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.     

Phase stability and thermal conductivity of ytterbia and yttria co-doped zirconia

Rare earth oxides doping has been extensively investigated as one of the effective methods to lower thermal conductivity of 4.55 mol% Y2O3stabilized ZrO2(YSZ) thermal barrier coatings(TBCs).In the present work,5–6 mol% Yb2O3and Y2O3co-doped ZrO2ceramics were synthesized by solid reaction sintering at 1600 1C.The phase stability of the samples after heat treatment at 1500 1C was investigated.Yb2O3and Y2O3co-doped zirconia,especially when Yb2O3/Y2O3≥1,contained less monoclinic phase than single Yb2O3or Y2O3phase doped zirconia,indicating that co-doped zirconia was more stable at high temperature than YSZ.The thermal conductivity of the 3 mol% Yb2O3+3 mol% Y2O3co-doped ZrO2was 1.8 W m 1K 1at 1000 1C,which was more than 20% lower than that of YSZ.     

Properties of garnet-type Li6La3ZrTaO12 solid electrolyte films fabricated by aerosol deposition method

The garnet-type Li_6La_3ZrTaO_(12)(LLZT) solid electrolyte films were fabricated by aerosol deposition(AD)method.Ball-milled LLZT powder with a cubic garnet structure and a particle size of 1-2 urn was used as raw material and deposited directly on a SUS316L or a glass substrate via impact consolidation.As-deposited LLZT film has a cubic garnet structure but contains Li_2CO_3 and La_2Zr_2O_7 phases.SEM observation revealed that the film consists of LLZT particles fractured into submicron size.The impurity phase formation during AD process was caused by the local heating by the collision between LLZT particles and deposition surface and reaction with CO_2.The Li~+ ion conductivity of LLZT film was estimated to be 0.24 × 10~(-5)S cm~(-1) at room temperature.Electronic conductivity of LLZT film was confirmed to be around 10~(-12) S cm~(-1),indicating the dominant Li~+ ion conduction of LLZT film.     

Preparation and catalytic effect of porous Co3O4 on the hydrogen storage properties of a Li-B-N-H system

A porous Co_3O_4 with a particle size of 1–3 μm was successfully prepared by heating Co-based metal organic frameworks MOF-74(Co) up to 500 °C in air atmospheric conditions. The as-prepared porous Co_3O_4 significantly reduced the dehydrogenation temperatures of the LiBH_4-2LiNH_2 system and improved the purity of the released hydrogen. The LiBH_4-2LiNH_2-0.05/3Co_3O_4 sample started to release hydrogen at 140 °C and released hydrogen levels of approximately 9.7 wt% at 225 °C. The end temperature for hydrogen release was lowered by 125 °C relative to that of the pristine sample. Structural analyses revealed that the as-prepared porous Co_3O_4 is in-situ reduced to metallic Co, which functions as an active catalyst, reducing the kinetic barriers and lowering the dehydrogenation temperatures of the LiBH_4-2LiNH_2 system. More importantly, the porous Co_3O_4-containing sample exhibited partially improved reversibility for hydrogen storage in the LiBH_4-2LiNH_2 system.     

Mineralogical alteration of thermally treated siderite in air: Mössbauer spectroscopy results

Mineralogical alternation of thermally treated siderite in air atmosphere has been systematically analyzed by Mössbauer effects. It was preliminarily estimated from the area of subspectra that 4%, 39% and 62% of magnetite were formed at 410 °C, 490 °C and 510 °C respectively. After being incrementally heated at 530 °C the spectra consist of two sextets of Fe₃O₄. Sextet of γ-Fe₂O₃ with hyperfine field of 50T was observed at 550 °C. Spectra at 580 °C consisted of two sextets with hyperfine fields caused by γ-Fe₂O₃ and α-Fe₂O₃. Fe₃O₄ disappeared and the amount of γ-Fe₂O₃ decreased, while the quantity of α-Fe₂O₃ increased to 34% and 77% at 640 °C and 690 °C, respectively. During the early stage of decomposition and oxidation, FeO was probably produced but quickly oxidized to magnetite and unidentified in our experiment. These results, in good agreement with the X-ray diffraction analyses and microscopic observation, provide an interpretation to anomalous magnetic property changes of siderite-bearing rock samples.     

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.     

