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1.
采用3种含铝化合物(AlPO_4、Al_2O_3和AlF_3)对富锂锰基材料Li_(1.2)[Mn_(0.54)Co_(0.13)Ni_(0.13)] O_2进行表面包覆改性,研究了表面包覆对富锂锰基材料的首圈库伦效率和循环性能的影响。结果表明与原始的Li_(1.2)[Mn_(0.54)Co_(0.13)Ni_(0.13)] O_2的库伦效率(71.0%)相比经过AlPO_4表面包覆改性的Li_(1.2)[Mn_(0.54)Co_(0.13)Ni_(0.13)] O_2库伦效率最高达到了86.3%。经过50圈循环后相比于原始的Li_(1.2)[Mn_(0.54)Co_(0.13)Ni_(0.13)] O_2的容量保持率(58.9%),由Al_2O_3表面包覆改性的容量保持率提高最大,为96.1%。经过AlF_3表面包覆改性的Li_(1.2)[Mn_(0.54)Co_(0.13)Ni_(0.13)] O_2综合性能最佳,其首圈库伦效率达到了81.1%,容量保持率达到了92.4%。  相似文献   

2.
采用典型的湿化学法制备了2%(wt)FeF_3包覆的Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2材料,并且通过XRD,SEM及TEM等技术来分析材料的微观结构和形貌。结果显示,在Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2材料表面包覆着一层5~20 nm厚的FeF_3薄膜。通过电化学性能测试发现,2%(wt)FeF_3@Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2样品的首次库伦效率更高,高倍率性能更佳,循环性能更加稳定。在0.5C倍率下循环100次后,其容量保持率仍有94.2%,放电比容量为190.6 m Ah×g~(-1)。同时电化学阻抗结果表明,FeF_3包覆层能够抑制Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2和电解液之间的副反应,稳定材料的层状结构。  相似文献   

3.
采用钛酸四丁酯[Ti(OC_4H_9)_4]水解和900℃高温烧结工艺制得不同Ti~(4+)含量掺杂下的Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]_(1-x)Ti_xO_2正极材料。采用XRD、SEM等表征方法对Ti~(4+)掺杂前后的Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2颗粒的微观结构、表面形貌进行分析研究,发现掺杂前后材料的结构并未明显变化。电化学测试结果表明,虽然Ti~(4+)表现为非电化学活性,使得掺杂有Ti~(4+)的正极材料其首次充放电比容量有所降低,但是在高倍率性能及循环性能测试中,Ti~(4+)掺杂改性效果表现明显。其中当Ti~(4+)掺杂量为x=0.02时,其倍率性能及循环性能最佳。在5C高倍率下放电,Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]_(0.98)Ti_(0.02)O_2样品的放电比容量要比未掺杂样品高出约20 m A·h/g。而且经过100次循环后,Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]_(0.98)Ti_(0.02)O_2样品的放电比容量仍有187.9 m A·h/g,容量保持率高达96.8%。而未掺杂样品的100次循环后容量保持率仅有91.2%。  相似文献   

4.
采用分步共沉淀反应并通过控温煅烧制备得到了均匀的具有微纳结构的Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2微米棒,借助Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2微米棒表面多孔结构吸附偏钒酸铵溶液并通过后期煅烧制备了Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2-V_2O_5复合材料。利用X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)等表征了产物成分、形貌和结构。通过计算得到的晶胞参数表明,与10%(质量分数)偏钒酸铵复合得到的产物具有更好的层状结构。通过恒流充放电等方法对材料的电化学性能进行测试。结果表明,与质量分数为10%五氧化二钒复合的富锂材料首次库伦效率从86%提高到111%,放电容量也有很大程度的提高。这种方法是解决富锂首次效率低问题的一种有效途径。  相似文献   

5.
采用湿法融合技术及高温固相法合成Li_3VO_4包覆的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2正极材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等方法研究材料的结晶相、形貌、微观结构。研究表明,Li_3VO_4均匀地包覆在Li Ni0.8Co0.1Mn0.1O_2表面,未改变原材料的材料结构和形貌,包覆层厚度为1~2 nm。不同含量的Li_3VO_4对LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2正极材料进行修饰研究表明,3%(质量)Li_3VO_4包覆的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2在1 C下100次循环后容量保持率为94.13%,具有最佳的倍率性能和循环性能。此外,循环伏安(CV)和交流阻抗(EIS)分析表明,Li_3VO_4能提高Li+电导率,抑制活性材料与电解液之间的副反应,提高材料的电化学性能。  相似文献   

