Subsolidus phase relations in the system MgO-ZnO-SiO2 at high pressure

The subsolidus phase relations were determined experimentally in the system MgO-ZnO-SiO2 at 1.0 GPa and 1 200℃, by use of the high-pressure apparatus "piston-cylinder". The results showed characteristics of the phases assemblage different from that in similar ternary systems. It is impossible to form complete Mg2SiO4-Zn2SiO4 olivine and Mg2Si2O6-Zn2Si2O6 pyroxene solid solution. This is controlled by the properties of Zn2+ with an outer layer of electron (Ar)3d10, different from others transition metal ions, like Fe2+ , Ni2+ , Co2+ .     

尖晶石型Li4Ti5O12的合成及其性能

采用高温固相法、溶胶-凝胶法和热聚合法制备锂离子电池负极材料Li₄Ti₅O_12.通过X-射线衍射、扫描电镜显微镜、电化学阻抗和恒流充放电表征产物的结构、形貌及电化学性能.3种方法制备的Li₄Ti₅O₁₂均为尖晶石结构,用高温固相法所得的粉体颗粒较大,而用溶胶-凝胶法所得粉体颗粒最小,其平均粒度在200~350 nm范围内,表现出较好的电化学性能;溶胶-凝胶法制备的样品粉末在0.2 C倍率下首次放电容量为174.5 mAh/g,经过25次循环后容量衰减仅5.7%.     

MgFeSiO4 prepared via a molten salt method as a new cathode material for rechargeable magnesium batteries

Well-crystallized MgFeSiO₄ microparticles were synthesized at different temperatures by a simple molten salt method using KCl flux. As a new cathode for rechargeable magnesium batteries, the material shows a reversible Mg²⁺ intercalation-deintercalation process. In 0.25 mol/L Mg(AlCl₂EtBu)₂/THF electrolyte, MgFeSiO₄ synthesized at 900??C can deliver a 125.1 mAh/g initial discharge capacity and a 91.4% capacity retention on the 20th cycle at a rate of 0.1C (about 15.6 mA/g). The results show that MgFeSiO₄ could be a good host for Mg²⁺ intercalation, and a potential cathode material for high-energy rechargeable magnesium batteries.     

Synthesis and modification of well-ordered layered cathode oxide LiNi<Subscript>2/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript>

Oxalic-acid-based co-precipitation method was employed to prepare LiNi_2/3Mn_1/3O₂ sample with a high-ordered structure. Li⁺, Ni²⁺ and Mn²⁺ acetates were used as starting materials. The influence of the amount of lithium source in the starting materials on Li⁺ content, disorder of Li⁺-Ni²⁺ ions, and electrochemical performance has been investigated. Rietveld refinement shows that the sample prepared with 20% excess Li-source in the starting materials exhibits a perfect ordered structure. A specific discharge capacity is as high as 172 mAh/g at C/20 in the voltage range of 4.35–2.7 V. However, the cyclability is not satisfactory: about 25.3% fade in capacity was observed over 50 cycles. Chemically stable SiO2 was coated on the surface of LiNi_2/3Mn_1/3O₂ particles. A significant improvement in cyclability was attained with 3 wt% SiO2 coating, which is ascribable to the protection of LiNi_2/3Mn_1/3O₂ particles from being dissolved into the electrolyte.     

三价铁离子掺杂对钛酸锂结构和化学性能的影响

采用溶胶凝胶法制备Li4-x/3FexTi5-2x/3O12(x=0,0.03,0.06,0.09)粉体活性材料,并优化了最佳掺杂量为x=0.03。通过X射线衍射(XRD)、扫描电镜(SEM)、恒流充放电测试对材料进行结构、形貌及电化学性能表征。结果表明:掺杂适量的铁离子不会改变钛酸锂的尖晶石结构和形貌。1C时,Li3.99Fe0.03Ti4.98O12首次放电比容量为145.40 m A·h/g;纯相的首次放电比容量仅为116.95 m A·h/g。     

Synthesis of LiCo<Subscript>0.3</Subscript>Ni<Subscript>0.7</Subscript>O<Subscript>2</Subscript> as cathode materials for lithium ion batteries by citric acid-assisted sol-gel method

