La、Ce、Yb掺杂对LiNi0.5Mn1.5O4高电压正极材料性能的影响

采用低温燃烧法制备出不同稀土元素掺杂的高电压镍锰酸锂(LiNi_(0.5)Mn_(1.5)O_4)正极材料,探究了不同掺杂比例(物质的量分数0.5%、1%、2%)和不同掺杂稀土元素(La、Ce、Yb)对样品性能的影响,并通过X射线衍射、拉曼光谱、电子顺磁共振和恒电流间歇滴定等技术探究了其影响机理。从X射线衍射图可以看出,稀土掺杂可以抑制Li_xNi_(1-x)O杂质相的产生;电感耦合等离子谱结果表明,掺杂进入的稀土元素与设计比例基本相符;从拉曼光谱图可以看出,稀土元素可以使样品的有序相增多,其中Ce掺杂样品的有序相最多;结合电子顺磁共振波谱氧空位测试,发现Ce掺杂诱导了样品中有序相比例增加,从而使样品的稳定性提高;经恒电流间歇滴定技术测试发现,Ce掺杂镍锰酸锂样品的扩散系数比未掺杂样品高了约15倍;在不同掺杂比例上,1%掺杂量时样品性能最佳。在3种最佳掺杂量的稀土元素样品中,Ce掺杂的样品性能最优,首次放电比容量可以达到133.3mAh·g~(-1),比未掺杂样品放电比容量高且首次效率提高了 18%,在1C下循环200次后,容量保持率为102%,比未掺杂样品提高了 8%。     

Structural and optoelectrical properties of nanocrystalline Gd-doped CdO films prepared by sol gel method

Gd-doped CdO thin films with various Gd concentrations have been prepared on glass and Si wafer substrates using sol gel technique. The films were characterised by X-ray fluorescence (XRF), X-ray diffraction (XRD), optical absorption spectroscopy, and dc-electrical measurements. XRF method was used to determine the %Gd content in the films while XRD was used to study the influence of Gd doping on the detailed crystalline structure. Experimental data indicate that Gd³⁺ doping with level of less than 2.4% slightly enlarge the CdO crystalline unit cell. The bandgap (E _g) of Gd-doped CdO suffers narrowing by about 13% due to a small (0.2%) doping level but with %Gd doping level larger than 2.4%, E _g becomes wider than that of undoped CdO. The electrical behaviours of the Gd-doped CdO films show that they are degenerate semiconductors. The 2% Gd-doped CdO film shows increase in its mobility by about 92%, conductivity by 320%, and carrier concentration by 127%, relative to undoped CdO film. From transparent-conducting-oxide point of view, the Gd doping of CdO by sol gel method is not effective. Finally, the absorption in the NIR spectral region was investigated to be due to the free electrons.     

Theoretical studies on the transport property of oligosilane with p‐n junction

The electron transport properties of a novel p‐n junction nanowire caused by boron‐doping and phosphorus‐doping are investigated using density functional theory combined with the nonequilibrium Green's functions formalism. A satisfying rectification is observed. This is a reasonable result after the analysis of the molecular‐projected self‐consistent Hamitonian (MPSH) states, transmission spectra, the frontier orbitals, and the dipole moments. In contrast, the undoped chain has no rectification character. In addition, a negative differential resistance behavior is also observed at V = 1.8 ～ 2.2 V in the doped nanowire and it could be illustrated from the MPSH states and the transmission spectra. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Electronic properties of the linear ladder polymer,poly[4-(3-pyridyl),8-methyl,2,3–6,7-quinolino] (PPMQ)

Electronic paramagnetic resonance (EPR) and conductivity of pristine and iodine-doped PPMQ were studied. The pristine polymer EPR signal exhibited a Lorentzian line shape. Unpaired spin density measurements indicated that the spin concentrations of the undoped polymer lie in the range of one spin per 150–190 repeat units at room temperature. The peak-to-peak width doubled, the line shape became asymmetric and the spin concentration in the polymer increased slightly after doping with iodine. EPR saturation experiments show that the spin lattice relaxation time T₁ is sensitive to trace impurity. Considerable reduction of T₁ after doping with iodine shows strong coupling between the spin system and N-iodonium nucleus. Conductivity increases up to 5 orders of magnitude by iodine doping; at room temperature, the best value found was 0.017 S/cm. The activation energy for conductance after doping is about half that of pristine polymer.     

