Piezoelectric properties of the Pb(Sc1/2Nb1/2) O3-Pb(Mg1/3Nb2/3) O3-PbTiO3 ternary ceramic materials near the morphotropic phase boundary

Abstract

The physical and electrical properties of xPb(Sc_1/2Nb_1/2)O₃-yPb(Mg_1/3Nb_2/3)O₃-zPbTiO₃(PSMNT 100x/100y/100z) ternary ceramic materials near the morphotropic phase boundary (MPB) were investigated. The MPB follows on almost linear region between the PSMNT 58/00/42 and PSMNT 00/68/32 MPB compositions of the binary systems. The maximum piezoelectric constant, d ₃₃ = 680 pC/N, were found at PSMNT 29/33/38, where ε^T ₃₃/ε₀ = 3,800, and electromechanical coupling factors, (k _p = 70%, k₃₁ = 43%, and k ₃₃ = 76%) and T _c = 207°C were obtained. The maximum electromechanical coupling factors, (k _p = 72%, k ₃₁ = 45%, and k ₃₃ = 77%) were found at PSMNT 29/34/37, where ε^T ₃₃/ε₀ = 3,000, d ₃₃ = 640 pC/N, and T _c = 205°C were obtained. These values are better than those of PZT.     

Study of the Electrical Properties of Pb(Mg,Ni)1/3Nb2/3O3-PbTiO3 System Across the Morphotropic Phase Boundary

Phase transitional behavior and electrical properties of (1 – x)Pb(Mg,Ni)_1/3Nb_2/3O₃-xPbTiO₃ ceramics (PMNN-PT with Mg/Ni = 1:1, x = 0.20–0.40) across the morphotropic phase boundary (MPB) were examined. X-ray diffraction and dielectric measurement reveal that two phases, pseudocubic and tetragonal phases, coexist in the composition range x = 0.30–0.36. The maximum d ₃₃ (about 570 pC/N) was observed at the composition x = 0.32–0.34. Dielectric and ferroelectric properties exhibit abnormal high near the MPB. An unusual peak shoulder occurred in the dielectric measurement upon thermal cycling for poled samples. This phenomenon was considered to be associated with the macro to micro domain transition and depolarization.     

Piezoelectric properties and dielectric behavior of Bi1/2Na1/2[Ti1−x (Sb1/2Nb1/2) x ]O3 lead-free piezoelectric ceramics

New lead-free piezoelectric ceramics of ABO₃ perovskite type, Bi_1/2Na_1/2[Ti_1−x (Sb_1/2Nb_1/2) _x ]O₃, were synthesized by conventional solid state reaction. The effect of the replacement of complex ions of (Sb_1/2Nb_1/2)⁴⁺ in the B cationic site on structural and electrical properties was investigated. The XRD analysis showed that all samples exhibited a single phase of perovskite structure. Piezoelectric and dielectric measurement revealed that the substitution of (Sb_1/2Nb_1/2)⁴⁺ ions lead to an increase in piezoelectric constant(d ₃₃), electromechanical coupling factor(k _t), relative dielectric constant(ɛ _r),and loss tangent (tanδ), while excess of (Nb_1/2Sb_1/2)⁴⁺ ions results in a decrease in d ₃₃, k _t, ɛ _r, but an increase in tanδ. Temperature dependence of dielectric constant ɛ _r measurement indicated these compounds were relaxor ferroelectric. At low frequency and high temperature, dielectric constant increased sharply attributed to the superparaelectric clusters after (Sb_1/2Nb_1/2)⁴⁺ ions substitution.     

湿法球磨制备LiCo_(1/3)Mn_(1/3)Ni_(1/3)O_2材料及表征

以六水合硝酸镍、硝酸钴和二氧化锰为原料,以柠檬酸为分散剂和燃料,采用球磨工艺对原料进行混合,在950℃于空气气氛中保温10 h制备了层状结构的LiCo_(1/3)Mn_(1/3)Ni_(1/3)O_2正极材料.通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)和电化学性能测试手段对所制备材料的结构、形貌及电化学性能进行表征.结果表明:所合成的材料为单相的六方层状结构,颗粒大小均匀.在2.75～4.3 V电压区间,以0.1 C恒电流充放电,首次充/放电比容量为184.3/156.7mAh/g,充/放电效率为85%.0.5 C倍率下充放电,材料首次放电比容量为151.3 mAh/g,经过30次循环后比容量保持在1 50.8 mAh/g左右,循环性能优异.     