Synthesis characterization and improved electrochemical performance of Li_2FeSiO_4/C as cathode for lithium-ion battery by metal doping

In this paper, Li_2FeSi_(0.98)M_(0.02)O_4/C(M = Mg, Zn, Co, Mn, Ni) was synthesized as cathode material for lithium ion battery by solid-state method. The results show that the materials doped with Mg and Zn at the Si-sites have good initial discharge capacity. Then Li_2FeSi_(1-x)M_xO_4/C(M = Mg, Zn; x = 0.01, 0.02, 0.03, 0.05) were also synthesized via solid-state method. It is concluded that Li_2FeSi_(0.99)Mg_(0.01)O_4/C and Li_2FeSi_(0.98)Zn_(0.02)O_4/C have better initial discharge capacity which is 125 mAh/g and 166.2 mAh/g, respectively. The capacity of Li_2Fe_(0.98)Zn_(0.02)SiO_4/C is 157.3 m Ah/g after 10 cycles at 0.1 C, and the capacity retention rate is 94.6%. The Li~+ diffusion coefficient of Li_2FeSi_(0.98)Zn_(0.02)O_4/C is higher than that of pure phase materials by one order of magnitude. The Li_2FeSi_(0.99)Mg_(0.01)O_4/C and Li_2FeSi_(0.98)Zn_(0.02)O_4/C were tested by XRD and SEM. XRD patterns indicate that the crystal structure of Li_2FeSiO_4 is not changed after being doped with metal ion at the Si-site. The SEM image indicates that no obvious agglomeration is detected in these materials. Li_2FeSi_(0.98)Zn_(0.02)O_4/C processes better electrochemical performance analyzed by EDS、XPS and FT-IR spectra. The data prove that Si~(4+) is successfully replaced by Zn~(2+) in the crystal structure of Li_2FeSiO_4.     

Effect of B2O3 on the aqueous tape casting and microwave properties of Li2O–Nb2O5–TiO2 ceramics

The effect of B2O3 addition on the aqueous tape casting, sintering, microstructure and microwave dielectric properties of Li2O-Nb2O5-TiO2 ceramics has been investigated. The tape casting slurries exhibit a typical shear-thinning behavior without thixotropy, but the addition of B2O3 increases the viscosity of the slurries significantly. It was found that doping of B2O3 can decrease the tensile strength, strain to failure and density of the green tapes. The sintering temperature could be lowed down to 900℃ with the addition of 2 wt% B2O3 due to the liquid phase effect. No secondary phase is observed. The addition of B2O3 does not induce much degradation on the microwave dielectric properties. Optimum microwave dielectric properties of εr 67, Q×f 6560 GHz are obtained for Li2O-Nb2O5-TiO2 ceramics containing 2 wt% B2O3 sintered at 900 1C. It represents that the ceramics could be promising for multilayer low-temperature co-fired ceramics (LTCC) application.     

Microstructure, mechanical and thermo-physical properties of hot-pressed Al2O3-GdAlO3-ZrO2 ceramics with eutectic composition

A low cost chemical co-precipitation method was employed to fabricate nanoscale Al_2O_3-GdAlO_3-ZrO_2 powder with eutectic composition. A careful control of reaction conditions was required during the preparation. The synthesized nanopowders exhibited a particle size of 20-200 nm, and were highly dispersive and uniform. The results showed that calcination temperature had an important influence on the phase constituents of the nanopowders. With increasing the calcination temperature, a phase transformation from θ-Al_2O_3 to α-Al_2O_3 and a thermal decomposition from Gd_3 Al_5O_(12)(GdAG) to GdAlO_3 and α-Al_2O_3 occurred in sequence. A calcination temperature of 1300 ℃ was needed for the crystallization of α-Al_2 O_3. These nanosized powders were consolidated via hot pressing to produce a fully densified ceramic composite with eutectic composition. The Al_2O_3-GdAlO_3-ZrO_2 ceramic hot-pressed at 1500 ℃ exhibited a relative density of 99.4%, a flexural strength of 485 MPa and a fracture toughness of 6.5 MPa m~(1/2). The ceramic had a thermal conductivity of 1.9 W m K~(-1) at 1200 ℃ and a thermal expansion coefficient of 9.49 ×10~(-6) K~(-1) at 1100 ℃.     