Some Electrochemical Characteristics of Boron‐ and Phosphorus‐Doped Glassy Carbon Electrodes

Three glassy carbon (GC) samples: undoped and doped with boron or phosphorus, prepared at 1000 °C, were compared in respect to hydrodynamic current‐potential curves in acidic medium, cyclic voltammograms for Fe^3+/2+ and Fe(CN)₆^3?/4? and argentometric titrations of halides. Some experiments were also carried out using standard Tokai and Sigri GC and Ag electrode. It appeared that GC doped with boron and phosphorus exhibited significant increase in hydrogen evolution overpotential. As for the electrode kinetics (ΔE_p criterion), no significant difference was observed between doped and undoped electrodes. In the potentiometric titrations the phosphorus‐doped electrode was advantageous over the other GC and Ag electrodes as it enabled more precise end‐point detection.     

溶胶-凝胶法合成Li1-xNaxMn2O4及其作为水系锂离子电池正极材料的电化学性能

用溶胶凝胶法合成了Na⁺离子掺杂的Li_1-xNa_xMn₂O₄(x=0,0.01,0.03,0.05)。X射线衍射图表明Na⁺取代Li⁺进入Li_1-xNa_x Mn₂O₄晶格中,扫描电镜图看出产物是粒径为100~300 nm的颗粒。恒流充放电测试结果表明,Li_0.97Na_0.03Mn₂O₄在2C倍率下循环100圈后放电容量保持率比未掺杂的LiMn₂O₄从51.2%提升到84.1%。循环伏安测试表明Na⁺离子掺杂降低了材料极化且增大了锂离子扩散系数。10C倍率下Li_0.97Na_0.03Mn₂O₄仍有79.0 mAh·g^-1的放电容量,高于未掺杂样品的52.1 mAh·g^-1。Na⁺离子掺杂可以稳定材料结构并提高锂离子扩散系数,从而提高LiMn₂O₄的电化学性能,是一种可行的改性方法。     

溶胶-凝胶法合成Li_(1-x)Na_xMn_2O_4及其作为水系锂离子电池正极材料的电化学性能

用溶胶凝胶法合成了Na+离子掺杂的Li_(1-x)Na_xMn_2O_4(x=0,0.01,0.03,0.05)。X射线衍射图表明Na+取代Li+进入Li_(1-x)Na_xMn_2O_4晶格中,扫描电镜图看出产物是粒径为100~300 nm的颗粒。恒流充放电测试结果表明,Li_(0.97)Na_(0.03)Mn_2O_4在2C倍率下循环100圈后放电容量保持率比未掺杂的LiMn_2O_4从51.2%提升到84.1%。循环伏安测试表明Na+离子掺杂降低了材料极化且增大了锂离子扩散系数。10C倍率下Li0.97Na0.03Mn2O4仍有79.0 m Ah·g-1的放电容量,高于未掺杂样品的52.1 m Ah·g~(-1)。Na+离子掺杂可以稳定材料结构并提高锂离子扩散系数,从而提高LiMn_2O_4的电化学性能,是一种可行的改性方法。     

Direct Solvothermal Synthesis of B/N‐Doped Graphene

Heteroatom‐doping into graphitic networks has been utilized for opening the band gap of graphene. However, boron‐doping into the graphitic framework is extremely limited, whereas nitrogen‐doping is relatively feasible. Herein, boron/nitrogen co‐doped graphene (BCN‐graphene) is directly synthesized from the reaction of CCl₄, BBr₃, and N₂ in the presence of potassium. The resultant BCN‐graphene has boron and nitrogen contents of 2.38 and 2.66 atom %, respectively, and displays good dispersion stability in N‐methyl‐2‐pyrrolidone, allowing for solution casting fabrication of a field‐effect transistor. The device displays an on/off ratio of 10.7 with an optical band gap of 3.3 eV. Considering the scalability of the production method and the benefits of solution processability, BCN‐graphene has high potential for many practical applications.     