Li(Ni1/3Co1/3Mn1/3)1-ySnyO2材料的合成及性能研究

采用碳酸盐共沉淀法制备Li(Ni1/3Co1/3Mn1/3)1-ySnyO2(y=0,0.01,0.02,0.05,0.10)。通过XRD、SEM测试对其晶型结构、组织形貌进行了分析,交流阻抗法(AC)和充放电性能测试对其电化学性能进行了研究。实验表明,制备的样品均具有较好的层状结构,其中Li(Ni1/3Co1/3Mn1/3)0.98Sn0.02O2性能最佳,以0.5C循环充放电时,首次放电比容量达到173.31mAh/g,30次循环后,放电比容量为149.55mAh/g,容量保持率为86.29%。     

Li(Ni1/3Co1/3Mn1/3)O2正极材料的电化学性能

用共沉淀法制备出(Ni1/3Co1/3Mn1/3)(OH)2,与LiOH·H2O混合后,在900℃下焙烧12 h,得到锂离子电池正极材料Li(Ni1/3Co1/3Mn1/3)O2.在2.70～4.35 V,电流为40 mA/g时,循环性能稳定.当截止电压升高到4.60 V时,容量可达190 mAh/g.循环伏安实验表明,材料的结构在循环过程中保持稳定.     

锂离子电池正极材料Li(Ni1/3Co1/3Mn1/3)O2的Ag表面修饰

采用银镜反应法对Li(Ni1/3Co1/3Mn1/3)O2材料进行了Ag表面修饰.表面元素分布测试表明,Ag均匀分布在Li-(Ni1/3Co1/3Mn1/3)O2颗粒表面.未经表面修饰的材料在C/5、C/2和1 C倍率下放电容量分别为168、160、146 mAh/g,经过Ag表面修饰的材料在C/5、C/2和1 C倍率...     

Li（Ni（1/3）Co（1/3）Mn（1/3））（1-x）ZnxO2固溶体的XRD及XPS研究

采用共沉淀法制备了不同Zn掺杂量的Li（Ni1/3Co1/3Mn1/3）1-xZnxO2（x=0-0.08）固溶体,通过X射线衍射（XRD）和光电子能谱（XPS）分析,研究了不同Zn掺杂量对Li（Ni1/3Co1/3Mn1/3）1-xZnxO2固溶体晶体结构和过渡金属表面化学状态的影响。实验结果表明：当Zn掺杂量x小于0.006时,固溶体材料具有稳定的层状结构;微量Zn的掺杂能够增强晶体材料的整体键能。     

Dielectric and piezoelectric properties of La2O3 doped (Bi0.5Na0.5)0.92(Ba0.8Sr0.2)0.08 TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.92(Ba_0.8Sr_0.2)_0.08 TiO₃+x mol% La₂O₃(x = 0, 0.1, 0.3, 0.5, 0.8) were synthesized by conventional solid state reaction. The crystal structure of all compositions is mono-perovskite ascertained by XRD. The grain size decreased and diffuse phase transition behavior was more evident with the increasing amount of La₂O₃. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p showed the maximum value of 165 pC/N and 0.322 at 0.3% and 0.1% La₂O₃ addition, respectively, and rapidly decreased when La₂O₃ addition over 0.5%. The loss tangent tanδ linearly increased and the mechanical quality factor Q_m linearly decreased with the increasing amount of La₂O₃.     

Fabrication and operation limit of lead-free PTCR ceramics using BaTiO3–(Bi1/2Na1/2)TiO3 system

The electric properties of BaTiO₃–(Bi_1/2Na_1/2)TiO₃ (BT–BNT) solid solution ceramics were studied as a lead-free PTCR (positive temperature coefficient of resistivity) thermistor material usable over 130°C. For determining the maximum switching temperature T _s, the phase diagram of BT–BNT binary system was clarified. Two semiconductorization processes and their electric properties are described. The lanthanum(La)-doped BBNT ceramics sintered in air still showed dielectric behaviors, but the niobium(Nb)-doped ones had a low resistivity at room temperature, ρ _RT, on the order of 10³ Ωcm and showed a PTC behavior. Sintering under a low O₂ atmosphere produces BT–BNT ceramics with less than 10² Ωcm compared to those prepared in air. Our current research produced the BBNT ceramics with T _s values around 210°C by increasing the (Bi_1/2Na_1/2) content in the ceramics.     

