this fragment. CH(A2Delta) has a single rotational distribution when produced at 16 eV, which results in Trot(CH(A2Delta))=4895+/-140 K in v'=0 and 2590+/-110 K in v'=1. From thermodynamic calculations, it is evident that CH(A2Delta) is produced along with CN(X2Sigma+)+H2. These products can be formed by a two step mechanism (via excited CH3* and ground state CN(X2Sigma+)) or a process similar to the "roaming" atom mechanism; the data obtained here are insufficient to definitively conclude whether either pathway occurs. A comparison of the CH(A2Delta) and CN(B2Sigma+) rotational distributions produced by 16 eV photons allows the ratio between the two excited fragments at this energy to be determined. An expression that considers the rovibrational populations of both band systems results in a CH(A2Delta):CN(B2Sigma+) ratio of (1.2+/-0.1):1 at 16 eV, thereby indicating that production of CH(A2Delta) is significant at 16 eV. 相似文献
14.
The C(2)H + O((3)P) --> CH(A) + CO reaction is investigated using Fourier transform visible emission spectroscopy. The O((3)P) and C(2)H radicals are produced by simultaneous 193 nm photolysis of SO(2) and C(2)H(2) precursors, respectively. The nascent vibrational and rotational distributions of the CH(A) product are obtained under time-resolved, but quasi-steady-state, conditions facilitated by the short lifetime of the CH(A) emission. The vibrational temperature of the CH(A) product is found to be appreciably hotter (2800 +/- 100 K) than the rotational distributions in the v' = 0 (1400 +/- 100 K) and v' = 1 (1250 +/- 250 K) levels. The results suggest that the reaction may proceed through an electronically excited HCCO() intermediate; moreover, the vibrational excitation compared to rotational excitation is higher than expected based on a statistical distribution of energy and may be the result of geometrical changes in the transition state. The CH(A) emission is also observed in a C(2)H(2)/O/H reaction mixture using a microwave discharge apparatus to form O atoms, with subsequent H atom production. The nascent rotational and vibrational distributions of the CH(A) determined by the microwave discharge apparatus are very similar to the CH(A) distributions obtained in the photodissociation experiment. The results support the idea that the C(2)H + O((3)P) reaction may play a role in low-pressure C(2)H(2)/O/H flames, as previously concluded. 相似文献
15.
CH2+O2反应的反应机理 总被引:3,自引:0,他引:3
The mechanisms of the CH2+ O2→ H2O+ CO and CH2+ O2→ H2+ CO2 reactions have been studied by performing ab initio CAS(8,8)/6-31G(d,p) calculations, and five intermediates(IMn) and eight transitions(TSn) have been located along the reaction paths. The predicted path for the CH2+ O2→ H2O+ CO is: CH2+ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS5→ H2O+ CO. For the CH2+ O2→ H2+ CO2 reaction, there are two paths: (i) CH2+ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS6→ H2+ CO2 and (ii) CH2+ O2→ TS1→ IM1→ TS2→ IM2→ TS3→ IM3→ TS4→ IM4a→ TS7→ IM4b→ TS8→ H2+ CO2, with the latter path more favorable energetically. 相似文献
16.
The reaction dynamics of methylene radical CH2(X3B1) with N2O was investigated by Time-Resolved Fourier Transform Infrared Spectroscopy(TR-FTIRS). Pure CH2(X3B1) radicalwas produced via laser photolysis of ketene at 351 nm. Nascent viabrationally excited products CO, NO and HCN were observed. Some reaction pathways which may lead to these products were proposed and a possible reaction mechanism was outlined. 相似文献
17.
The composition adsorption isotherms (ya~xg curve) for acetone-n-hexane, benzene-n-hexane, toluene-n-hexane and n-pentance-n-hexane vapor mixtures on silica gel with different surface coverage (θ) at 25℃ were measured. The experimental results indicated that the ya ~ xg curves approached gradually down to corresponding binary liquid-vapor equllibrium curves with increasing of surface coverage. Therefore, the binary adsorbed phases are similarly with the binary liquid phase. Except for acetone-n-hexane system, which had a minimum boiling point, the composition adsorption isotherms of the other three binary systems could be simulated by equation of relative volatility. 相似文献
18.
The microdisk electrode voltammetric behaviors of C_(60) are reported in this communication. This was accomplished by use of a mixed solvent system as Acetonotrile:Xylene=1:4 and a supporting electrolyte as 0.1 mol·L~(-1) Bu_4NPF_6. Au, Pt and Hg (Pt) were used as working electrode. In this new conditions, the successive six step reduction of C60 were obtained at below 15 ℃. It was found that the former five steps are all the single electron reversible reduction, but behaviors of the sixth steps are like EC' processes. Several electrochemical data were determined. 相似文献
19.
The UV/VIS spectra for pyridine solution of complexes [Fe_2MO(CH_3COO)_6Py_2]·Py and THF solution of complexes Fe_2MO(CCl_3COO)_6(THF)_3 were studied. The d-d transitions were assigned and the ligand field parameters(B,D_q,β) were calculated for the related metal ions according to ligand field theory (Tanabe-Sugano diagram) in terms of O_h symmetry and reasonably good fits were obtained for the calculated and observed frequencies. The calculated results show that (1) the larger the ionic potential for M~(2+) ion, the larger the values of B, D_q for Fe~(3+) ion (2) the ligand field parameters of metal ions vary in parallel with the electronagativity of R in RCOO~-. 相似文献
20.
Single photon dissociation of bromoform using synchrotron radiation has been investigated by Fourier transform visible fluorescence spectroscopy (FTVIS). The photodissociation of bromoform in the 12-18 eV energy range results in several products, among which are the CH(A2Delta) and CH(B2Sigma) radicals. Vibrational and rotational state distributions of the CH(A2Delta) are determined from their fluorescence spectra. From the threshold photon energy above which emission from the CH(A2Delta) radicals is observed, the most likely process leading to CH(A) formation is CHBr3 --> CH + 3Br rather than CHBr3 --> CH + Br + Br2. The rotational Boltzmann temperatures in the CH(A --> X) emission spectra for v' = 0 and v' = 1 range between 1570 and 3650 K, depending on the excitation photon energy. From the high rotational excitation, the results suggest that the mechanism for the loss of three bromine atoms is most likely sequential. A small negative emission anisotropy of the CH(A) radicals [(Ipar - Iper)/(Ipar + 2Iper) = -0.024 +/- 0.005] is constant across the action spectrum; a small net absorption dipole of CHBr3 in the vacuum ultraviolet is parallel to the 3-fold symmetry axis of the CHBr3 molecule. The state distributions of the CH(A2Delta) radicals from multiphoton dissociation of bromoform using the 266 nm output (three photons) of a femtosecond laser (Boltzmann temperatures: T(v'=0)(rot)= 4250 +/- 300 K; T(v'=1)(rot)= 3100 +/- 550 K) are compared to those from the single photon dissociation results (Boltzmann temperatures: T(v'=0)(rot)= 3650 +/- 150 K; T(v'=1)(rot)= 2400 +/- 200 K) at the same total excitation energy under collision free conditions. The analysis of the CH(A) rotational populations shows hotter rotational populations for the femtosecond experiment, also suggesting sequential dissociation of the bromoform in the femtosecond experiment. The duration of the femtosecond laser pulse is approximately 180 fs, setting a limit on the time scales for the multiple dissociations. 相似文献