Temperature stability of magnetoresistance （MR） and MR enhancement in Lal-x（Srl-yAgy）xMn03 system.

Polycrystalline samples of La12x(Sr12yAgy)x MnO3 (y = 0.0, 0.2, 0.4, 0.6, 1.0) were prepared by the solid-state reaction method. The temperature stability of magnetoresistance and magnetoresistance enhancement in La1-x(Sr1-yAgy)x MnO 3 system with both univalent and bivalent elements doped at A site and with unchanged value of Mn3+ /Mn4+ ratio were explored through the measurements of X-ray diffraction patterns, magnetiza-tion-temperature (M-T) curves, resistivity-temperature (q-T) curves and magnetoresistance-temperature (MR-T) curves. The results are as follows: there are two peaks in the q-T curves of the samples with Ag doping, one is caused by resistance change during the paramagnetism-ferromagnetism transition, and the other is from boundary-dependent scattering of conduction electrons on the boundaries of grains. The peak value of MR increases with increasing Ag doping content, and it increases from 8.2 % for y = 0.2 to 29.6 % for y = 1.0 under the magnetic field of B = 0.8 T; MR remains a constant of 12 % in the temperature range of 218-168 K for the sample with y = 1.0, and the temperature stability of MR is in favor of the practical application of MR.     

Electric transport properties and temperature stability of magnetoresistance of composite system between La8/9Sr1/45Na4/45MnO3 and Sb2O3

The samples ofLa8/9Sr1/45Na4/45MnO3 （LSNMO）/x/2（Sb2O3） were prepared by the solid-state reaction method. The electric transport properties and the temperature stabil-ity of magnetoresistance （MR） of the samples were studied through the measurements of X-ray diffraction patterns, resistivity-temperature （ρ-T） curves, mass magnetization-temperature （σ-T） curves, and magnetoresistance-temper-ature （MR-T） curves. The results indicate that the p-Tcurves of the original material LSNMO show two peaks, and the phenomenon of two peaks of ρ-T curves disappears for the composite samples, which can be explained by a competition between surface-phase resistivity induced by boundary-dependent scattering and body-phase resistivity induced by paramagnetism-ferromagnetism transition. For all the sam-ples in the low temperature range, MR increases continu-ously with the decrease of temperature, which shows a characteristic of low-field magnetoresistance. However, MR basically keeps the same in the high temperature range. The paramagnetism-ferromagnetism transition is observed in the high temperature range due to a composite between perov-skite manganite and insulator, which can enhance the tem-perature of MR appearance in the high temperature range and make it to appear near room temperature. For the sample with x = 0.12, MR remains constant at the value of 7.5 % in the temperature range of 300-260 K, which achieves a tem-perature stability of MR near room temperature. In addition,for the sample with x = 0.16, MR is above 6.8 % in the high temperature range of 318-252 K （△T = 66 K）. MR almost remains constant in this temperature range, which favors the practical application of MR.     

Research on charge ordering and magnetic properties in La0.3Ca0.7Mn1-xWxO3 system

The perovskite manganite sample La0.3Ca0.7Mn1-xWxO3 （x = 0.08, 0.12） was prepared by the solid-state reaction method. The effect of W doping on the Mn site to La0.3Ca0.7MnO3 charge ordering phase and the changing process of magnetic properties were studied through the measurement of the M-T curve, M-H curves, and ESR curves of the sample. The results showed that when x = 0.08, the charge ordering （CO） phase exists in the system, the transition temperature Tco= 275 K, and the system exhibits PM when T 〉 275 K. The system transforms from spin-disordering paramagnetism to spin-ordering antiferromagnetism in the charge ordering state with the temperature decreasing from 275 K to 230 K. The long-range antiferromagnetism forms and AFM/CO states coexist between 230 K and 5 K. There is a little ferromagnetic component in the AFM/CO background in a low temperature range. When x = 0.12, the CO phase in the system has almost melted completely. There is a little remnant of the CO phase below 150 K. The system exhibits paramagnetism when T 〉 150 K and transforms from paramagnetism to ferromagnetism when T〈 150 K.     

