The improvement of the high-rate charge/discharge performances of LiFePO4 cathode material by Sn doping

Nanocrystalline LiFePO₄ and LiFe_0.97Sn_0.03PO₄ cathode materials were synthesized by an inorganic-based sol–gel route. The physicochemical properties of samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and elemental mapping. The doping effect of Sn on the electrochemical performance of LiFePO₄ cathode material was extensively investigated. The results showed that the doping of tin was beneficial to refine the particle size, increase the electrical conductivity, and facilitate the lithium-ion diffusion, which contributed to the improvement of the electrochemical properties of LiFePO₄, especially the high-rate charge/discharge performance. At the low discharge rate of 0.5 C, the LiFe_0.97Sn_0.03PO₄ sample delivered a specific capacity of 158 mAh g⁻¹, as compared with 147 mAh g⁻¹ of the pristine LiFePO₄. At higher C-rate, the doping sample exhibited more excellent discharge performance. LiFe_0.97Sn_0.03PO₄ delivered specific capacity of 146 and 128 mAh g⁻¹ at 5 C and 10 C, respectively, in comparison with 119 and 107 mAh g⁻¹ for LiFePO₄. Moreover, the doping of Sn did not influence the cycle capability, even at 10 C.     

水热法制备树叶状LiFePO4/C复合正极材料

采用柠檬酸辅助水热法合成了高分散性树叶状LiFePO₄/C复合正极材料。利用X射线衍射、傅里叶红外光谱、扫描电镜、高分辨率透射电镜和选区电子衍射分析了材料的形貌结构。结果表明,柠檬酸对树叶状LiFePO₄/C复合材料的形成具有促进作用。该材料的最大暴露晶面为(010)晶面,且分散性较好。与颗粒状LiFePO₄/C材料相比,该材料呈现出更高的放电比容量和更好的倍率性能,在0.1C和5C倍率下,放电比容量分别为158和126mAh·g^-1,其原因是由于锂离子沿[010]方向的扩散距离缩短,从而使锂离子扩散系数显著增大。     

Oxalic acid-assisted preparation of LiFePO4/C cathode material for lithium-ion batteries

LiFePO₄/C composite is synthesized by oxalic acid-assisted rheological phase method. Fe₂O₃ and LiH₂PO₄ are chosen as the starting materials, sucrose as carbon sources, and oxalic acid as the additive. The crystalline structure and morphology of the products are characterized by X-ray diffraction and field emission scanning electron microscopy. The charge–discharge kinetics of LiFePO₄ electrode is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the introduction of appropriate amount of oxalic acid leads to smaller particle sizes, more homogeneous size distribution, and some Fe₂P produced in the final products, resulting in reduced polarization, impedance, and improved Li⁺ ion diffusion coefficient. The best cell performance is delivered by the sample with R = 1.5 (R of the molar ratio of oxalic acid to LiH₂PO₄). Its discharge capacity is 154 mAh g⁻¹ at 0.2 C rate and 120 mAh g⁻¹ at 5.0 C rate. At the same time, it exhibits an excellent cycling stability; no obvious decrease even after 1,000 cycles at 1.0 C rate.     

Synthesis and electrochemical characterization of LiFePO<Subscript>4</Subscript>/C-polypyrrole composite prepared by a simple chemical vapor deposition method

A LiFePO₄/C-polypyrrole (LiFePO₄/C-PPy) composite as a high-performance cathode material is successfully prepared through a simple chemical vapor deposition (CVD) method. According to the transmission electron microscope (TEM) analysis, the surface of the LiFePO₄/C is surrounded with PPy in the LiFePO₄/C-PPy composite. The as-prepared LiFePO₄/C-PPy material shows outstanding rate capability at 20°C and good cycle performance at 55°C in comparison with those of the bare LiFePO₄/C material against Li anode. After 700 cycles, the discharge capacity of LiFePO₄/C-PPy could still remain 110 mA h g⁻¹ with the retention of 82% at 5 C rate at 55°C. This could be ascribed to the fact that PPy coating on LiFePO₄/C could significantly improve the ionic conductivity of the LiFePO₄/C-PPy composite and could greatly reduce the electrode resistance. Furthermore, the PPy coating on LiFePO₄/C could effectively decrease the dissolution of Fe in the LiPF₆ electrolyte and subsequently suppress the reduction of Fe ions on anode.     