Ferromagnetism and structural deformation in monolayer alpha lead oxide induced by N and F doping: New insights from first principles

We study the structural, electronic, and magnetic properties of monolayer α-PbO_0.875A_0.125 (A = N, F), which are calculated using first principles. As a result, N doping induces local ferromagnetism centered at the N²⁻ site, originating from the spin-down N 2p valence states. On the other hand, F doping induces nonmagnetism and induces ab-plane deformation, where F⁻ receives one electron to its nearest-neighboring Pb^1.75+ ions. N doping redshifts the bandgap of the undoped system and transforms it to be indirect, while F doping blueshifts the bandgap through the Burstein-Moss effect. The hybridization of Pb 6p and O 2p orbitals is stronger near the A site than that of the crystal structure edge. Our result shows new insights, predicting possible experimental results for future functional device applications.     

硼和氟掺杂ZSM-5分子筛的制备及其甲醇制丙烯反应性能

采用两步水热晶化法,通过在合成体系中加入硼酸、氟化铵、氟硼酸铵,合成出了硼和氟改性的ZSM-5分子筛。利用X射线衍射、氮气吸附-脱附、29Si固体核磁共振波谱、傅里叶变换红外光谱、扫描电子显微镜以及NH₃程序升温脱附等测试手段对样品进行了表征。结果表明：硼和氟掺杂条件下可以合成具有较高结晶度的ZSM-5分子筛,杂原子掺杂提高了分子筛的硅铝比;硼和氟掺杂可以显著降低ZSM-5分子筛的Lewis酸量,但提高了Brønsted酸量;硼和氟共同作用可以降低ZSM-5分子筛的颗粒尺寸。甲醇制丙烯评价结果显示：较低的Lewis酸量和适宜的Brønsted酸性有利于提高丙烯选择性和催化剂寿命;NH₄BF₄改性的ZSM-5分子筛（Z5-BF2）表现出较高的丙烯选择性和较长的催化剂寿命。     

Effects of Cr doping on the electrochemical performance of Li3V2(PO4)3 cathode material for lithium ion batteries

A series of Cr-doped Li₃V_2 − x Cr _x (PO₄)₃ (x = 0, 0.1, 0.25, and 0.5) samples are prepared by a sol–gel method. The effects of Cr doping on the physical and chemical characteristics of Li₃V₂(PO₄)₃ are investigated. Compared with the XRD pattern of the undoped sample, the XRD patterns of the Cr-doped samples have no extra reflections, which indicates that Cr enters the structure of Li₃V₂(PO₄)₃. As indicated by the charge–discharge measurements, the Cr-doped Li₃V_2 − x Cr _x (PO₄)₃ (x = 0.1, 0.25, and 0.5) samples exhibit lower initial capacities than the undoped sample at the 0.2 C rate. However, both the discharge capacity and cycling performance at high rates (e.g., 1 and 2 C) are enhanced with proper amount of Cr doping (x = 0.1). The highest discharge capacity and capacity retention at the rates of 1 and 2 C are obtained for Li₃V_1.9Cr_0.1(PO₄)₃. The improvement of the electrochemical performance can be attributed to the higher crystal stability and smaller particle size induced by Cr doping.

     

Density functional study on electronic and optical properties of C (or N)-doped cubic cerium dioxide

Density functional calculations were performed on electronic and optical properties of C (or N)-doped cubic cerium dioxide (CeO₂). When O is replaced by C (or N) in CeO₂, obvious band-gap (E_g) reduction is observed. Meanwhile, it is interesting to find that the substitutional doping of C (or N) in CeO₂ obviously increases the O 2p–Ce 4f transition intensity and also the refractive index. The increase in the O 2p–Ce 4f transition intensity on going from undoped, N-doped and C-doped CeO₂ was related to the covalent character of the Ce–O bond. Compared with the undoped CeO₂, the C (or N)-doped CeO₂, with steep absorption peaks at lower energy, can be used for visible-light absorption applications.     

CO2 Capture,Separation and Reduction on Boron-Doped MoS2, MoSe2 and Heterostructures with Different Doping Densities: A Theoretical Study