Microwave absorbing properties of La0.8Ba0.2MnO3 nano-particles

La0.8Ba0.2MnO3 nano-particles were synthesized by sol-gel process, and the crystal structure and morphology＇ were characterized by XRD and SEM, respectively. The complex permittivity and permeability were determined by microwave vector network analyzer in the frequency range of 2-18 GHz. The relationship between reflection coefficient and microwave frequency of La0.8Ba0.2 MnO3 was calculated based on measured data. The results show that the average diameter of La0.8Ba0.2MnO3 crystal powders is about 80 nm and the crystal structure is perovskite when being calcined at 800 ℃ for 2 h. The microwave absorbing peak is 13 dB at 6.7 GHz and the effective absorbing bandwidth above 10 dB reaches 1.8 GHz for the sample with the thickness of 2.6 mm. The microwave absorption can be attributed to both the dielectric loss and the magnetic loss from the loss tangents of the sample, but the former is greater than the latter.     

Enhancement of room-temperature magnetoresistance in La0.5Sm0.2Sr0.3MnO3/（Ag2O）x/2

La0.5Sm0.2Sr0.3MnO3/(Ag2O)x/2 (x = 0.00, 0.04, 0.08, 0.25, 0.30) samples were prepared by the solid-state reaction method, and their transport behaviors, transport mechanism, and magnetoresistance effect were studied through the measurement and fitting of ρ-T curves. The results show that the element Ag takes part in reaction when the doping amount is small. Ag is mainly distributed at the grain boundary of the host material and is in metallic state when the doping amount is relatively large; then the system becomes a two-phase composite. A small amount of Ag doping can apparently increase grain-boundary magnetoresistance induced by the spin-dependent scattering. The resistivity of the sample doped with 30 mol% Ag is one order of magnitude smaller than that of low-doped samples, and its magnetoresistance in the magnetic field of 0.5 T and at 300 K is strengthened apparently reaching 9.4%, which is connected not only with the improvement of the grain-boundary structure of the host material but also with the decrease of material resistivity.     

Effect of second introduced phase on magnetotransport properties of La2/3Sr1/3MnO3/0.33（CuO,ZnO, Al2O3） composites

The structure, magnetic and magnetotransport properties of La2/3Sr1/3MnO3（LSMO）/0.33（CuO, ZnO, Al2O3） composites were investigated to explore the role of second introduced phase. The microstructural analysis shows two kinds of grain boundaries： LSMO/LSMO and LSMO/second phase/LSMO. Two maximal resistivities appear in LSMO/0.33CuO and LSMO/0.33ZnO composites while the resistivity of LSMO/0.33Al2O3 decreases monotonically with increasing the temperature from 200 K to 400 K. Moreover, the temperature dependence of magnetoresistance（MR） of LSMO/0.33A1203 that decreases monotonically with increasing the temperature is different from that of LSMO/0.33CuO and LSMO/0.33ZnO. A developed two-channel model consisting of scattering model and tunneling model was proposed to fit the resistivity—temperature curves of these composites. The role of second introduced phase and the magnetotransport mechanism of these composites were elucidated.     

MAGNETIC PROPERTIES OF Nd_2(Fe_(1-x)M_x)_(14)B(M=C,Si)ALLOYS

The magnetic properties of Nd_2(Fe_(1-x)M_x)_(14)B(M=C and Si) compounds have been investi-gated.Substituting Fe by small amount of metalloid C and Si atoms,the compounds are intetragonal structure and have uniaxial anisotropy.The substitution of C for part of Fe de-creases the Curie temperature of the compounds and the intrinsic coercivity of bond samples atlow temperature.The replacement of Fe by Si makes the Curie temperature increase with amaximum at the vicinity of x=0.15.When the range of the content of Si is 0≤x≤0.10,thecoercivity distinctly increases at room temperature.from 62.7 kA/m at x=0 to138.7kA/m at x=0.06,where the residual magnetization has a maximum:in the mean timethe saturation magnetization decreases only by a small amount.     