Structural and electrochemical characterization of LiFePO4/C prepared by a sol–gel route with long- and short-chain carbon sources

A fast and convenient sol–gel route was developed to synthesize LiFePO₄/C composite cathode material, and the sol–gel process can be finished in less than an hour. Polyethyleneglycol (PEG), d-fructose, 1-hexadecanol, and cinnamic acid were firstly introduced to non-aqueous sol–gel system as structure modifiers and carbon sources. The samples were characterized by X-ray powder diffraction, field emission scanning electron microscopy, and elemental analysis measurements. Electrochemical performances of LiFePO₄/C composite cathode materials were characterized by galvanostatic charge/discharge and AC impedance measurements. The material obtained using compound additives of PEG and d-fructose presented good electrochemical performance with a specific capacity of 157.7 mAh g⁻¹ at discharge rate 0.2 C, and the discharge capacity remained about 153.6 mAh g⁻¹ after 50 cycles. The results indicated that the improved electrochemical performance originated mainly from the microporous network structure, well crystalline particles, and the increased electronic conductivity by proper carbon coating (3.11%).     

高振实密度圆饼状LiFePO4/C的制备及电化学性能

以乙二醇为溶剂,采用溶剂热法一步合成圆饼状LiFePO₄,然后以葡萄糖为碳源与合成的LiFePO₄前躯体高温烧结得到碳包覆的LiFePO₄/C复合材料,其振实密度高达1.3 g·cm^-3。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对LiFePO₄/C复合材料进行了物相和形貌表征,研究结果表明制备得到的LiFePO₄呈圆饼状,且生成的圆饼是由单晶LiFePO₄纳米片堆积而成。此外,LiFePO₄颗粒表面碳层包覆均匀。将制备的LiFePO₄/C用作锂离子电池正极材料,电化学性能测试表明其具有高的充放电比容量(在0.1C时放电,其初始放电比容量为157.7 mAh·g^-1)与良好的循环性能(500次循环后容量保持率为82.4%)。     

高振实密度圆饼状LiFePO_4/C的制备及电化学性能

以乙二醇为溶剂,采用溶剂热法一步合成圆饼状LiFePO_4,然后以葡萄糖为碳源与合成的LiFePO_4前躯体高温烧结得到碳包覆的LiFePO_4/C复合材料,其振实密度高达1.3 g·cm~(-3)。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对LiFePO_4/C复合材料进行了物相和形貌表征,研究结果表明制备得到的LiFePO_4呈圆饼状,且生成的圆饼是由单晶LiFePO_4纳米片堆积而成。此外,LiFePO_4颗粒表面碳层包覆均匀。将制备的LiFePO_4/C用作锂离子电池正极材料,电化学性能测试表明其具有高的充放电比容量(在0.1C时放电,其初始放电比容量为157.7 mAh·g~(-1))与良好的循环性能(500次循环后容量保持率为82.4%)。     

Improved properties of polymer electrolyte by ionic liquid PP1.3TFSI for secondary lithium ion battery

A new kind of polymer electrolyte is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP1.3TFSI), polyethylene oxide (PEO), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). IR and X-ray diffraction results demonstrate that the addition of ionic liquid decreases the crystallization of PEO. Thermal and electrochemical properties have been tested for the solid polymer electrolytes, the addition of the room temperature molten salt PP1.3TFSI to the conventional P(EO)₂₀LiTFSI polymer electrolyte leads to the improvement of the thermal stability and the ionic conductivity (x = 1.27, 2.06 × 10⁻⁴ S cm⁻¹ at room temperature), and the reasonable lithium transference number is also obtained. The Li/LiFePO₄ cell using this polymer electrolyte shows promising reversible capacity, 120 mAh g⁻¹ at room temperature and 164 mAh g⁻¹ at 55 °C.     