6.
以Zr(NO_3)_4·5H_2O和CH_3COOLi·2H2_O为原料,采用湿化学法,将Li_2ZrO_3包覆在LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2锂离子电池正极材料的表面,研究Li_2ZrO_3不同包覆比例对LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2电化学性能的影响。SEM、TEM、EDS谱图分析表明,Li_2ZrO_3层均匀地包覆在LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2表面,其厚度约为8 nm。与纯相相比,1%(质量分数)Li_2ZrO_3包覆的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2复合材料在1.0 C下首次放电比容量为184.7 mA·h·g~(-1)、100次循环之后放电比容量为169.5 mA·h·g~(-1),其容量保持率达到91.77%,表现出良好的循环稳定性。循环伏安(CV)和电化学阻抗(EIS)测试结果表明,Li_2ZrO_3包覆层抑制了正极材料与电解液之间的副反应,减小了材料在循环过程中的电荷转移阻抗,从而提高了材料的电化学性能。  相似文献   

7.
采用锂镧锆氧(Li_7La_3Zr_2O_(12))快离子导体包覆Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2正极材料,获得了核壳结构复合材料,并探讨表面活性剂在包覆过程的作用机制。利用热重分析、X射线粉末衍射、扫描电子显微镜和电化学性能测试等方法进行结构和性能分析。结果表明,以Tween 20为表面活性剂,600℃合成的Li_7La_3Zr_2O_(12)包覆的富锂正极复合材料的粒径均匀,首次放电比容量达273.2 m A·h/g,1C倍率下45次循环后的容量保持率为86.6%,显示出较好的电化学性能。Li_7La_3Zr_2O_(12)快离子导体壳层提高了电极/电解液界面Li~+的扩散速率,抑制了电解质与活性材料之间的副反应,进而提高了材料的首次Coulomb效率和循环稳定性。  相似文献   

8.
采用聚苯胺-聚乙二醇(PANI-PEG)双导电聚合物对Li_(1.17)Mn_(0.50)Ni_(0.16)Co_(0.17)O_2正极材料进行表面改性。利用XRD、SEM、TEM测试手段对包覆前后样品的晶体结构和表面形貌进行了表征,并对其电化学性能进行了系统研究。其中3%(wt)的PANI-PEG改性的Li_(1.17)Mn_(0.50)Ni_(0.16)Co_(0.17)O_2正极材料表现出最佳的初始库伦效率(83.0%),最高的放电比容量(100圈后192.0 mA·h·g~(-1)/1C)和最高的倍率性能(130 mA·h·g~(-1)/5C)。  相似文献   

9.
《应用化工》2017,(4):681-684
采用沉淀法对层状LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2正极材料进行Y_2O_3表面包覆,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、电化学交流阻抗(EIS)及恒流充放电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,Y_2O_3均匀包覆在LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2材料的表面,并没有改变材料的晶体结构,且Y_2O_3包覆的正极材料表现出良好的电化学性能。在2.5~4.5 V电压范围和20 mA/g电流密度下,包覆0.5%Y_2O_3材料的首次放电容量190.5 mAh/g,50次循环后,材料的容量保持率达到99.9%,而未包覆材料的首次放电容量略低(187.0 mAh/g),且容量衰减较快,50次循环后,材料的容量保持率仅有92.7%。此外,包覆0.5%Y_2O_3的材料在400 mA/g下放电容量仍有150 mAh/g,表现出优异的倍率性能。  相似文献   

10.
《应用化工》2022,(4):681-684
采用沉淀法对层状LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2正极材料进行Y_2O_3表面包覆,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、电化学交流阻抗(EIS)及恒流充放电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,Y_2O_3均匀包覆在LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2材料的表面,并没有改变材料的晶体结构,且Y_2O_3包覆的正极材料表现出良好的电化学性能。在2.54.5 V电压范围和20 mA/g电流密度下,包覆0.5%Y_2O_3材料的首次放电容量190.5 mAh/g,50次循环后,材料的容量保持率达到99.9%,而未包覆材料的首次放电容量略低(187.0 mAh/g),且容量衰减较快,50次循环后,材料的容量保持率仅有92.7%。此外,包覆0.5%Y_2O_3的材料在400 mA/g下放电容量仍有150 mAh/g,表现出优异的倍率性能。  相似文献   