养护温度对LiNO3抑制碱硅酸反应及其膨胀的影响

研究了38℃和60℃下石英玻璃在掺LiNO_3的Na OH溶液中碱硅酸反应过程,采用酸化处理法确定体系中SiO_2分布,采用等离子发射光谱(ICP)分析溶液中Na、Si和Li元素浓度变化,采用X射线衍射(XRD)和扫描电子显微镜(SEM)表征反应产物的组成和形貌;并检测了38℃和80℃湿气养护下掺LiNO_3的沸石化珍珠岩混凝土微柱的膨胀性。结果表明:加入LiNO_3降低了溶液中石英玻璃的溶蚀率和SiO_2的溶解度,减缓了ASR的反应速率;不同养护温度下形成的含锂产物不同,提高温度有利于Li_2SiO_3晶体的形成。对于混凝土微柱,掺锂试件早期抑制效果良好,后期仍膨胀;相同锂掺量下80℃湿气养护的试件膨胀率却明显低于38℃时的膨胀率。可见,高温养护下LiNO_3抑制ASR膨胀的效果不能很好地评价在低温下的作用效果。     

Electrochemistry study on PEO-LiClO<Subscript>4</Subscript>-ZSM5 composite polymer electrolyte

Allsolid-statelithiumpolymerbatteriesmaybeoneofthebestchoicesforelectrochemicalpowersourceofthefuturecharacterizedbyitshighenergydensities,goodcyclability,reliabilityandsafety[1,2].PEO-LiXbasedpoly-merelectrolyteshadreceivedextensiveattention[4,5],foritspotentialcapabilitytobeusedascandidatematerialforthetraditionalliquidelectrolytes,sinceWrightetal.foundthatthecomplexofPEOandalkalinesaltshadtheabilityofionicconductivityin1973[3].ThegeneralconceptofthetransportofLi+inthepolymerelectrolytewa…     

锂离子电池负极材料Li4Ti5O12的研究进展

Li₄Ti₅O₁₂材料具有稳定、安全、寿命长等显著优点,是锂离子电池负极材料的研究热点。介绍了Li₄Ti₅O₁₂的结构特点和储能机制,对制备Li₄Ti₅O₁₂的高温固相合成法、微波合成法、溶胶凝胶法以及其他制备方法进行讨论和概述,同时对离子掺杂、表面包覆和形貌调控等改性研究进行了总结和评述。最后,对Li₄Ti₅O₁₂的发展前景进行了展望。     

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.     

Novel approaches to produce Al2O3– TiC/TiCN– Fecomposite powders directly from ilmenite

Al2O3 –TiC/TiCN–Fe composite powders were successfully prepared directly from ilmenite at 1300–1400℃.The effects of Al/C ratio,sintering atmosphere,and reaction temperature and time on the reaction products were investigated.Results showed that the nitrogen atmosphere was bene cial to the reduction of ilmenite and the formation of Al2O3 –TiC/TiCN–Fe composite powders.When the reaction temperature was between 600 and 1100℃,the intermediate products,TiO2,Ti3O5 and Ti4O7 were found,which changed to TiC or TiCN at higher temperature.Al/C ratio was found to affect the reaction process and synthesis products.When Al addition was 0.5 mol,the Al2O3 phase did not appear.The content of carbon in TiCN rose when the reaction temperature was increased.     

The electrical property of MnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> and its application for SUS 430 metallic interconnect

The conductivity of MnCo₂O₄ spinel, the best route to form the MnCo₂O₄ protective coating applied by the sol-gel process, and its effect on the intermediate temperature oxidation behavior of SUS 430 alloy, a typical material for the interconnect of solid oxide fuel cell (SOFC), was investigated. The phase structure and surface morphology of the coating and surface oxides were characterized by XRD, SEM and EDS; the “4-probe” method was employed to determine the conductivity of MnCo₂O₄ spinel and the area specific resistance (ASR) of the surface oxides. The conductivity of MnCo₂O₄ spinel is excellent, which is 2 orders of magnitude better than that of MnCr₂O₄ spinel. Long-term thermally cyclic oxidation at 750°C in SOFC cathode atmosphere and ASR measurement have shown that calcined in reducing atmosphere followed by pre-oxidation in the air is the best technique for forming the MnCo₂O₄ protective coating, which enhances the oxidation resistance, and improves the electrical conductivity and adherence of coated SUS 430 alloy significantly. As a result, the MnCo₂O₄ spinel is the most potential candidate for SOFC metallic interconnect protective coating application.     

Li1+xAlxTi2-x(PO4)3(x=0~0.4)溶胶-凝胶法合成及其性质

以乙酸锂、硝酸铝、钛酸丁酯、磷酸二氢铵为原料,利用溶胶-凝胶法合成锂离子Li_1+xAl_xTi_2-x(PO₄)₃(x=0~0.4)固体电解质体系,检测结果表明：Li_1+xAl_xTi_2-x(PO₄)₃体系具有较好的结晶性,合成的粉末与烧结片之间的结晶性与结构差异不大;当Al³⁺掺杂量逐步增加时,离子电导率逐渐增大,并在x=0.3时达到最大值,但掺杂量进一步增加时,离子电导率迅速下降;活化能的变化趋势与离子电导率相反.     

