Biomimetic Synthesis of Metal Ion‐Doped Hierarchical Crystals Using a Gel Matrix: Formation of Cobalt‐Doped LiMn2O4 with Improved Electrochemical Properties through a Cobalt‐Doped MnCO3 Precursor

We have synthesized spinel type cobalt‐doped LiMn₂O₄ (LiMn_2?yCo_yO₄, 0≤y≤0.367), a cathode material for a lithium‐ion battery, with hierarchical sponge structures via the cobalt‐doped MnCO₃ (Mn_1‐xCo_xCO₃, 0≤x≤0.204) formed in an agar gel matrix. Biomimetic crystal growth in the gel matrix facilitates the generation of both an homogeneous solid solution and the hierarchical structures under ambient condition. The controlled composition and the hierarchical structure of the cobalt‐doped MnCO₃ precursor played an important role in the formation of the cobalt‐doped LiMn₂O₄. The charge–discharge reversible stability of the resultant LiMn_1.947Co_0.053O₄ was improved to ca. 12 % loss of the discharge capacity after 100 cycles, while pure LiMn₂O₄ showed 24 % loss of the discharge capacity after 100 cycles. The parallel control of the hierarchical structure and the composition in the precursor material through a biomimetic approach, promises the development of functional materials under mild conditions.     

LiCoO2梯度包覆LiNi0.96Co0.04O2电极材料的电化学性能

镍钴酸锂(LiNi0.8Co0.2O2)与目前商业用锂离子电池正极材料钴酸锂(LiCoO2)相比,具有成本低、实际比容量高和环境友好等优势。但LiNi0.8Co0.2O2的充放循环性能还有待提高,对其进行阳离子掺杂或表面修饰可以改善其电化学性能,这方面的研究已经成为热点。Fey等人[1]用溶胶凝胶法制     

流变相法合成LiNi0.85Co0.15O2的结构与电化学性能

以一种新型的软化学方法——流变相法, 成功地合成了锂离子电池正极材料LiNi_0.85Co_0.15O₂. 将在600～850 ℃氧气氛下处理6 h后得到的LiNi_1－yCo_yO₂ (y＝0.10, 0.15, 0.20, 0.25), 进行X射线粉末衍射(XRD)与电化学测试. 测试结果表明, 流变相前体经过800 ℃烧结后合成的LiNi_0.85Co_0.15O₂晶胞参数a＝0.2866 nm, c＝1.4193 nm及晶胞体积V＝0.1010 nm³, 以0.1 C倍率在3.0～4.3 V (vs. Li^＋/Li)放电时, 首次放电容量可以达到198.2 mAh/g, 20次循环后, 其放电容量仍在174 mAh/g以上.     

Preparation of hierarchical LiNixCoyMnzO2 from solvothermal [NixCoyMnz](OH)2 via regulating the ratio of Ni,Co, and Mn and its excellent properties for lithium-ion battery cathode

The ternary-layered oxide (LiNi_xCo_yMn_zO₂) has become the most promising cathode material for lithium-ion batteries due to the advantages of higher discharge platform, better conductivity, and higher theoretical capacity. The [Ni_xCo_yMn_z](OH)₂ with different ratios of nickel, cobalt, and manganese (NCM) was prepared by solvothermal method, and then ternary cathode material LiNi_xCo_yMn_zO₂ was obtained by mixing lithium and calcining. In this paper, ternary cathode materials with different ratios of NCM were prepared by the solvothermal method. The structure and morphology of the materials were analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The effects of the ratio on the electrochemical properties of the materials were investigated by constant current charge and discharge test and electrochemical impedance spectroscopy test. The synthesized lithium-nickel-cobalt-manganese oxide belongs to the hexagonal system and has an α-NaFeO₂ layered structure, which is an R-3m space group. The NCM ternary cathode materials with different morphologies were obtained by changing the ratio of NCM. The sample with NCM ratio of 5:3:2 has a unique sheet-like spherical shape and has the best rate performance.     