11.
《Ceramics International》2019,45(16):20016-20021
Li-rich Mn-based layered oxide Li1.2Mn0.54Ni0.13Co0.13O2 (LMNCO) has received great interest due to its high discharge capacity. However, the fast capacity attenuation seriously hinders its wide application. LMNCO particles are synthesized via a co-precipitation method. To enhance the cycle stability, (Ni0.4Co0.2Mn0.4)1-xTix(OH)2+2x surface layer is deposited on LMNCO precursor particles by a second co-precipitation process. Due to the mutual diffusion of elements during sintering, Ti is distributed in the 2–3 μm shell of particles. The cells are cycled in a voltage window of 2.0–4.8 V at 0.5C. After 200 cycles, LMNCO exhibits a capacity retention of 43%, and LMNCO particles have been pulverized by the cycle process. In contrast, the structural integrity of coated particles is maintained, and therefore the cycle stability is evidently improved.  相似文献   

12.
《Ceramics International》2021,47(24):34492-34500
The zeolitic imidazolate frameworks 67 (ZIF-67) derivative Co3O4 composite lithium-rich manganese-based layered oxide was successfully synthesized by a simple solid-phase sintering method and systematically studied. The introduction of the derivatives does not excessively induce changes in the transition metal layered oxide structure as tested by XRD, SEM, TEM, and XPS. The electrochemical test and analysis show that the high surface area and porous structure of the ZIF-67 derivative Co3O4 can promote the contact efficiency of the electrode and the electrolyte, thereby delaying the structural phase change which caused by the long cycle process and suppressing the voltage attenuation. In particular, a composite ratio of 10:1 samples can most effectively improve the first coulomb efficiency, cycling stability, and structural stability of lithium-rich materials. The discharge specific capacity at 0.1 C is 258.9 mAh/g, and the first coulomb efficiency is 74.93%. Especially, the discharge specific capacity at 0.5 C is 234.1 mAh/g, and the capacity retention rate is 86.28% after 100 cycles.  相似文献   

13.
《Ceramics International》2016,42(14):15623-15633
Li-rich layered oxides are the most promising cathode candidate for new generation rechargeable lithium-ion batteries. In this work, La2O3-coated Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials were fabricated via a combined method of sol-gel and wet chemical processes. The structural and morphological characterizations of the materials demonstrate that a thin layer of La2O3 is uniformly covered on the surface of Li1.2Mn0.54Ni0.13Co0.13O2 particles, and the coating of La2O3 has no obvious effect on the crystal structure of Li-rich oxide. The electrochemical performance of La2O3-coated Li-rich cathodes including specific capacity, cycling stability and rate capability has been significantly improved with the coating of La2O3. The Li1.2Mn0.54Ni0.13Co0.13O2 coated with 2.5 wt% La2O3 exhibits the highest discharge capacity, improved cycling stability and reduced charge transfer resistance, delivering a large discharge capacity of 276.9 mAh g−1 in the 1st cycle and a high capacity retention of 71% (201.4 mAh g−1) after 100 cycles. The optimal rate capability of the materials is observed at the coating level of 1.5 wt% La2O3 such that the material exhibits the highest discharge capacity of 90.2 mAh g−1 at 5 C. The surface coating of La2O3 can effectively facilitate Li+ interfacial diffusion, reduce the structural change and secondary reactions between cathode materials and electrolyte during the charge-discharge process, and thus induce the great enhancement in the electrochemical properties of the Li1.2Mn0.54Ni0.13Co0.13O2 materials.  相似文献   