Li(Ni1/3Co1/3Mn1/3)1-2xMgxAlxO2的合成与电化学性能

采用溶胶-凝胶法在900℃于空气中煅烧合成了层状复合掺杂型正极材料Li(Ni1/3Co1/3Mn1/3)1-2xMgxAlxO2(x=0,0.01,0.02,0.05).通过X-射线衍射(XRD)、扫描电镜(SEM)和电化学测试等研究了掺杂元素对Li(Ni1/3Co1/3Mn1/3)O2的结构和电化学性能的影响.结果表明,适量Mg、Al掺入Li(Ni1/3Co1/3Mn1/3)O2后降低了材料的阳离子混排程度,且晶胞参数随着掺杂量的增加而增加.合成材料颗粒分布比较均匀,平均粒径约为0.5 μm.在充放电倍率为0.1 C和电压范围为3.0～4.3 V的条件下,与未掺杂样品相比,Mg-Al复合掺杂的样品具有更好的电化学性能和容量保持率.当x=0.02时,复合掺杂样品的首次放电容量和库仑效率分别为153 mAh/g和93.0%,20个循环后容量保持率达93.4%.因此Mg-Al复合掺杂锂离子电池正极材料Li(Ni1/3Co1/3Mn1/3)1-2xMgxAlxO2是很有前景的.     

Mg-F共掺杂对Li1.1(Ni1/3Co1/3Mn1/3)O2电化学性能的影响

采用溶胶-凝胶法合成正极材料层状Li1.1[Ni1/3Co1/3Mn(1/3-x)Mgx]O2-yFy(0≤x≤0.04,0≤y≤0.04)。通过原子吸收光谱(AAS)、X射线衍射(XRD)、扫描电镜(SEM)和电化学测试等手段研究了掺杂元素对材料结构和电化学性能的影响。结果表明,镁氟掺杂后的样品具有单相的典型六方晶系结构,合成材料颗粒分布比较均匀。在充放电倍率为0.1 C和电压范围为3.0￣4.3 V的条件下,与未掺杂样品相比,Li1.1[Ni1/3Co1/3Mn(1/3-0.04)Mg0.04]O2-0.04F0.04具有较高的放电比容量和容量保持率。其首次放电比容量和库仑效率分别为158 mAh/g和91.3%,20个循环后容量保持率达92.1%。Li1.1[Ni1/3Co1/3Mn(1/3-0.04)Mg0.04]O2-0.04F0.04是一种有前景的锂离子电池新型正极材料。     

Li:(Ni+Co+Mn)对Lix Ni1/3Co1/3Mn1/3O2性能的影响

以共沉淀氢氧化物为前驱体制备了层状LixNi1/3Co1/3Mn1/3O2(x＞1)正极材料,并采用X射线衍射光谱法(XRD)、扫描电子显微镜(SEM)、充放电测试表征了其结构与性能.研究了不同的Li与M摩尔比对材料性能的影响.结果表明:随着Li与M摩尔比的升高,样品显示电化学性能提高,尤其是循环性能和倍率性能.当Li与M摩尔比大于1.20时放电容量开始下降.Li与M摩尔比为1.20的试样在截止电压为2.75～4.4 V范围里首次放电比容量达到160.5 mAh/g.     

石墨/Li(Ni1/3Co1/3Mn1/3)O2电池储存后的衰减机理

用充放电测试、电化学阻抗(EIS)、循环伏安(CV)、场发射扫描电镜(FE-SEM)和X射线能谱(EDX)等方法,研究了石墨/Li(Ni1/3Co1/3Mn1/3)O2电池高温储存后的性能变化.在55℃下储存后,Li(Ni1/3Co1/3Mn1/3)O2正极的容量衰减较大,同时阻抗增大,动力学性能下降.储存后的容量衰减...     