The synthesis process of LiCo0.3Ni0.7O2 was investigated by FT-IR, mass spectroscopy, elemental analysis, SEM, BET, TG/DTA and XRD in this paper. The results revealed that lithium and transition metal ions were trapped homogeneously on an atomic scale throughout the precursor. Li2CO3, NiO and CoO are the intermediate products obtained after decomposition of the precursor and Li2CO3 undergoes direct reactions with NiO and CoO to form LiCo0.3Ni0.7O2. Moreover, the kinetics of formation of LiCo0.3Ni0.7O2 by dtrate sol-gel method is faster than the case of the conventional solid-state reaction between lithium carbonate and corresponding reactants. The single phase of LiCo0.3Ni0.7O2 was synthesized at temperature as low as 550℃. The discharge capacity of LiCo0.3Ni0.7O2 increases from 127 to 185 mAh/g as the caldnation temperature increasing from 550 to 750℃. After 100 cycles, the discharge capacity of the sample calcined at 750℃ is 155 mAh/g. The electrochemical study shows that the LiCo0.3Ni0.7O2 has high discharge capacity and good cycling behavior for lithium ion batteries.     

Morphological evolution and kinetic enhancement of Li2FexMn1-xSiO4/C cathodes for Li-ion battery

Li_2MnSiO_4-based cathode materials possess reasonable work potentials and high theoretical capacities,while the practical energy/power densities are constrained by their inferior kinetics of Li~+ diffusion.In this work,the Pmn2_1-structure Li_2Fe_xMn_(1-x)SiO_4/C materials were synthesized via a solvothermal method and evaluated as Liion cathode materials,with notable morphological evolutions and tunable crystallographic habits observed after solvothermal process.The Li_2Fe_(0.33)Mn_(0.67)SiO_4/C material delivers an initial reversible capacity of 250.2mAh g~(-1)at 0.1 C(～1.51 Li~+insertion/extraction,1 C=166 mA g~(-1)),excellent high-rate capability(52.2 mAh g~(-1)at 5 C),and good long-term cyclability(64.6%after 196 cycles at 2 C).The enhanced electrochemical properties are attributed to the boosted ion/electron transports induced by preferred morphological and structural characteristics of Li_2Fe_(0.33)Mn_(0.67)SiO_4/C.     

Li3N film modified separator with homogenization effect of lithium ions for stable lithium metal battery

Lithium metal anode with high theoretical capacity is considered to be one of the most potential anode materials of the next generation. However, the growth of lithium dendrite seriously affects the application of lithium metal anode and the development of lithium metal batteries (LMBs). Herein, an ultrathin Li₃N film modified separator to homogenize the lithium ions and protect the lithium metal anode was reported. Due to the intrinsic properties of Li₃N, the functional separator possessed good thermal stability, mechanical properties and electrolyte wettability, and the homogenization of the lithium ion was realized without increasing the interface impedance. With this functional separator, the Li/Li symmetrical cell could achieve a long cycle with low overpotential for 1000 ​h at a current density of 1 ​mA ​cm⁻². Furthermore, when the full battery was assembled with LiFePO₄ and the discharge capacity could be maintained at 151 mAh g⁻¹ after 400 cycles at 1 ​C. In addition, the full battery also showed good rate performance, and provided a high discharge capacity of 114 mAh g⁻¹ at 5 ​C.     

LiFe1-x Mgx PO4/C的制备和性能研究

以乙酸镁为掺杂元素、蔗糖为碳源,采用固相反应法制备镁掺杂磷酸铁锂包覆碳复合材料LiFe1-xMgxPO4/C(x=0.01,0.02,0.03,0.04).利用X射线衍射(XRD)分析其结构,扫描电镜(SEM)观察其形貌,恒电流法测定其电化学性能.研究结果表明镁离子掺杂没有影响材料的结构,而是提高了其放电容量和循环性能.在这些样品中,LiFe0.98Mg0.02位PO4/C的容量最高,首次放电达到140.0 mAh/g;并且在80次循环后容量没有衰减反而增加到148.6 mAh/g左右.     