Designing high-performance materials for CO₂ capture and conversion is of great significance to reduce the greenhouse effect and alleviate the energy crisis. The strategy of doping is widely used to improve activity and selectivity of the materials. However, it is unclear how the doping densities influence the materials’ properties. Herein, we investigated the mechanism of CO₂ capture, separation and conversion on MoS₂, MoSe₂ and Janus MoSSe monolayers with different boron doping levels using density functional theory (DFT) simulations. The results indicate that CO₂, H₂ and CH₄ bind weakly to the monolayers without and with single-atom boron doping, rendering these materials unsuitable for CO₂ capture from gas mixtures. In contrast, CO₂ binds strongly to monolayers doped with diatomic boron, whereas H₂ and CH₄ can only form weak interactions with these surfaces. Thus, the monolayers doped with diatomic boron can efficiently capture and separate CO₂ from such gas mixtures. The electronic structure analysis demonstrates that monolayers doped with diatomic doped are more prone to donating electrons to CO₂ than those with single-atom boron doped, leading to activation of CO₂. The results further indicate that CO₂ can be converted to CH₄ on diatomic boron doped catalysts, and MoSSe is the most efficient of the surfaces studied for CO₂ capture, separation and conversion. In summary, the study provides evidence for the doping density is vital to design materials with particular functions.     

Positron annihilation studies in highT c superconductor YBa2Cu3Cd x O y (x=0, 0.05)

Positron lifetime and Doppler broadening of the annihilation line measurements were performed in highT _c superconducting samples YBa₂Cu₃Cd _x O _y ,x=0, 0.05 and 6.9<y<7, as a function of temperature in the region of 14–300 K. It was found that the positron lifetime and theS parameter values are lower in the Cd doped sample than those in the undoped one. It was also observed that the positron annihilation parameters show similar temperature dependence for the undoped and Cd doped samples. We conclude that the Cd doping in highT _c superconductor YBa₂Cu₃Cd _x O _y , 6.9<y<7 fills defects associated with oxygen vacancies probably in oxygen deficient regions which can trap positrons.     

Synthesis and Microstructural Properties of Fe-TiO2 Nanocrystalline Particles Obtained by a Modified Sol-Gel Method

A series of iron/titanium oxide nanocrystalline particles with Fe/Ti molar ratios up to 0.15 were synthesized by a modified sol-gel technique using Ti(IV)-isopropoxide and anhydrous Fe(II)-acetate. The precursors were mixed and subsequently hydrolyzed with water molecules generated in situ by an esterification reaction between acetic acid and ethanol. As-synthesized samples were amorphous for XRD, independently of the relative amount of doped iron. The undoped samples and samples with the molar ratio Fe/Ti = 0.01, treated at up to 500°C, contained anatase as the dominant phase and rutile as the minor phase. The samples with the Fe/Ti molar ratio of 0.15, treated at the same temperature, contained anatase (major phase), rutile (minor phase) and a very small amount of an unidentified phase. The crystallite size of the dominant phase in the samples was estimated from the XRD line broadening using the Scherrer formula. Thermogravimetric analysis showed that weight loss was accelerated and completed at lower temperatures as the relative concentration of iron in the Fe-TiO₂ samples increased. The strong exothermic peak in the DTA curve between 300 and 450°C in the undoped TiO₂ sample shifted to the lower temperatures and became much more asymmetrical with increased iron doping. This DTA peak corresponded to the amorphous-to-anatase-transition and it included several steps such as (i) the thermal degradation of strongly bound organic molecules, (ii) the condensation of unhydrolyzed –OR groups, (iii) the sintering and growth of particles and (iv) the rearrangement of newly formed chemical bonds. The center of the most intense Raman band of the E _g mode at 143.8 cm^–1 in the undoped TiO₂ sample continually shifted to higher wave numbers and the full-width at half maximum increased with iron doping. Transmission electron microscopy revealed decrease of the mean particle size from 16.3 nm in undoped sample to 9.7 nm in the highest iron doped sample. The particle size distribution becomes narrower with iron doping. The narrowest particle size distribution was found in sample with the Fe/Ti molar ratio of 0.05, calcined at 500°C. Scanning electron microscopy of undoped samples calcined at 580°C showed irregular aggregates having a relatively flat surface. On the contrary, the samples doped with 15 mol% of iron and treated at the same temperature exhibited a non-uniform sponge-like surface with distributed micrometer holes.     