(La1-xTbx)2/3Sr1/3MnO3薄膜的巨磁电阻效应

利用脉冲激光沉积法制备了（La1-xTbx)2/3Sr1/3MnO3系列薄膜样品。在77－300K的温度范围内,对样品的微观结构、磁化强度、电阻率和巨磁电阻效应等物理性质进行了系统研究。随着Tb含量x的增大,铁磁－顺磁转变温度随之下降,在x=0. 33样品中,最大磁化场μ0H=1.2T时,观察到34％的巨磁电阻。本文对其机理进行了研究和讨论。     

Dielectric properties of Pb[(Mg1/3Nb2/3),Ti]O3 with Bi modification

Bi(Mg_2/3Nb_1/3)O₃ was partially substituted into a Pb(Mg_1/3Nb_2/3)O₃⋅PbTiO₃ perovskite system and resultant changes in the phase developments and dielectric properties were investigated. Two major structures of columbite and rutile, along with a small fraction of Mg₄Nb₂O₉ (α-Al₂O₃ structure), were developed in the B-site precursor system, whereas only a perovskite was observable after the addition of PbO and Bi₂O₃. The replacement of Bi for Pb resulted in a great reduction in the maximum dielectric constants as well as a substantial decrease in the dielectric maximum temperatures.     

镍钴锰三元材料-磷酸铁锂复合及性能研究

镍钴锰酸锂Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2与磷酸铁锂按照一定的质量比球磨混合制得复合材料,电化学测试结果表明,电池的循环性能随着Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2的增加而不断提升,当Li(Ni_(1/3)Co_(1/3)Mn_(1/3))O_2与LiFePO_4的质量比为7∶3时性能达到最佳,初始放电比容量为150.7 m Ah/g,循环60次后的放电比容量为147.6 m Ah/g,容量保持率高达97.96%;同时复合材料的平均工作电压为3.72 V(vs.Li+/Li),显著高于LiFePO_4的3.40 V(vs.Li+/Li)的放电电压平台,表现出更好的循环性能和更高的比容量。     

Effects of Al2O3 on the piezoelectric properties of Pb(Mn1/3Nb2/3)O3-PbZrO3-PbTiO3 ceramics

Piezoelectric properties of Al₂O₃-doped Pb(Mn_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ ceramics were investigated. The constituent phases, microstructure, electromechanical coupling factor, dielectric constant, piezoelectric charge and voltage constants were analyzed. Diffraction peaks for (002) and (200) planes were identified by X-ray diffractometer for all the specimens doped with Al₂O₃. The highest sintered density of 7.8 g/cm³ was obtained for 0.2 wt% Al₂O₃-doped specimen. Grain size increased by doping Al₂O₃ up to 0.3 wt%, and it decreased by more doping. Electromechanical coupling factor, dielectric constant, piezoelectric charge and voltage constants increased by doping Al₂O₃ up to 0.2 wt%, and it decreased by more doping. This might result from the formation of oxygen vacancies due to defects in O^{2 −} ion sites and the substitution of Al³⁺ ions.     

锂离子蓄电池LiNi1/3Co1/3Mn1/3O2正极材料的性能表征

采用共沉淀法制备了层状Li1.05Ni1/3Co1/3Mn1/3O2正极材料.以C为负极,在1 C、2.7～4.2 V下的初始放电比容量达145.5 mAh·g-1,循环100次后容量保持率为98.4%.并采用X光电子能谱(XPS)、循环伏安法(CV)和交流阻抗法(EIS)对层状LiN1/3Co1/3Mn1/3O2材料中的各元素氧化态分布和嵌/脱锂动力学过程进行了系统研究.XPS实验结果表明LiN1/3Co1/3Mn1/3O2中Co,Ni,Mn的主要氧化态分别为 3. 2, 4价.还有少量的Ni3 和Mn3 ,并从晶体场理论解释了其氧化态分布机制.而LiN1/3Co1/3Mn1/3O2的循环伏安曲线上主要存在3.95 V氧化峰和3.69 V还原峰,分别对应于Ni3 /Ni4 的氧化还原反应.     

Li与Ni+Co+Mn摩尔比对LixNi1/3Co1/3Mn1/3O2结构和性能的影响

采用氢氧化物共沉淀前驱体高温固相反应制备了层状LixNi1/3Co1/3Mn1/3O2(0.95≤x≤1.14)正极材料,应用ICP-OES、AAS对材料进行了成分分析,并采用X射线衍射光谱法(XRD)、晶格精修、扫描电子显微镜法(SEM)、差示扫描量热法(DSC)以及充放电测试表征了n(Li)∶n(Ni Co Mn)对材料结构和性能的影响。结果表明:x≥1.00时,随x值的增大,峰I003/I004的比值R、首次放电比容量及DSC峰值温度均呈现先增后减的趋势,并在x=1.05附近具有极大值;晶格精修表明阳离子混排率呈现先减后增的趋势,在x=1.08附近具有最小混排率。