Enhanced low-temperature performance of slight Mn-substituted LiFePO<Subscript>4</Subscript>/C cathode for lithium ion batteries

Low temperature performance of LiFePO₄/C cathode was remarkably improved by slight Mn-substitution. Electrochemical measurements showed that about 95% of the discharge capacity of LiFe_0.98Mn_0.02PO₄/C cathode at 20°C was obtained at 0°C, compared to 85% of that of LiFePO₄/C cathode. The LiFe_0.98Mn_0.02PO₄/C sample also presented enhanced rate performance at −20°C with the discharge capacities of 124.4 mA h/g (0.1C), 99.8 mA h/g (1C), 80.7mAh/g (2C) and 70 mA h/g (5C), respectively, while pristine LiFePO₄/C only delivered capacities of 120.5 mA h/g (0.1C), 90.7 mA h/g (1C), 70.4 mA h/g (2C) and 52.2 mA h/g (5C). Cyclic voltammetry measurements demonstrated an obvious improvement of the lithium insertion-extraction process of the LiFePO₄/C cathode by slight Mn-substitution. The results of FSEM observation and electrical conductivity measurement indicated that slight Mn-substitution minimized the particle size of LiFe_0.98Mn_0.02PO₄/C and also obviously improved the electrical conductivity of the compound, thus obviously enhances the interface reaction process on the cathode.     

Solid electrolyte composite Li_4P_2O_7-Li_3PO_4 for lithium ion battery

The researches on solid electrolyte have been significantly increasing due to the safety problem in lithium ion battery.The lithium phosphates are chosen due to environmentally friendly.In the present study Li_4 P_2 O_7 was synthesized by solid state reaction using NH_4 H_2 PO_4 and Li_2 CO_3 with the ratio 1:2 at various temperatures of600 ℃,800 ℃ and 900℃.The products were characterized by x-ray diffraction,scanning electron microscopy and impedance spectroscopy.The x-ray diffraction showed that all samples consisted of two phases.It was found that the products consisted of 52.44% Li_4 P_2 O_7 and 47.56% LiPO_3;93.56% Li_4 P_2 O_7 and 6.44% Li_3 PO_4;and46.27% Li_4 P_2 O_7 and 53.67% Li_3 PO_4 under the synthesizing temperature of 600 ℃,800℃ and 900 ℃,respectively.The highest ionic conductivity of 3.85 ×10~(-5) S/m was achieved for composite Li_4 P_2 O_7-Li_3 PO_4 with the highest content of 93.56% Li_4 P_2 O_7.This conductivity is higher compared with single phase of LiPO_3,Li_3 PO_4 and Li_4 P_2 O_7.The increase in ionic conductivity may be due to the mixed anion effects related to the phosphate networks,and it also corresponds to the existence of anorthic phase Li_4 P_2 O_7 with the space group P-1(2).The crystal lattice analysis showed that the reactant Li_4 P_2 O_7 consisted of diphosphate groups P_2 O_7.The lithium tetrahedral LiO_4 were linked to P_2 O_7 groups formed a continuous framework containing large voids,available for Li~+ ion transport,and thus it exhibited high conductivity.A composite Li_4 P_2 O_7-Li_3 PO_4 is a promising solid electrolyte for solid state battery.     

Y2O2S:Eu3+,Zn2+,Ti4+荧光体的缺陷及红色长余辉发光性质

采用高温固相法合成了红色长余辉材料Y2O2S:Eu3+,Zn2+,Ti4+,实现了余辉发光中心和缺陷中心之间的能量传递。通过XRD、荧光发射和激发光谱、余辉发射光谱与衰减曲线、色坐标和热释光谱测试手段对Y2O2S:Eu3+,Zn2+、Y2O2S:Eu3+,Ti4+、Y2O2S:Eu3+,Zn2+,Ti4+和Y2O2S:Eu3+,Mg2+,Ti4+进行了结构与性能的表征,发现其荧光发射与余辉发射基本一致,红色余辉发光主峰位于625 nm附近,来源于Eu3+的5D0→7F2跃迁发射。相比而言,Y2O2S:Eu3+,Zn2+,Ti4+余辉发光性能最好,可持续1.5 h左右。     

Embedding Co3O4 nanoparticles into graphene nanoscrolls as anode for lithium ion batteries with superior capacity and outstanding cycling stability