ZrO_2包覆的层状富锂正极材料0.6Li[Li_(1/3)Mn_(2/3)]O_2·0.4LiNi_(5/12)Mn_(5/12)Co_(1/6)O_2的电化学性能

采用喷雾干燥法合成了富锂层状氧化物正极材料0.6Li[Li_(1/3)Mn_(2/3)]O2·0.4LiNi_(5/12)Mn_(5/12)Co_(1/6)O_2(简称LNMCO),并使用Zr(CH3COO)4进行ZrO_2的包覆改性。TEM测试结果显示纳米级的ZrO_2颗粒附着在LNMCO的表面。包覆质量分数为1.5%的ZrO_2包覆样品的首圈库伦效率和放电比容量有着显著提升,在室温下其首圈库伦效率和放电比容量(电流密度:20 m A·g-1,电压:2.0~4.8 V)分别为87.2%,279.3 m Ah·g-1,而原样则为75.1%,224.1 m Ah·g-1,循环100圈之后,1.5%ZrO_2包覆样品的放电比容量为248.3 m Ah·g-1,容量保持率为88.9%,高于原样的195.9 m Ah·g-1和87.4%。     

ZrO2包覆的层状富锂正极材料0.6Li[Li1/3Mn2/3]O2·0.4LiNi5/12Mn5/12Co1/6O2的电化学性能

采用喷雾干燥法合成了富锂层状氧化物正极材料0.6Li[Li_1/3Mn_2/3]O₂·0.4LiNi_5/12Mn_5/12Co_1/6O₂(简称LNMCO),并使用Zr (CH₃COO)₄进行ZrO₂的包覆改性。TEM测试结果显示纳米级的ZrO₂颗粒附着在LNMCO的表面。包覆质量分数为1.5%的ZrO₂包覆样品的首圈库伦效率和放电比容量有着显著提升,在室温下其首圈库伦效率和放电比容量(电流密度：20 mA·g^-1,电压：2.0~4.8 V)分别为87.2%,279.3 mAh·g^-1,而原样则为75.1%,224.1 mAh·g^-1,循环100圈之后,1.5% ZrO₂包覆样品的放电比容量为248.3 mAh·g^-1,容量保持率为88.9%,高于原样的195.9 mAh·g^-1和87.4%。     

锂离子电池正极材料LiNi0.5Co0.4Al0.1O2的合成与性能

采用高温固相法制备了锂离子电池正极材料LiNi_0.5Co_0.4Al_0.1O₂。采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)对材料的结构及表观形貌进行分析。通过恒电流充放电以及循环伏安法进行了电化学性能测试。测试结果表明,充放电电压在3~4.5 V之间,在0.2C倍率下首次放电比容量达到159.9 mAh·g^-1,经50次循环充放电后放电容量为142.6 mAh·g^-1,表现出良好的电化学性能。     

锂离子电池正极材料LiNi0.5Co0.4Al0.1O2的合成与性能

采用高温固相法制备了锂离子电池正极材料LiNi_0.5Co_0.4Al_0.1O₂,采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)对材料的结构及表观形貌进行分析。通过恒电流充放电以及循环伏安法进行了电化学性能测试。测试结果表明,充放电电压在3~4.5V之间,在0.2C倍率下首次放电比容量达到159.9mAh·g^-1,经50次循环充放电后放电容量为142.6mAh·g^-1,表现出良好的电化学性能。     

Effects of Zn, Al and Ti substitution on the electrochemical properties of LiNiO2 synthesized by the combustion method