Hydrothermal synthesis, characterization and nonlinear optical effect of orthorhombic phase Ca2B6O11 · H2O

Hydrothermal treatment of calcium oxide and boric acid mixtures at temperatures between 234 °C and 300 °C has produced a colorless, transparent, orthorhombic compound Ca₂B₆O₁₁ · H₂O. Of the seven known members of the series of hydrated dicalcium hexaborate containing boron-oxygen six-membered ring anionic group (B₃O₈)^-7, only the title compound has been found to have the nonlinear optical effect. The second harmanic generation (SHG) effect of its crystal is larger than that of KH₂PO₄ (KDP). The reflection spectrum has shown that this compound has no absorption in the experimental wavelength range (800–240 nm). Its crystal structure is favorable for generating the nonlinear optical effect.     

Structure evolution of Y2O3 nanoparticle/Fe composite during mechanical milling and annealing

Fe-25 wt% Y2O3composite powders have been fabricated by mechanical milling(MM) Fe powders of 100 μm in diameter and Y2O3nanoparticles in an argon atmosphere for the milling periods of4,8,12,24,36,and 48 h,respectively.The features of these powders were characterized by using X-ray diffraction(XRD),scanning electron microscopy(SEM),electron probe micro analyzer(EPMA) and transmission electron microscopy(TEM).The experimental results showed that the mean particle size and crystalline size of MM powders decreased with the milling time increasing.All the elements distributed homogenously inside the powders after 48 h of MM.The lattice constant of the matrix α-Fe kept constant with the milling time,and no solid solution took place during MM process.After 8 h of MM,the α-Fe in each powder became nanocrystalline.After 48 h of MM,Y2O3changes from nanostructure into amorphous structure,and the crystalline size of α-Fe further decreased to 10 nm.The Y2O3in the powders mechanically milled for 48 h kept the amorphous structure after being annealed at 400 1C,and starts to crystallize when the powders are annealed at 600 1C.The amorphous Y2O3contains a small amount of Fe,and crystalline FeYO3appears at 800 1C.     

Improved hydrogen desorption properties of Co-doped Li<Subscript>2</Subscript>BNH<Subscript>6</Subscript>

The hydrogen desorption properties of Li 2 BNH 6 were improved by doping with cobalt. With the addition of CoCl 2 (7 wt%), more than 8 wt% of hydrogen was released from Li 2 BNH 6 at temperatures below 210°C, which is approximately 90°C lower than that of pristine Li 2 BNH 6 . X-ray diffraction, Fourier transform-infrared and Raman characterizations revealed that the dehydrogenation was a stepwise process with the formation of intermediates Li 4 BN 3 H 10 and LiBH 4 and final products of Li 3 BN 2 and LiH. The introduction of Co greatly accelerated the dehydrogenation of Li 4 BN 3 H 10 . X-ray absorption near-edge structure measurements revealed that Co and CoB species formed during ball milling of CoCl 2 with LiBH 4 and LiNH 2 , which may function as catalyst in the subsequent dehydrogenation.     

Mn0.8Zn0.2Fe2O4 nanoparticulates spinel ferrites:An approach to enhance the antenna field strength for improved magnitude versus offset（MVO）

Electromagnetic signals in deep reservoir are very weak so that it is difficult to predict about the presence of hydrocarbon in seabed logging(SBL) environment.In the present work,Mn0.8Zn0.2Fe2O4 nanoferrites were prepared by a sol–gel technique at different sintering temperatures of450 °C,650 °C and 850 °C to increase the strength of electromagnetic(EM) antenna.XRD,FESEM,Raman spectroscopy and HRTEM were used to analyze the phase,surface morphology and size of the nanoferrites.Magnetic properties of the nanoferrites were also measured using an impedance network analyzer.However,nanoferrites sintered at 850 °C with initial permeability of 200 and Q factor of 50 were used as magnetic feeders with the EM antenna.Lab scale experiments were performed to investigate the effect of magnetic field strength in scale tank.SPSS and MATLAB softwares were also used to confirm the oil presence in scale tank.It was observed that the magnitude of the EM waves for the antenna was increased up to 233%.Finally,the correlation values also show 208% increase in the magnetic field strength with the presence of the oil.Therefore,antenna with Mn0.8Zn0.2Fe2O4 nanoferrites based magnetic feeders can be used for deep water and deep target hydrocarbon exploration.