稀土空位锰氧化物(La(1-x-y)Yy)2/3Ca1/3MnO3的结构和输运性质

用固相反应法制备了La(1-x)2/3Cai/3MnO3(V-LCMO)和(La(0.7-x)Y0.3)2/3Cai/3MnO3)(V-LYCMO)(x=0,0.02,0.04,0.08,0.10)系列La空位锰氧化物样品.X射线衍射(XRD)分析表明:所有的样品均为单相,具有正交对称性(Pnma).La(1-x)2/3Cai/3MnO3系统和(La(0.7-x)Y0.3)2/3Cai/3MnO3系统的晶格参数以及Mn-O键长和Mn-O-Mn键角随La空位浓度不同而改变,说明在室温系统中存在Jahn-Teller效应.对于V-LYCMO系统,其晶格参数、Mn-O键长和Mn-O-Mn键角都比V-LCMO相应的值更小,这可能与离子半径小的Y3 部分替代La3 导致更大的晶格畸变有关.V-LCMO系统随着空位浓度的增大,绝缘体-金属的转变温度TMI几乎不变.在x=0.04时MR值在温度TMI处达到最大值,约为220%(8T).而对V-LYCMO系统,其转变温度TMI约为50 K,在温度40～50 K左右最大的磁电阻值超过106%.认为很大的磁电阻效应与用离子半径小的Y部分替代离子半径大的La有关,它会破坏双交换作用,从而导致Jahn-Teller效应.     

Behavior of Mn2+ in perovskite manganites with nominal composition La0.6-xNdxSr0.1MnO3

The fact that there are Mn2+ at the A sites in the ABO3 perovskite phase of manganites with the nominal composition La0.6-xNdxSr0.1MnO3 showed by detailed experimental study and theoretical calculations.The magnetic moments of these Mn2+ are antiparallel to those of the Mn ions at the B sites.The content of the Mn2+ increases as the average ionic radius,(rA),of the ions at A sites decreases,resulting in the experimentally observed phenomenon that the content of the Mn3O4 phase in the manganites decreases with decreasing 〈rA〉.     

Spin-valve magnetoresistance in Co/Si/（Co/Cu/Co） multilayers

A series of Co/Si/（Co/Cu/Co） multilayers and Co/Si/Co sandwiches were prepared by high vacuum electron-beam evaporation. It was found that a Si spacer （≥0.9 nm） could greatly decrease the interlayer coupling in Co/Si/Co sandwiches and there was no magnetoresistance（MR） or spin-valve MR in them due to the high resistivity of Si spacer. While in Co/Si/（Co/Cu/Co） multilayers, we observed a spin-valve MR of about 0.5% through a nominal 2.7 nm Si spacer at room temperature. The spin-valve MR in Co/Si/（Co/Cu/Co） multilayers was attributed to the enhanced spin polarization of conduction electrons caused by the top Co/Cu/Co sandwich with GMR mechanism and high spin-dependent scattering at Co/Cu interface.     

颗粒尺寸对多晶La2／3Ca1／3Mn1-xCuxO3低场磁电阻的影响

采用溶胶-凝胶法制备了不同颗粒尺寸的La2/3Ca1/33Mn1-xCuxO3(x=0.04)系列试样。X射线衍射实验说明Cu掺杂和不同温度烧结没有改变晶体的结构。电阻-温度实验曲线表明，随颗粒尺寸的减少，半导体-金属转变温度（Tp）向低温方向移动。磁电阻曲线显示，随颗粒尺寸的减少，与颗粒晶界有关的磁电阻在25K恒温、0.4T低场下由25%增加到了51%。实验结果表明，在La2/3Ca1/3MnO3中少量Cu掺杂和小颗粒尺寸可以实质性地提高与颗粒晶界有关的低场磁电阻效应。     

