Na+掺杂对LiNi1/3Co1/3Mn1/3O2结构和电化学性质的影响

采用高温固相法成功制备了不同Na+掺杂浓度的Li_1-xNa_xNi_1/3Co_1/3Mn_1/3O₂锂离子电池正极材料,探究了Na元素掺杂对层状氧化物正极材料结构以及电化学性能的影响。通过X射线粉末衍射仪和扫描电子显微镜表征了材料的结构和形貌,结果表明,当x≤0.3时,样品不会出现其它杂相;当x＞0.3时,样品中会出现NaNi_1/3Co_1/3Mn_1/3O₂的杂相。同时随着掺杂浓度的增加,样品的阳离子混排度逐渐增加。电化学性能结果表明,少量Na+的掺入可以提高LiNi_1/3Co_1/3Mn_1/3O₂在0.2C,0.5C下的放电比容量并增强其循环稳定性,但会损坏材料的倍率性能。     

Sn~(4+)掺杂对正极材料Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2性能的影响

采用共沉淀法合成掺杂的Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3-x)Sn_xO_2的正极材料,通过X射线光谱、扫描电镜、充放电测试等技术对Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3-x)SnxO_2材料的结构、形貌、电化学性能进行表征。结果表明,采用共沉淀法Sn4+能有效掺杂进正极材料Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2的体相结构。掺杂量x=0.04时,在2.8~4.2V、0.2C倍率下掺杂的正极材料首次充放电比容量为138.5mA·h/g,30次循环后的容量保持率为96.96%。掺杂Sn4+对Li_(1/3)Ni_(1/3)Co_(1/3) Mn_(1/3)O_2正极材料改性后,材料仍保持典型的α-NaFeO_2层状结构,且晶型良好,表明Sn4+掺杂能够有效改善材料的电化学性能。     

Transport Properties of Polycrystalline La2/3Ca1/3Mn1-xCuxO3

The infuence of Cu dopant (x) and sintering temperature(Ts) on the troansport propeties of La2/3Ca1/3Mn1-xCuxO3 series samples prepared by Sol-Gel technique was investigated.X-ray diffraction patterns show that all the samples with different Cu dopant and sintering temperatures (Ts) are of single phase without obvious latice distortion.Experimental results indicate that the insulator-metal transition temperature is diectly related to the sintering temperature and Cu dopant x.It is interesting to observe that a proper amount of Cu dompant can substantially improve magnetoresistance effects.     

锌对Li（Ni_（1/3）Co_（1/3）Mn_（1/3））O_2电极首次脱锂过程电化学性能的影响

共沉积法制备不同含锌量的锂离子电池正极材料Li（Ni1/3Co1/3Mn1/3）O2.采用交流阻抗谱分析该正极材料在首次脱锂过程中的电化学特性以及锌对电极阻抗和锂离子扩散系数的影响.电极阻抗图谱分析结果表明：3.7～4.4V为电极发生电化学反应的电位区间;锌减小了电极材料的SEI膜阻抗和电荷转移阻抗;少量固溶锌提高了锂离子在材料固相中的扩散能力.     

空位掺杂La(1-χ)2/3Ca1/3MnO3的结构及磁电阻效应

利用标准的固相反应法在1 200 ℃烧结了La(1-χ)2/3Ca1/3MnO3(χ=0,0.02,0.04,0.08,0.10)样品,冷却后,取出部分在1 350 ℃进行再烧结.利用X射线衍射(XRD)和扫描电镜(SEM)对其晶体结构及表面微观结构进行了研究.X射线衍射测量分析表明样品均为单相,单胞仍然具有正交对称性结构(空间群为Pnma),随着掺杂浓度的增加,晶格常数和晶胞体积逐渐减小.通过扫描电镜研究表明,样品随着掺杂浓度增加,晶粒逐渐增大,均匀性变好;样品在1 350 ℃再烧结条件下,平均粒度要大,空隙度变小.样品随着掺杂浓度的增加,电阻在逐渐增大,磁电阻在逐渐减小.     

La2O3掺杂对(Bi1/2Na1/2)0.94Ba0.06TiO3陶瓷性能与微结构的影响

采用传统陶瓷工艺方法制备了La2O3掺杂(Bi1/2Na1/2)0.94Ba0.06TiOa(BNBT6)无铅压电陶瓷,系统地研究了La2O3掺杂对该体系陶瓷介电、压电性能与微观结构的影响.结果表明:该体系具有很高的压电常数,是单一的钙钛矿结构,La2O3的添加对晶粒生长具有一定的抑制作用,线收缩率和相对密度增大.室温介电常数随着La2O3掺杂量的增加而增大.与不添加La2O3的陶瓷样品相比,添加少量La2O3可以使体系的弛豫特征更为明显.当掺杂量为0.1 wt%时,该体系陶瓷具有较好的综合性能:d3a=160 pC/N,kp=0.322.当掺杂量达到0.5 wt%以后,陶瓷的压电性能严重降低.     