Electrochemical study on lithium iron phosphate/hard carbon lithium-ion batteries

The electrochemical performances of lithium iron phosphate (LiFePO₄), hard carbon (HC) materials, and a full cell composed of these two materials were studied. Both positive and negative electrode materials and the full cell were characterized by scanning electron microscopy, transmission electron microscopy, charge–discharge tests, and alternating current (a.c.) impedance techniques. Experimental results show that the LiFePO₄/HC full cell exhibits a gradually decreased cell voltage, and it is capable of delivering a reversible discharge capacity of 122.1 mAh g⁻¹ at 0.2-C rate. At the higher rate of 10 C, the efficiency of the full cell remains almost unchanged from that of 0.2 C. Furthermore, the LiFePO₄/HC battery demonstrated a long life of 2,450 cycles with 40% of capacity change at a 10-C high rate. The internal resistance of the full cell is rather low as it is revealed from a.c. impedance measurements. These properties make the LiFePO₄/HC battery an attractive option for high rate and long cycle life power applications.     

鸟巢状分级结构LiFePO_4的合成及其电化学性能研究

采用溶剂热法,以乙二醇为溶剂,P123为软模板剂,制备了锂离子电池正极材料磷酸铁锂(LiFePO4),其振实密度约为1.2g·cm-3。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)和BET对样品的成分、晶型,形貌和孔结构进行了表征。结果表明:鸟巢状LiFePO4由单晶纳米片组成,具有开放的三维多孔分级结构。通过时间单因素实验探讨鸟巢状分级结构LiFePO4的生长机理,其生长过程可以概括为:成核——定向生长——团聚——定向生长。电化学性能测试结果表明材料在0.1C倍率下充放电时,其首次放电比容量达132.5 mAh·g-1。     

Synthesis and electrochemical properties of K-doped LiFePO4/C composite as cathode material for lithium-ion batteries

Li_1 − x K _x FePO₄/C (x = 0, 0.03, 0.05, and 0.07) composites were synthesized at 700 °C in an argon atmosphere by carbon thermal reduction method. Based on X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analysis, the composite was ultrafine sphere-like particles with 100–300 nm size, and the lattice structure of LiFePO₄ was not destroyed by K doping, while the lattice volume was enlarged. The electrochemical properties were investigated by four-point probe conductivity measurements, galvanostatic charge and discharge tests, cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the capacity performance at high rate and cyclic stability were improved by doping an appropriate amount of K, which might be ascribed to the fact that the doped K ion expands Li ion diffusion pathway. Among the doped materials, the Li_0.97K_0.03FePO₄/C samples exhibited the best electrochemical activity, with the initial discharge capacity of 153.7 mAh g⁻¹ at 0.1 C and the capacity retention rate of about 92% after 50 cycles at above 1 C, 11% higher than undoped sample. Remarkably, it still showed good cycle retention at a high current rate of 10 C.     

Synthesis and characterization of macroporous Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C composites as cathode materials for Li-ion batteries

The macroporous Li₃V₂(PO₄)₃/C composite was synthesized by oxalic acid-assisted carbon thermal reaction, and the common Li₃V₂(PO₄)₃/C composite was also prepared for comparison. These samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and electrochemical performance tests. Based on XRD and SEM results, the sample has monoclinic structure and macroporous morphology when oxalic acid is introduced. Electrochemical tests show that the macroporous Li₃V₂(PO₄)₃/C sample has a high initial discharge capacity (130 mAh g⁻¹ at 0.1 C) and a reversible discharge capacity of 124.9 mAh g⁻¹ over 20 cycles. Moreover, the discharge capacity of the sample is still 91.5 mAh g⁻¹, even at a high rate of 2 C, which is better than that of the sample with common morphology. The improvement in electrochemical performance should be attributed to its improved lithium ion diffusion coefficient for the macroporous morphology, which was verfied by cyclic voltammetry and electrochemical impedance spectroscopy.     

多元醇法合成具有不同长径比的棒状LiFePO4/C材料

以三价铁盐为铁源,采用多元醇还原法在低温下制备出了具有不同长径比的棒状LiFePO₄材料. 通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、循环伏安(CV)、交流阻抗谱(EIS)和恒电流充放电测试等手段分析了不同回流反应时间下制备出的前驱体和最终的LiFePO₄/C 样品. 结果表明：回流反应时间对LiFePO₄的形貌和特性有明显的影响. 通过把回流反应时间从4 h延长至16 h,材料的形貌由不规则的短棒状颗粒变为规则的长棒状颗粒,且棒的直径明显变小. 当回流反应时间为10 h 时,样品复合了多种形貌,有利于电子的传输,在低倍率下具有优秀的性能,0.1C放电比容量为163 mAh·g^-1;当回流反应时间为16 h 时,样品具有最大的长径比,有利于锂离子的扩散,在高倍率下具有良好的性能,1C、3C、5C、10C、20C倍率下放电比容量分别为135、125、118、110、98 mAh·g^-1,循环性能良好,几乎无衰减.     