LiNi_{1 ? y} Ti _y O₂ (0.000 ≤ y ≤ 0.100) and LiNi_0.990M_0.010O2 (M = Zn, Al, and Ti) were synthesized by the combustion method. The effects of Zn, Al and Ti substitution for Ni of LiNiO₂ on the electrochemical properties of LiNiO₂ were investigated. LiNi_0.995Ti_0.005O₂ has the largest first discharge capacity (188.1 mA h/g) among the Ti-substituted samples. LiNi_0.990Ti_0.010O₂ has a relatively large first discharge capacity (185.5 mA h/g) and a relatively good cycling performance. Among LiNi_0.990M_0.010O₂ (M = Ni, Zn, Al, and Ti), LiNiO₂ has the largest discharge capacities at a rate of 0.1 C from n = 1(189.3 mA h/g) to n = 10. LiNi_0.990Al_0.010O₂ has the lowest discharge capacities from n = 1 to n = 10, but it has the best cycling performance. LiNi_0.990Zn_0.010O₂ showed poor crystallinity, LiNi_0.990Ti_0.010O₂ showed high cation mixing, and LiNi_0.990Al_0.010O₂ had good crystallinity and showed low cation mixing. Fewer occurrence of phase transitions and the least change of the ?dx/|dV| vs. voltage curve at the second cycle from the curve at the first cycle of LiNi_0.990Al_0.010O₂ suggest that Al substitution stabilizes the structure and leads to a good cycling performance.     

5 V正极材料LiNi0.5Mn1.5O4的自蔓延燃烧合成及性能

通过自蔓延燃烧方法合成了性能优良的高电位5V锂离子电池正极材料LiNi0.5Mn1.5O4,利用傅立叶红外光谱(FTIR)、热分析(DSC/TG)、X射线衍射(XRD)、透射电镜(TEM)等方法对前驱物及样品的结构和物化性质等进行了分析和表征,考察了材料的电化学性能。结果表明,所制备样品具有单一的尖晶石相结构,具有4.7V充放电平台;在3.5V到5.2V之间进行充放电性能测试具有131mAh·g-1以上的可逆容量;在2C倍率下循环100次后的容量保持率为96%以上。     

BiFeO<Subscript>3</Subscript>-coated spinel LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> with improved electrochemical performance as cathode materials for lithium-ion batteries

Spinel LiNi_0.5Mn_1.5O₄ cathode material is a promising candidate for next-generation rechargeable lithium-ion batteries. In this work, BiFeO₃-coated LiNi_0.5Mn_1.5O₄ materials were prepared via a wet chemical method and the structure, morphology, and electrochemical performance of the materials were studied. The coating of BiFeO₃ has no significant impact on the crystal structure of LiNi_0.5Mn_1.5O₄. All BiFeO₃-coated LiNi_0.5Mn_1.5O₄ materials exhibit cubic spinel structure with space group of Fd3m. Thin BiFeO₃ layers were successfully coated on the surface of LiNi_0.5Mn_1.5O₄ particles. The coating of 1.0 wt% BiFeO₃ on the surface of LiNi_0.5Mn_1.5O₄ exhibits a considerable enhancement in specific capacity, cyclic stability, and rate performance. The initial discharge capacity of 118.5 mAh g^?1 is obtained for 1.0 wt% BiFeO₃-coated LiNi_0.5Mn_1.5O₄ with very high capacity retention of 89.11% at 0.1 C after 100 cycles. Meanwhile, 1.0 wt% BiFeO₃-coated LiNi_0.5Mn_1.5O₄ electrode shows excellent rate performance with discharge capacities of 117.5, 110.2, 85.8, and 74.8 mAh g^?1 at 1, 2, 5, and 10 C, respectively, which is higher than that of LiNi_0.5Mn_1.5O₄ (97.3, 90, 77.5, and 60.9 mAh g^?1, respectively). The surface coating of BiFeO₃ effectively decreases charge transfer resistance and inhibits side reactions between active materials and electrolyte and thus induces the improved electrochemical performance of LiNi_0.5Mn_1.5O₄ materials.     