油酸对化学共沉淀法制备La0.7（Ca0．53Sr0．47）0.3MnO3多晶的电阻温度系数的影响

研究了化学共沉淀法制备La0.7(Ca0.53Sr0.47)0.3MnO3多晶过程中添加油酸作分散剂的工艺,用DTG/TA、XRD和R-T(电阻-温度)系统测试了所制样品的性能.结果表明:添加油酸,共沉淀法制备La0.7(Ca0.53Sr0.47)0.3MnO3多晶比不添加的烧结温度低,也比同相反应法低.油酸的用量为0.1～O.2L/mol能明显提高La0.7(Ca0.53Sr0.47)0.3MnO3的电阻一温度转变点和电阻温度系数.     

La1/3Sr2/3Mn1-xFexO3(x=0,0.05)中电荷有序现象的超声研究

系统研究了La1／3Sr2／3Mn1-xFexO3(x=0，0．05)单相多晶样品在20--300K温区内的电荷输运性质和超声特性，结果表明，La1／3Sr2／3MnO3样品在235K存在明显的电荷有序现象，但是极少量的Fe取代Mn就会有效地抑制电荷有序现象的发生，伴随电荷有序现象的发生声速出现极大的软化，其相对变化超过5％，这表明La1／3Sr2／3Mn1-xFexO3中存在剧烈的电-声子相互作用，分析指出该电-声子耦合主要起源于Jahn-Teller效应。     

球形LiNi1/3Co1/3Mn1/3O2的合成及其电化学性能

以化学共沉淀法制备的球形Ni1/3Co1/3Mn1/3CO3为前驱体合成了球形LiNi1/3Co1/3Mn1/3O2,研究LiNi1/3Co1/3Mn1/3O2合成工艺对产物形貌的影响.结果表明直接以前驱体Ni1/3Co1/3Mn1/3CO3与Li2CO3反应合成的LiNi1/3Co1/3Mn1/3O2的一次颗粒较大,以前驱体分解后的氧化物与Li2CO3反应合成的LiNi1/3Co1/3Mn1/3O2的一次颗粒相对细小;合成的LiNi1/3Co1/3Mn1/3O2均为具有层状结构的纯相物质;球形正极材料LiNi1/3Co1/3Mn1/3O2充放电过程中存在一个材料活化的过程,在前10周期充放电时,电池容量处于增加的状态;在2.7～4.3 V的电压范围内1 C倍率下电池的放电比容量达到149 mA·h/g,0.2 C倍率下为158 mA·h/g,经50次循环后容量无衰减.     

Li(Mn1/3Ni1/3Co1/3)1-yMyO2(M=Al,Mg,Ti)正极材料的制备及性能

采用液相共沉淀合成锰镍钴氢氧化物前驱体, 在前驱体中掺入元素M(M=Al, Mg, Ti), 与锂结合生成Li(Mn1/3Ni1/3Co1/3)0.98M0.02O2材料, 结果表明掺杂可有效提高材料的循环性能. X射线衍射结果表明 随掺钛量增大(0≤y≤0.15), 晶格畸变增大, 半高宽变大, 晶粒粒径增大; 其中掺钛量y=0.1的材料电化学性能表现最好, 以20 mA/g电流充放电, 在2.5～4.6 V电压区首次放电容量可达215 mA·h/g.     