钌配合物敏化La3+掺杂纳米多孔TiO2电极的光电性能研究

在染料敏化太阳能电池中,TiO2膜和敏化剂决定着电池的总体效率和机械性能。本文以4-甲基吡啶为原料,经过偶联、氧化、配位和配体交换反应合成了cis-RuL2(SCN)2, (L=2,2’-联吡啶-4,4’-二羧酸),通过溶胶-凝胶法制备了TiO2膜。为了提高TiO2膜的光电性能,将不同浓度的La(NO3)3 (0.1%、0.3%、0.5%和0.7%) 加入到溶胶中,采用cis-RuL2(SCN)2将掺杂前后的TiO2膜进行敏化。利用X射线衍射仪、原子力显微镜和X射线光电子能谱对所得薄膜进行结构表征。结果表明,当La离子的浓度为0.5%时,太阳能电池的效率最高,短路电流和开路电压比未掺杂的分别提高了0.54 mA/cm2和30.41 mV。     

Enhancing Light Absorption and Charge Transfer Efficiency in Carbon Dots through Graphitization and Core Nitrogen Doping

Single-source precursor syntheses have been devised for the preparation of structurally similar graphitic carbon dots (CDs), with (g-N-CD) and without (g-CD) core nitrogen doping for artificial photosynthesis. An order of magnitude improvement has been realized in the rate of solar (AM1.5G) H₂ evolution using g-N-CD (7950 μmol_H2 (g_CD)⁻¹ h⁻¹) compared to undoped CDs. All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a-CD) yet undoped g-CD display limited photosensitizer ability due to low extraction of photogenerated charges. Transient absorption spectroscopy showed that nitrogen doping in g-N-CD increases the efficiency of hole scavenging by the electron donor and thereby significantly extends the lifetime of the photogenerated electrons. Thus, nitrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis.     

Boron Doped Carbon Dots with Unusually High Photoluminescence Quantum Yield for Ratiometric Intracellular pH Sensing

Herein we report that boron doping in carbon dots results in increased photoluminescence (PL) quantum yield, which could be used for ratiometric intracellular pH sensing in cancer cell lines. Using a mixture of citric acid monohydrate, thiourea, and boric acid, microwave-assisted synthesis of boron doped blue emitting carbon dots (B-Cdots) with an average size of 3.5±1.0 nm was achieved. For B-Cdots, the maximum quantum yield (QY) was observed to be 25.8 % (11.1 % (w/w) H₃BO₃ input concentration), whereas, the same was calculated to be 16.9 % and 11.4 % for Cdots (synthesized from citric acid monohydrate and thiourea only) and P-Cdots (phosphorus doped carbon dots; synthesized using citric acid monohydrate, thiourea and phosphoric acid) (11.1 % (w/w) H₃PO₄ input concentration), respectively. The observed luminescence efficiencies as obtained from steady state and time-resolved photoluminescence measurements suggest an alternative emission mechanism due to boron/phosphorus doping in carbon dots. We furthermore demonstrated facile composite formation using B-Cdots and another carbon dots with orange emission in presence of polyvinyl alcohol (PVA), resulting in white light emission (0.31, 0.32; λ_ex 380 nm). The white light emitting composite enabled ratiometric pH sensing in the aqueous medium and showed favorable uptake properties by cancerous cells for intracellular pH sensing as well.     

Thermal Analysis of Sulfide Ge—Ga Glasses Doped by Praseodymium

The present study shows the dependence of the temperature of glass transition — T _g upon the presence and quantity of doping Pr atoms. Substantial effect of the form — chemical nature of compound from which the doping atoms are incorporated into the glass has been displayed as well. With the increase of the content of sulfidic form T _g values approach the level of undoped glasses. Thus, if the studied glasses are doped by sulfidic form, bonded areas atoms of Pr so atoms of S. Glasses doped by halogenous source of Pr behave differently; the shift of the T _g value does not change with the amount of the dopand, displaying the anion deficiency of glass stoichiometry in studied interval of halogenous dopands. Generally, a very slight non-stability of the glass against the oxidation in temperature region of glass transition is observed.This revised version was published online in November 2005 with corrections to the Cover Date.     

An improved method for the polymerization of ethynylferrocene. Conducting properties of doped polyethynylferrocene

The catalytic activity of the [Rh(cod)Cl]₂ complex (cod  cis, cis-cyclo-octa-1,5-diene) with respect to the polymerization of ethynylferrocene (EFc) was examined. A good yield (about 80%) of polyethynylferrocene (PEFc) was obtained in benzene by addition of sodium hydroxide as co-catalyst. PEFc was insoluble in most organic solvents. The conductivity (s̀) of the undoped polymer is about 10⁻¹¹ ohm⁻¹ cm⁻¹; upon doping PEFc with iodine in tetrahydrofuran the conductivity can be increased to 10-100 ohm⁻¹ cm⁻¹. The influence of other doping agents was also examined.