Synthesis and electrochemical performances of Li4Ti4.95Zr0.05O12/C as anode material for lithium-ion batteries

Spinel Li₄Ti_5 − x Zr _x O₁₂/C (x = 0, 0.05) were prepared by a solution method. The structure and morphology of the as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The electrochemical performances including charge–discharge (0–2.5 V and 1–2.5 V), cyclic voltammetry, and ac impedance were also investigated. The results revealed that the Li₄Ti_4.95Zr_0.05O₁₂/C had a relatively smaller particle size and more regular morphology than that of Li₄Ti₅O₁₂/C. Zr⁴⁺ doping enhanced the ability of lithium-ion diffusion in the electrode. It delivered a discharge capacity 289.03 mAh g⁻¹ after 50 cycles for the Zr⁴⁺-doped Li₄Ti₅O₁₂/C while it decreased to 264.03 mAh g⁻¹ for the Li₄Ti₅O₁₂/C at the 0.2C discharge to 0 V. Zr⁴⁺ doping did not change the electrochemical process, instead enhanced the electronic conductivity and ionic conductivity. The reversible capacity and cycling performance were effectively improved especially when it was discharged to 0 V.     

Low-temperature behavior of Li3V2(PO4)3/C as cathode material for lithium ion batteries

The electrochemical performance of Li₃V₂(PO₄)₃/C was investigated at various low temperatures in the electrolyte 1.0 mol dm⁻³ LiPF₆/ethyl carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1:1:1). The stable specific discharge capacity is 125.4, 122.6, 119.3, 116.6, 111.4, and 105.7 mAh g⁻¹ at 26, 10, 0, −10, −20, and −30 °C, respectively, in the voltage range of 2.3–4.5 V at 0.2 C rate. When the temperature decreases from −30 to −40 °C, there is a rapid decline in the capacity from 105.7 to 69.5 mAh g⁻¹, implying that there is a nonlinear relationship between the performance and temperature. With temperature decreasing, R _ct (corresponding to charge transfer resistance) increases rapidly, D (the lithium ion diffusion coefficients) decreases sharply, and the performance of electrolyte degenerates obviously, illustrating that the low-temperature electrochemical performance of Li₃V₂(PO₄)₃/C is mainly limited by R _ct, D _Li, and electrolyte.     

采用复合锂源制备的LiFePO4/C材料及其碳含量优化

采用Li_2CO_3与Li OH·H_2O为复合锂源制备LiFePO_4/C材料,同时优化了材料中的碳含量。由于氢氧化锂的熔点低于碳酸锂,在同样的烧结温度下,采用复合锂源可以获得更佳的熔融状态,在高温合成过程中使锂离子具有更高的扩散性,能够更顺利地得到高纯度的LiFePO_4晶相。通过优化碳包覆量达到提高导电性与控制晶粒尺寸的目的,使材料晶相结构完整,纯度高,表现出优秀的加工性能与电化学性能。所制得的LiFePO_4/C材料放电克容量达到158.2 m Ah·g~(-1),在全电池中经过100 d存储后容量保持率仍然高于94.0%,具有优异的长期可靠性。     

Electrochemical properties of tetravalent Ti-doped spinel LiMn2O4

Ti-doped spinel LiMn₂O₄ is synthesized by solid-state reaction. The X-ray photoelectron spectroscopy and X-ray diffraction analysis indicate that the structure of the doped sample is Li( Mn^{3 +} Mn_{1 - x} ^{4 +} Ti_x^{4 +} )O₄ {\hbox{Li}}\left( {{\hbox{M}}{{\hbox{n}}^{3 + }}{\hbox{Mn}}_{1 - x\,}^{4 + }{\hbox{Ti}}_x^{4 + }} \right){\hbox{O}}{}_4 . The first principle-based calculation shows that the lattice energy increases as Ti doping content increases, which indicates that Ti doping reinforces the stability of the spinel structure. The galvanostatic charge–discharge results show that the doped sample LiMn_1.97Ti_0.03O₄ exhibits maximum discharge capacity of 135.7 mAh g⁻¹ (C/2 rate). Moreover, after 70 cycles, the capacity retention of LiMn_1.97Ti_0.03O₄ is 95.0% while the undoped sample LiMn₂O₄ shows only 84.6% retention under the same condition. Additionally, as charge–discharge rate increases to 12C, the doped sample delivers the capacity of 107 mAh g⁻¹, which is much higher than that of the undoped sample of only 82 mAh g⁻¹. The significantly enhanced capacity retention and rate capability are attributed to the more stable spinel structure, higher ion diffusion coefficient, and lower charge transfer resistance of the Ti-doped spinel.     