不同金属离子价态的前驱体制备球形LiNi1/3Mn1/3Co1/3O2的性能比较

利用共沉淀法和控制结晶氧化法在不同条件下分别制备出低价态球形Ni1/3Co1/3Mn1/3(OH)2和高价态球形Ni1/3Co1/3Mn1/3OOH前驱体,并分别和LiOH·H2O在不同温度烧结合成出球形锂离子正极材料Li(Ni1/3Co1/3Mn1/3)O2.XPS分析表明,制备的高价态球形Ni1/3Co1/3Mn1/3OOH前驱体其过渡金属Ni、Co和Mn的价态分别是2+,3+,4+,XRD分析表明,高价态球形Ni1/3Co1/3Mn1/3OOH前驱体比低价态球形Ni1/3Co1/3Mn1/3(OH)2前驱体具有较高的活性,能够在低温下合成出Li(Ni1/3Co1/3Mn1/3)O2,而且制备的产物结晶度高,阳离子混排程度小,具有规整的层状a-NaFeO2结构.充放电实验表明,由高价态球形Ni1/3Co1/3Mn1/3OOH前驱体制备的Li(Ni1/3Col/3Mn1/3)O2具有优良的充放电性能和循环性能.     

Surface modification of spherical LiNi1/3Co 1/3 Mn1/3O2 with Al2O3 using heterogeneous nucleation process

To improve the cycle stability at high voltage and high charge/discharge rate, spherical LiNi1/3Co1/3Mn1/3O2 was coated with Al2O3 by using heterogeneous nucleation process, and the physical and electrochemical properties were studied. The SEM images show that there is a uniform coating on the modified spherical LiNi1/3Co1/3Mn1/3O2. The electrochemical tests indicate that the properties of LiNi1/3Co1/3Mn1/3O2 coated with 0.5% aluminum oxide are the best. The initial capacities are 150 and 173 mA.h/g at the rate of I C in the voltage range of 2.7-4.3 V and 2.7-4.6 V, respectively, and the discharge capacities maintain about 99% and 85% after 30 cycles, respectively. While those of the bare LiNi1/3Co1/3Mn1/3O2 are only 90% and 75%, respectively. The CV tests of LiNi1/3Co1/3Mn1/3O2 show that Al203-coating can restrain the oxide-reduction peak currents fading during the charge/discharge course.     

Synthesis of LiNi1/3CO1/3Mn1/3O2 cathode material via oxalate precursor

Using oxalic acid and stoichiometrically mixed solution of NiCl2, CoCl2, and MnCl2 as starting materials, the triple oxalate precursor of nickel, cobalt, and manganese was synthesized by liquid-phase co-precipitation method. And then the LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery were prepared from the precursor and LiOH-H2O by solid-state reaction. The precursor and LiNi1/3Co1/3Mn1/3O2 were characterized by chemical analysis, XRD, EDX, SEM and TG-DTA. The results show that the composition of precursor is Ni1/3Co1/3Mn1/3C2O4·2H2O. The product LiNi1/3Co1/3Mn1/3O2, in which nickel, cobalt and manganese are uniformly distributed, is well crystallized with a-NaFeO2 layered structure. Sintering temperature has a remarkable influence on the electrochemical performance of obtained samples. LiNi1/3Co1/3Mn1/3O2 synthesized at 900 ℃ has the best electrochemical properties. At 0.1C rate, its first specific discharge capacity is 159.7 mA·h/g in the voltage range of 2.75-4.30 V and 196.9 mA·h/g in the voltage range of 2.75-4.50 V; at 2C rate, its specific discharge capacity is 121.8 mA·h/g and still 119.7 mA·h/g after 40 cycles. The capacity retention ratio is 98.27%.     

LiOH-Li_2CO_3低共熔混合锂盐体系合成LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2

利用低共熔组成的0.24LiCO3-0.76LiOH混合锂盐体系,与钴、镍、锰的球形氢氧化物按1.1:1混合,无需前期球磨,直接经二段控温程序制备出锂离子正极材料LiNi1/3Co1/3Mn1/3O2。X射线衍射分析表明合成的Li(Ni1/3Co1/3Mn1/3)O2结晶度高,具有规整的层状α-NaFeO2结构,扫描电镜显示产物颗粒均匀,振实密度高达2.89g·cm-3,显著高于用单一锂盐制备的同样产品(2.4g·cm-3)。充放电测试表明,材料具有良好的电性能,首次充放电容量为176和166mhA·g-1,循环50次后,材料的电性能没有明显的衰减。