Co_3O_4 is a promising high-performance anode for lithium ion batteries(LIBs), but suffers from unsatisfied cyclability originating duo to low electrical conductivity and large volume expansion during charge and discharge process. Herein, we successfully constructed the Co_3O_4 nanoparticles embedded into graphene nanoscrolls(GNSs) as advanced anode for high-performance LIBs with large capacity and exceptional cyclability. The onedimensional(1 D) Co_3O_4/GNSs were synthesized via liquid nitrogen cold quenching of large-size graphene oxide nanosheets and sodium citrate(SC) modified Co_3O_4 nanoparticles, followed by freeze drying and annealing at400 °C for 2 h in nitrogen atmosphere. Benefiting from the interconnected porous network constructed by 1 D Co_3O_4/GNSs for fast electron transfer and rapid ion diffusion, and wrinkled graphene shell for significantly alleviating the huge volume expansion of Co_3O_4 during lithiation and delithiation. The resultant Co_3O_4/GNSs exhibited ultrahigh reversible capacity of 1200 mAh g~(-1) at 0.1 C, outperforming most reported Co_3O_4 anodes.Moreover, they showed high rate capability of 600 m Ah g-1 at 5 C, and outstanding cycling stability with a high capacity retention of 90% after 500 cycles. Therefore, this developed strategy could be extended as an universal and scalable approach for intergrating various metal oxide materials into GNSs for energy storage and conversion applications.     

钴掺杂Mn3O4作为模板制备锂离子电池正极LiMn2O4

以水热合成的钴掺杂Mn₃O₄作为模板,通过固相反应制备尖晶石LiMn₂O₄。XRD谱图和SEM照片显示制备的LiMn₂O₄具有岩石状结构并呈现良好的结晶性,同时Co的引入能够引起LiMn₂O₄晶格的收缩。作为锂离子电池正极材料,Co含量的增加能够提高循环稳定性但降低材料放电比容量,3% Co掺杂的LiMn₂O₄在0.5 C的电流密度下,经过100次循环后,剩余放电比容量达101.6 mAh·g^-1;在10 C的电流密度下,放电比容量可维持在81.0 mAh·g^-1,优于未掺杂的LiMn₂O₄。这是由于Co的引入能够稳定LiMn₂O₄晶体结构并抑制循环中的姜-泰勒扭曲。     

锂钒氧化物的制备与电化学性能研究

以Li_2CO_3和NH_4VO_3为原料,采用非熔融态的固相反应法合成了锂离子电池正极材料锂钒氧化物.通过TG-DTA,XRD分析确定了合成反应的主要历程.XRD测试表明,580℃焙烧10h获得的产物为单一相层状结构,晶型发育良好.循环伏安测试表明,Li~+在材料中嵌入脱出的机理不同,嵌入是分步进行的.恒电流充放电测试表明,锂钒氧化物的初始容量为252.9mAh.g-1,55次循环后容量保持率高达97.07%,循环性能优良.交流阻抗测试表明,材料具有较高的离子电导率,有利于提高其电化学性能.     

锌掺杂对Li4Ti5O12负极材料电化学性能的影响

通过溶胶凝胶法制备Li4Ti5O12及锌掺杂Li4-2x/3ZnxTi5-x/3O12(x=0.05,0.10,0.15,0.20)活性材料,并优化了最佳掺杂量为x=0.10。通过X射线衍射(XRD)、扫描电镜(SEM)、恒流充放电测试对材料进行结构、形貌及电化学性能表征。结果表明:掺杂适量的锌离子不会改变钛酸锂的尖晶石结构和形貌,1C时,Li3.93Zn0.10Ti4.97O12放电比容量升高且容量保持率为99.74%;而纯相的容量保持率仅为94.30%。     

Investigation of the electronic structure and photoluminescence properties of Eu3＋ in Sr2Mgl_xZnxSi207 （0 〈x 〈 1）

Undoped and Eu 3+-doped Sr 2 Mg 1-x Zn x Si 2 O 7 (0≤x≤1) powder crystals were obtained by conventional solid-state reaction.X-ray diffraction,inductively coupled plasma analysis,and Fourier transform infrared spectroscopy results implied that a complete solid-solution formed between Sr 2 MgSi 2 O 7 and Sr 2 ZnSi 2 O 7 as well as local structural adjustment.Excitation spectra exhibited O 2-Eu 3+ charge transfer (CT) bands centered at 250 nm for Sr 2 MgSi 2 O 7:Eu 3+ and 258 nm for Sr 2 ZnSi 2 O 7:Eu 3+.Emission spectra exhibited a major band around 616 nm,which showed the environment around Eu 3+ was non-centrosymmetric in both Sr 2 MgSi 2 O 7:Eu 3+ and Sr 2 ZnSi 2 O 7:Eu 3+.In addition,first principles calculations within the local density approximation (LDA) of density functional theory (DFT) were used to calculate the electronic structure of Sr 2 MgSi 2 O 7 and Sr 2 ZnSi 2 O 7.Calculated results were correlated with experimental UV-vis reflection spectra and the observed shift of the O 2-Eu 3+ CT band.     