Synthesis and electrochemical properties of dual doped spinels LiNi_xAl_yMn_(2-x-y)O_4 via facile novel chelated sol–gel method as possible cathode material for lithium rechargeable batteries

LiMn_2O_4 and LiNi_xAlyMn_(2-x-y)O_4(x= 0.50;y = 0.05-0.50) powders have been synthesized via facile solgel method using Behenic acid as active cheiating agent.The synthesized samples are subjected to physical characterizations such as thermo gravimetric analysis(TG/DTA),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),field-emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM) and electrochemical studies viz.,galvanostatic cycling properties,electrochemical impedance spectroscopy(EIS) and differential capacity curves(dQ/dE).Finger print XRD patterns of LiMn_2O_4 and LiNi_xAl_yMn_(2-x-y)O_4 fortify the high degree of crystallinity with better phase purity.FESEM images of the undoped pristine spinel illustrate uniform spherical grains surface morphology with an average particle size of 0.5 μm while Ni doped particles depict the spherical grains growth(50nm) with ice-cube surface morphology.TEM images of the spinel LiMn_2O_4 shows the uniform spherical morphology with particle size of(100 nm) while low level of Al-doping spinel(LiNio.5Alo.05Mn1.45O4) displaying cloudy particles with agglomerated particles of(50nm).The LiMn_2O_4 samples calcined at 850℃ deliver the discharge capacity of 130 mAh/g in the first cycle corresponds to 94%coiumbic efficiency with capacity fade of 1.5 mAh/g/cycle over the investigated 10 cycles.Among all four dopant compositions investigated,LiNi_(0.5)Al_(0.05)Mn_(1.45)O_4 delivers the maximum discharge capacity of 126 mAh/g during the first cycle and shows the stable cycling performance with low capacity fade of 1 mAh/g/cycle(capacity retention of 92%) over the investigated 10 cycles.Electrochemical impedance studies of spinel LiMn_2O_4 and LiNi_(0.5)Al_(0.05)Mn_(1.45)O_4 depict the high and low real polarization of 1562 and 1100 Ω.     

凝胶燃烧法合成5V级正极材料LiNi_(0.5)Mn_(1.5)O_4及其高倍率放电性能

采用聚乙烯吡咯烷酮(PVP)作为络合剂和燃料以凝胶燃烧法制备了具有优异高倍率放电性能的亚微米LiNi0.5Mn1.5O4材料.用热重/差热分析(TG/DTA)研究了凝胶的燃烧过程,用X射线衍射(XRD)、扫描电镜(SEM)和循环伏安(CV)研究了LiNi0.5Mn1.5O4材料的结构和形貌.结果表明材料为结晶良好的纯尖晶石相结构,由5μm左右的二次颗粒组成,颗粒大小分布均匀,一次晶粒发育良好,粒径在500nm左右.充放电测试表明材料的倍率性能和循环性能十分优异.在3.5至4.9V进行充放电测试,0.5C、1C、4C、8C和10C倍率下放电容量分别为131.9、127.6、123.4、118.4和113.7mAh·g-1.在10C大倍率放电条件下循环100、500和1000次的容量保持率分别为91.4%、80.9%和73.5%.     

Li3PO4‐Coated LiNi0.5Mn1.5O4: A Stable High‐Voltage Cathode Material for Lithium‐Ion Batteries

LiNi_0.5Mn_1.5O₄ is regarded as a promising cathode material to increase the energy density of lithium‐ion batteries due to the high discharge voltage (ca. 4.7 V). However, the interface between the LiNi_0.5Mn_1.5O₄ cathode and the electrolyte is a great concern because of the decomposition of the electrolyte on the cathode surface at high operational potentials. To build a stable and functional protecting layer of Li₃PO₄ on LiNi_0.5Mn_1.5O₄ to avoid direct contact between the active materials and the electrolyte is the emphasis of this study. Li₃PO₄‐coated LiNi_0.5Mn_1.5O₄ is prepared by a solid‐state reaction and noncoated LiNi_0.5Mn_1.5O₄ is prepared by the same method as a control. The materials are fully characterized by XRD, FT‐IR, and high‐resolution TEM. TEM shows that the Li₃PO₄ layer (<6 nm) is successfully coated on the LiNi_0.5Mn_1.5O₄ primary particles. XRD and FT‐IR reveal that the synthesized Li₃PO₄‐coated LiNi_0.5Mn_1.5O₄ has a cubic spinel structure with a space group of Fd$\bar 3$ m, whereas noncoated LiNi_0.5Mn_1.5O₄ shows a cubic spinel structure with a space group of P4₃32. The electrochemical performance of the prepared materials is characterized in half and full cells. Li₃PO₄‐coated LiNi_0.5Mn_1.5O₄ shows dramatically enhanced cycling performance compared with noncoated LiNi_0.5Mn_1.5O₄.     