Zn1/3Nb2/3含量对xPMnS-(1-x)PZN性能的影响

以xPMnS-（1-x）PZN 四元系压电陶瓷为研究对象,通过研究Zn1/3Nb2/3含量的变化对0.5PMnS-0.5aPZN材料结构与性能的影响,获得具有高压电活性的0.5PMnS-0.5aPZN陶瓷材料.结果表明,四方相结构的0.5PMnS-0.5aPZN材料压电活性优于三方相结构,性能最好的组成位于MPB（四方相边界）附近靠近四方相含量较高的区域,组成Zn1/3Nb2/3含量的变化影响了MPB的位置.     

Li-Ti共掺对Bi2(Zn1/3 Nb2/3)2O7陶瓷介电性能的影响

采用固相反应法制备(Bi1.975Li0.025)(Zn1/3Nh2/3-x/2Tix/2)2O7,陶瓷,研究了当Li 的替代量一定时,不同量的Ti4 替代Nb5 对BLXNT系介质材料介电性能的影响.研究结果表明:在取代的范围内仍然保持单斜焦绿石相;1MHz介电常数的温度系数由225.35×10-6/℃逐渐增加到416.48×10-6/℃;在-30℃≤T≤130℃,观察到BLZNT样品出现介电损耗弛豫现象,随着掺杂含量的增加,介电损耗弛豫峰向高温移动.     

Y3+取代Bi3+对Bi2(Zn1/3Nb2/3)2O7陶瓷烧结温度的影响

采用固相反应制备Bi2(Zn1/3Nb2/3)2O7微波陶瓷,并借助X射线、扫描电镜、LCR4284测试仪,研究Y3 取代Bi3 对Bi2(Zn1/3Nb2/3)2O7陶瓷烧结特性及介电性能的影响。研究结果表明:随着Y3 替代量的增加,晶粒尺寸减小,介电常数先减小后增大,烧结温度升高;适量的Y3 替代可以获得性能很好的BZN介质材料。     

Zn_(1/3)Nb_(2/3)含量对xPMnS-(1-x)PZN性能的影响

以xPMnS-(1-x)PZN四元系压电陶瓷为研究对象,通过研究Zn1/3Nb2/3含量的变化对0.5PMnS-0.5aPZN材料结构与性能的影响,获得具有高压电活性的0.5PMnS-0.5aPZN陶瓷材料。结果表明,四方相结构的0.5PMnS-0.5aPZN材料压电活性优于三方相结构,性能最好的组成位于MPB(四方相边界)附近靠近四方相含量较高的区域,组成Zn1/3Nb2/3含量的变化影响了MPB的位置。     

共沉淀法制备LaF3表面修饰LiNi1／3C01／3Mn1／302及性能研究

以LiNi1／3CO1／3Mn1／302为正极材料,采用共沉淀合成方法制备LaF3表面修饰LiNimCo1/3Mnm02正极材料,利用X射线衍射（XRD）、扫描电镜（SEM）和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明：经过LaF3表面修饰的LiNi1／3C01／3Mn1／302材料保持了LiNi1／3Co1／3Mn1/302层状结构,其中LaFs表面修饰量为0．59％时,在电压为2．75-4．50V范围内,以0．3mA／cm。电流密度下经恒电流充放电测试,其首次放电比容量为172．7mAh／g,经过50周充放电循环后放电比容量为163．5mAh／g,表现出较高的初始放电比容量和良好的抗过充电性能。     

Coating of LiNi1/3Mn1/3Co1/3O2 cathode materials with alumina by solid state reaction at room temperature

Alumina coated LiNi1/3Mn1/3Co1/3O2 particles were obtained by a simple method of solid state reaction at room temperature. The reaction mechanism of solid state reaction at room temperature was investigated. The structure and morphology of the coating materials were investigated by XRD, SEM and TEM. The electrochemical performances of uncoated and Al2O3-coated LiNi1/3Co1/3Mn1/3O2 cathode materials were studied within a voltage window of 3.00-4.35 V at current density of 30 mA/g. SEM, TEM and EDS analytical results indicate that the surface of LiNi1/3Mn1/3Co1/3O2 particles is coated with very fine Al2O3 composite, which leads to the improved cycle ability though a slight decrease in the first discharge capacity is observed. It is proposed that surface treatment by solid state reaction at room temperature is a simple and effective method to improve the cycle performance of LiNi1/3Co1/3Mn1/3O2 particles.     