快离子导体LiTi2(PO4)3在LiNi0.8Co0.1Mn0.1O2正极材料表面的原位反应包覆及其电化学性能

通过原位反应法,利用富镍层状金属氧化物LiNi_0.8Co_0.1Mn_0.1O₂（LNCM811）正极材料表面残余的氢氧化锂和碳酸锂,与C₈H₂₀O₄Ti和（NH₄）H₂PO₄反应,在LNCM811表面原位生成快离子导体LiTi₂（PO₄）₃（LTP）包覆层。这种原位反应的包覆方法有利于移除LNCM811表面有害的残留物氢氧化锂和碳酸锂。而且,获得的LTP均匀包覆层不仅可以有效地抑制LNCM811表面和电解液的直接接触及其副反应,还可以确保充放电循环过程中LNCM811正极材料的快速Li⁺传导。因此,在LTP包覆层的多重作用下,LTP包覆的LNCM811正极材料具有优异的循环稳定性和倍率性能：在0.2C时,首次放电比容量高达200.6 mAh·g^-1,200圈后的可逆容量依然有155.7 mAh·g^-1;在2C和5C的高电流密度下,200圈后的可逆容量仍然有126.4和111.9 mAh·g^-1。     

球磨辅助高温固相法制备Li1.0Na0.2Ni0.13Co0.13Mn0.54O2正极材料及其性能

以乙酸盐(乙酸锂、乙酸钠、乙酸钴、乙酸镍、乙酸锰等)为原材料,采用球磨辅助高温固相法制备Li_(1.0)Na_(0.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_2正极材料。借助XRD、SEM等表征材料的结构和形貌,利用循环伏安、恒流充放电、交流阻抗等方法研究材料的电化学性能。结果表明,钠的掺杂导致颗粒表面光滑度降低,形成Na_(0.77)Mn O_(2.05)新相。0.05C活化过程中,掺钠样品和未掺钠样品首次放电比容量分别为258.4 m Ah·g~(-1)和215.8 m Ah·g~(-1),库伦效率分别为75.2%和72.8%;2C放电比容量分别为116.3 m Ah·g~(-1)和106.2 m Ah·g~(-1)。研究发现,掺钠可减小首次充放电过程的不可逆容量,提高容量保持率;改善倍率性能与容量恢复特性;降低SEI膜阻抗和电荷转移阻抗;掺钠后样品首次循环就可以基本完成Li_2Mn O_3组分向稳定结构的转化,而未掺杂的样品需要两次循环才能逐步完成该过程;XPS结果表明,掺钠样品中Ni~(2+)、Co~(3+)、Mn~(4+)所占比例明显提高,改善了样品的稳定性和电化学性能;循环200次后的XRD结果表明掺钠与未掺钠材料在脱嵌锂反应中的相变化过程基本一致,良好有序的层状结构遭到破坏是循环过程中容量衰减的主要原因。     

鸟巢状分级结构LiFePO4的合成及其电化学性能研究

采用溶剂热法,以乙二醇为溶剂,P₁₂₃为软模板剂,制备了锂离子电池正极材料磷酸铁锂(LiFePO₄),其振实密度约为1.2g·cm^-3。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)和BET对样品的成分、晶型,形貌和孔结构进行了表征。结果表明：鸟巢状LiFePO₄由单晶纳米片组成,具有开放的三维多孔分级结构。通过时间单因素实验探讨鸟巢状分级结构LiFePO₄的生长机理,其生长过程可以概括为：成核定向生长团聚定向生长。电化学性能测试结果表明材料在0.1C倍率下充放电时,其首次放电比容量达132.5mAh·g^-1。