原位包覆导电聚吡咯的Li1.26Fe0.22Mn0.52O2富锂铁锰基正极材料的制备及电化学性能的提高

采用化学氧化聚合的方法成功合成了导电聚吡咯(PPy)包覆的纳米尺寸Li_1.26Fe_0.22Mn_0.52O₂(LFMO)正极材料。通过X射线衍射(XRD)检测样品的晶体结构,并通过扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察材料形态和微观结构。元素映射和傅里叶变换红外光谱结果表明,PPy导电网络存在于复合材料中,并且PPy均匀分布在LFMO颗粒上。通过恒流充放电测试和电化学阻抗谱(EIS)分析研究了所有样品的电化学性能,结果表明表面上的PPy显著降低了LFMO的电荷转移电阻。包覆PPy质量分数为2%的LFMO-2%PPy表现出极好的倍率性能和良好的循环稳定性,其在1C倍率下首次放电容量为206 mAh·g^-1,首圈库仑效率为87%,在1C和2C分别循环50圈后,其容量分别稳定在131和139 mAh·g^-1。     

Electrochemical characterization of polypyrrole–LiNi<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>O<Subscript>2</Subscript> composite cathode material for aqueous rechargeable lithium batteries

A series of polypyrrole (PPy)–LiNi_1/3Mn_1/3Co_1/3O₂ composite electrodes are formed by physical mixing of polypyrrole with LiNi_1/3Mn_1/3Co_1/3O₂ cathode material. LiNi_1/3Mn_1/3Co_1/3O₂ is synthesized by reaction under autogenic pressure at elevated temperature method. Highly resolved splitting of 006/102 and 108/110 peaks in the XRD pattern provide an evidence to well-ordered layered structure of the compound. The ratios of the intensities of 003 and 104 peaks are found to be >1, which indicate no pronounced mixing of the cation. Cyclic voltammetry and AC impedance studies revealed that the addition of polypyrrole significantly decreases the charge-transfer resistance of LiNi_1/3Mn_1/3Co_1/3O₂ electrodes. The electrochemical reactivity of PPy–LiNi_1/3Mn_1/3Co_1/3O₂ composite electrode is examined during lithium ion insertion and de-insertion by galvanostatic charge–discharge testing; 10 wt.% PPy–LiNi_1/3Mn_1/3Co_1/3O₂ composite electrode exhibits better electrochemical performance by increasing the reaction reversibility and capacity compared to that of the pristine LiNi_1/3Mn_1/3Co_1/3O₂ electrode. The cell with 10 wt.% PPy added cathode shows significant improvement in the electrochemical performance compared with that having pristine cathode. The capacity remains about 70% of the initial value after 50 cycles while for cell with pristine cathode only about 28% of initial capacity remains after 40 cycles.     

Cycling performance of LiNi<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>Mn<Subscript>2 − <Emphasis Type="Italic">y</Emphasis></Subscript>O<Subscript>4</Subscript> prepared by the solid-state reaction

In order to improve the cycling performance of LiMn₂O₄, a part of Mn in LiMn₂O₄ was replaced by Ni. LiNi _y Mn_{2 − y} O₄ (y = 0.02, 0.05, 0.10, 0.15, and 0.20) were synthesized by preheating a mixture of LiOH, MnO₂ (CMD), and NiO at 400°C for 10 h and then calcining at 850°C for 48 h in air with intermediate grinding. The voltage vs. discharge capacity curves at a current density of 300 μA/cm² between 3.5 and 4.3 V showed two plateaus, but the plateaus became unclear as the value of y increased. The sample with y = 0.02 had the largest first discharge capacity of 118.1 mA h/g. The LiNi_0.10Mn_1.90O₄ sample had a relatively large first discharge capacity of 95.0 mA h/g and snowed an excellent cycling performance.     