Zr~(4+)/F~– co-doped TiO_2(anatase) as high performance anode material for lithium-ion battery

Zr~(4+) and F~– co-doped TiO_2 with the formula of Ti_(0.97)Zr_(0.03)O_(1.98)F_(0.02) was facilely synthesized by a sol-gel template route.The crystal structure,morphology,composition,surface area,and conductivity were characterized by Raman spectroscopy,energy-dispersive X-ray analysis,scanning electron microscopy,Brunauer-Emmett-Teller measurements,X-ray photoelectron spectroscopy,and electrochemical impedance spectroscopy.The results demonstrate that Zr~(4+)and F~–homogeneously incorporated into TiO_2,forming solid solution with an anatase structure.Ti_(0.97)Zr_(0.03)O_(1.98)F_(0.02)shows outstanding electrochemical properties as Li-ion battery anode in comparison with Ti_(0.97)Zr_(0.03)O_2.In particular,upon 35-fold cycling at 1C-rate Zr~(4+)/F~–co-doped TiO_2delivers a reversible capacity of 163 mAh g~(–1),whereas Zr~(4+)-doped TiO_2gives only 34 mA h g~(–1).Additionally,Zr~(4+)/F~–co-doped TiO_2retains a capacity of 138 mA h g~(–1)during cycling even at 10 C.The enhance performance originates from improved conductivity of Zr~(4+)/F~–co-doped TiO_2material through generation of Ti~(3+)(serving as electron donors)into the crystal lattice and,possibly,due to F-doping blocked the anode surface from attack of HF formed as electrolyte decomposition product.     

Synthesis of layered LiMnO2 byin situ oxidation-intercalation and a study of the reaction mechanism and electrochemical performance

Using Mn(OH)₂ as precursor, LiOH as lithiating agent and (NH₄)₂S₂O₈ as oxidant, layeredo-LiMnO₂ was obtained by a novel method—in situ oxidation-intercalation under mild conditions (80 °C). The product was characterized by XRD, ICP, TEM and⁷Li-NMR. The results reveal that orthorhombic LiMnO₂ with high purity and good crystallinity can be obtained by this method. During electrochemical tests, a LiMnO₂/Li cell shows an initial reversible capacity of 208 mAh · g⁻¹ and a reversible capacity of 180 mAh · g⁻¹ after 30 cycles at room temperature.     

Electrochemical performance of a nickel-rich LiNi<Subscript>0.6</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode material for lithium-ion batteries under different cut-off voltages

A spherical-like Ni_0.6Co_0.2Mn_0.2(OH)₂ precursor was tuned homogeneously to synthesize LiNi_0.6Co_0.2Mn_0.2O₂ as a cathode material for lithium-ion batteries. The effects of calcination temperature on the crystal structure, morphology, and the electrochemical performance of the as-prepared LiNi_0.6Co_0.2Mn_0.2O₂ were investigated in detail. The as-prepared material was characterized by X-ray diffraction, scanning electron microscopy, laser particle size analysis, charge-discharge tests, and cyclic voltammetry measurements. The results show that the spherical-like LiNi_0.6Co_0.2Mn_0.2O₂ material obtained by calcination at 900℃ displayed the most significant layered structure among samples calcined at various temperatures, with a particle size of approximately 10 μm. It delivered an initial discharge capacity of 189.2 mAh·g-1 at 0.2C with a capacity retention of 94.0% after 100 cycles between 2.7 and 4.3 V. The as-prepared cathode material also exhibited good rate performance, with a discharge capacity of 119.6 mAh·g-1 at 5C. Furthermore, within the cut-off voltage ranges from 2.7 to 4.3, 4.4, and 4.5 V, the initial discharge capacities of the calcined samples were 170.7, 180.9, and 192.8 mAh·g-1, respectively, at a rate of 1C. The corresponding retentions were 86.8%, 80.3%, and 74.4% after 200 cycles, respectively.