共沉淀法制备LaF_3表面修饰LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2及性能研究

以LiNi1/3Co1/3Mn1/3O2为正极材料,采用共沉淀合成方法制备LaF3表面修饰LiNi1/3Co1/3Mn1/3O2正极材料,利用X射线衍射(XRD)、扫描电镜(SEM)和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明:经过LaF3表面修饰的LiNi1/3Co1/3Mn1/3O2材料保持了LiNi1/3Co1/3Mn1/3O2层状结构,其中LaF3表面修饰量为0.59%时,在电压为2.75～4.50V范围内,以0.3mA/cm2电流密度下经恒电流充放电测试,其首次放电比容量为172.7mAh/g,经过50周充放电循环后放电比容量为163.5mAh/g,表现出较高的初始放电比容量和良好的抗过充电性能。     

锂离子电池正极材料LiNi0.8Co0.2O2的合成及性能研究

以硝酸盐和淀粉为原料,采用溶胶-凝胶方法合成LiNi_0.8Co_0.2O₂锂离子电池正极材料,利用X射线衍射（XRD）、扫描电镜(SEM)和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明,合成材料为单一晶相的α-NaFeO₂型层状结构,颗粒小且分布均匀,在电压为2.75~4.50 V (vs. Li+/Li) 范围内,以0.2 mA/cm2电流密度下经恒电流充放电测试,其首次放电比容量为183.1 mAh/g,经过50周充放电循环后放电比容量为171.3 mAh/g,表现出较大的初始放电比容量和良好的循环性能。     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi0. 45 Co0. 10 Mn0. 4sO2 was synthesized from Li2CO3 and a triple oxide of nickel, cobalt and manganese at 950 ℃ in air. The structures and characteristics of LiNi0. 45 Co0.10 Mn0. 45 O2, LiCoO2 and LiMn2 O4 were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi0.4s Co0.10 Mn0. 45 O2 has a layered structure with hexagonal lattice. The commercial LicoO2 has sphere-like appearance and smooth surfaces, while the LiMn2 O4 and LiNi0.45 Co0. 10 Mn0. 45 O2 consist of cornered and uneven particles. LiNi0. 45 Co0.10 Mn0. 45 O2 has a large disLiMn2 O4 and LiCoO2, respectively. LiCoO2 and LiMn2 O4 have higher discharge voltage and better rate-capability than LiNi0. 45Co0.10 Mn0. 45 O2. All the three cathodes have excellent cycling performance with capacity retention of above 89.3 % at the 250th cycle. Batteries with LiMn2 O4 or LiNi0.45 Co0.10 Mn0. 45 O2 cathodes show better safety performance under abusive conditions than those with LiCoO2 cathodes.     

Synthesis and electrochemical characterization of LiNi0.78Co2Al0.02O2 cathode material in a novel co-precipitation method

LiNi0.78Co2Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.78Co2Al0.02O2 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry (3.0-4.2 V) illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared ma-terial was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles (0.2C,3.0-4.2 V, vs. Li /Li) with the capacity retention ratio of 97.7%.     

尖晶石型锰酸锂制备及其电化学性能

锰酸锂被认为是取代商品锂离子电池正极材料的LiCoO2候选材料.以二氧化锰、醋酸锰及氢氧化锂为原料,蒸馏水为分散剂,在空气气氛下进行分段烧结,控制烧结温度和时间,制备了锂离子电池正极材料锰酸锂.用X射线衍射仪,电子扫描电镜对产物的结构特征、微观表面形貌和恒流充放电性能进行了表征.结果表明:所制得正极材料为尖晶石型锰酸锂,结晶度高,无杂质相,材料颗粒的粒径均匀,首次放电比容量为117.3 mAh/g(0.5 mA/cm2,2.8~4.4 V,vs.Li+/Li);50次循环后,放电比容量为107.9 mAh/g,不可逆容量损失为9.4 mAh/g,比容量保持率为92.0%.得到了很好的综合电化学性能.     

Theoretic Diffraction Research on the Order-Disorder Effect of Transition Metal in Li(Ni1/3Co1/3Mn1/3)O2

Li(Ni_1/3Co_1/3Mn_1/3)O₂的(3b)位有序-无序效应研究

曹春晖^1,2, 张建¹, 杨传铮¹, 夏保佳¹

（1.上海微系统与信息技术研究所,上海 200050;

2.中国科学院大学, 北京100049）

创新点说明：

提出了有序度的概念,通过理论模拟了过渡金属在3b位不同有序度下的衍射情况。

研究目的：

借助理论衍射研究镍钴锰在三元材料中的占位情况,为实际得到的衍射数据分析起指导作用。

研究方法和结果：

借助Powercell程序模拟不同结构下的衍射情况。结果表明：对于Li(Ni1/3Co1/3Mn1/3)O2,基体衍射线的强度不随有序度而变化,有序度增加时,超点阵衍射线强度增加,但是即使对于有序度最大时,超点阵线的相对强度只有0.225%和0.043%。

结论：

3b位的有序无序很难通过常规的衍射实验观测到,必须提高X射线源的强度才可能观测到。

关键词：Li(Ni1/3Co1/3Mn1/3)O2, 有序-无序,超结构,衍射

     

Synthesis and electrochemical characterization of LiNi0.78Co0.2Al0.02O2 cathode material in a novel co-precipitation method

LiNi0.78 Co0.2 Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.rsCoo.2AI~0202 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry （3.0- 4. 2 V） illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared material was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles （0. 2C, 3.0 - 4. 2 V, vs. Li^＋/Li） with the capacity retention ratio of 97.7%.