Comparison of structure and electrochemical properties for 5 V LiNi0.5Mn1.5O4 and LiNi0.4Cr0.2Mn1.4O4 cathode materials

Spinel LiNi_0.5Mn_1.5O₄ and LiMn_1.4Cr_0.2Ni_0.4O₄ cathode materials have been successfully synthesized by the sol–gel method using citric acid as a chelating agent. The structure and electrochemical performance of these as-prepared powders have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and the galvanostatic charge–discharge test in detail. XRD results show that there is a small Li _y Ni_1-y O impurity peak placed close to the (4 0 0) line of the spinel LiNi_0.5Mn_1.5O₄, and LiMn_1.4Cr_0.2Ni_0.4O₄ has high phase purity, and the powders are well crystallized. SEM indicates that LiMn_1.4Cr_0.2Ni_0.4O₄ has a slightly smaller particle size and a more regular morphological structure with narrow size distribution than those of LiNi_0.5Mn_1.5O₄. Galvanostatic charge–discharge testing indicates that the initial discharge capacities of LiMn_1.4Cr_0.2Ni_0.4O₄ and LiNi_0.5Mn_1.5O₄ cycled at 0.15 C are 129.6 and 130.2 mAh g⁻¹, respectively, and the capacity losses compared to the initial value, after 50 cycles, are 2.09% and 5.68%, respectively. LiMn_1.4Cr_0.2Ni_0.4O₄ cathode has a higher electrode coulombic efficiency than that of the LiNi_0.5Mn_1.5O₄ cathode, implying that Ni and Cr dual substitution is beneficial to the reversible intercalation and de-intercalation of Li⁺.     

两步固相法合成LiFe1-xNbxPO4/C复合正极材料及其电化学性能

以LiH₂PO₄和FeC₂O₄·2H₂O为原料, 采用分步添加聚乙烯醇和葡萄糖两种碳源的方式, 通过两步固相法合成了碳包覆的LiFePO₄材料. 700℃下处理的产物结晶良好, 颗粒分布均匀, 具有良好的电化学性能, 0.1C和1C倍率下放电比容量分别为157.3 和138.3 mAh·g^-1. 在碳包覆的基础上, 选择高价Nb⁵⁺进行铁位取代获得了复合改性的LiFe_1-xNb_xPO₄/C (x=0.005, 0.01, 0.015, 0.02)材料. 优化的LiFe_0.99Nb_0.01PO₄/C 材料显示了良好的倍率充放电能力和循环稳定性, 0.1C和5C倍率下放电比容量分别为160.5 和136.0 mAh·g^-1, 5C倍率下循环50 次后比容量保持在134.8 mAh·g^-1, 容量保持率为99.1%. 循环伏安测试结果表明, Nb⁵⁺离子掺杂减少了锂离子扩散阻力, 降低了充放电过程中的动力学限制, 提高了电极的可逆性.     

Investigation on graphitic carbon foams – LiNiyPO4 (y = 0.8–1.0) composites

Graphitic carbon foams coated with olivine-structured lithium nickel phosphate (LiNi_yPO₄) (y = 0.8–1.0) as possible cathode materials for 5 V applications are investigated. The composites are prepared by soaking the foams into solutions containing lithium, nickel ions and phosphates, treated in flowing air then in flowing nitrogen. The structural, morphological and electrochemical properties are strongly dependent upon the Ni-content. The X-ray diffractograms, performed on powders prepared under very similar conditions, showed the formation of LiNiPO₄ phase with Li₄P₂O₇ and Li₂Ni₃(P₂O₇)₂. The morphological investigation revealed a dramatic change of the layer by decreasing the Ni-content. The voltammetric curves show values of the mean peak maxima in the anodic region between 5.1 and 5.2 V and in the cathodic region between 4.88 for (y = 1.0) and ∼5.18 V for (y = 0.9 and 0.8) respectively. The specific capacity of the composites (at the first cycle, a discharge rate of C/10 and room temperature) increases by decreasing the nickel content into the cathode material reaching a maximum of 122 mAh g⁻¹ for y = 0.8.