14.
《Ceramics International》2020,46(15):23773-23779
Lithium-rich layered oxides with high energy density have been intensively investigated as advanced lithium-ion batteries cathode materials. However, capacity degradation and voltage decay caused by irreversible lattice oxygen loss and structural transformation during cycling restrict their application. Herein, we proposed a high valance cations Nb5+ doping strategy and synthesized a series of Li1.2Mn0.54-x/3Ni0.13-x/3Co0.13-x/3NbxO2 (x = 0, 0.01, 0.02 and 0.03) cathode materials. The effects of Nb5+ doping on crystallographic structure and electrochemical property were systematically studied. In virtue of the large ionic radii and strengthened Nb–O bonds, the doped samples present commendable structural stability and expanded interlayer spacing for Li-ions migration, which ensures the upgraded cyclic stability and rate performance. In particular, the electrode with x = 0.02 delivers a discharge specific capacity of 265.8 mAh g-1 at 0.2 C with decelerated voltage decay, while 86.9% capacity are remained after long-term cycles. Moreover, excellent discharge specific capacity of 153.4 mAh g−1 is still attained at 5 C accompanied with enhanced Li-ion diffusion kinetics.  相似文献   

15.
《Ceramics International》2020,46(17):27010-27020
In this work, hierarchical flower-like Li1.2Ni0.13Co0.13Mn0.54O2 (LNCM) with exposed {010} planes assembled and double-sphere Li1.2Ni0.13Co0.13Mn0.54O2 without {010} planes as a comparison were successfully synthesized via a simple solvothermal method. The diffusion of Li+ could be enhanced in the flower-like LNCM with exposed {010} active planes, and the cathode exhibits a superior electrochemical performance especially in long-term cycling stability even at high current densities. The initial discharge capacity of this sample is 274 mA h g−1 at 0.1C (25 mA g−1), with corresponding initial coulombic efficiencies of 77%. Especially, the capacity retention reaches up to 98% at 1250 mA g−1 current density after 100 cycles. By comparing with other LNCM materials reported recently, our optimal cathode has a pretty outstanding electrochemical performance, which is promising for the next generation lithium ion batteries.  相似文献   

16.
《Ceramics International》2017,43(17):14836-14841
Molybdenum doping is introduced to improve the electrochemical performance of lithium-rich manganese-based cathode material. X-ray diffraction (XRD) results illustrate that the crystallographic parameters a, c and lattice volume V become larger with the increase of Mo content. The scanning electron microscope (SEM) shows that the molybdenum substitution increases the crystallinity of the primary particles. When evaluated as cathode material, the as-prepared Li[Li0.2Mn0.54-x/3Ni0.13-x/3Co0.13-x/3Mox]O2 (x = 0.007) delivers a discharge capacity of 155.5 mA h g−1 at 5 C (1 C = 250 mA g−1) and exhibits the capacity retention of 81.8% at 1 C after 200 cycles. The results of cyclic voltammetry (CV) and electronic impedance spectroscopy (EIS) tests reflect that the molybdenum substitution is able to significantly reduce the electrode polarization and lower the charge-transfer resistance. Within appropriate amount of Mo doping, the lithium ion diffusion coefficient of the material can reach to 8.92 × 10–15 cm2 s−1, which is ~ 30 times higher than that of pristine materials (2.65 × 10–16 cm2 s−1).  相似文献   

17.
《Ceramics International》2017,43(6):5267-5273
SmPO4 coated Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials were prepared by the precipitation method and calcined at 450 °C. The crystal structures and electrochemical properties of the pristine and coated samples are studied by X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, electron diffraction spectroscopy, galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). It has been found that the electrochemical performances of the Li-rich cathode material have been substantially improved by SmPO4 surface coating. Especially, the 2 wt% SmPO4-coated sample demonstrates the best cycling performance, with capacity retention of 88.4% at 1 C rate after 100 cycles, which is much better than that of 72.3% in the pristine sample. The improved electrochemical properties have been ascribed to the SmPO4 coating layer, which not only stabilizes the cathode structure by decreasing the loss of oxygen, but also protects the Li-rich cathode material from side reaction with the electrolyte and increases the Li+ migration rate at the cathode interface.  相似文献   

18.
采用碳酸盐共沉淀法和高温烧结工艺将一定量的Mo6+掺杂到Li1.20Mn0.54Ni0.13Co0.13O2正极材料中。利用XRD、SEM、EDS和恒流测试仪研究Mo6+掺杂对Li1.20Mn0.54Ni0.13Co0.13O2正极材料的晶体结构、微观形貌和电化学性能的影响。结果显示,Li1.20Mn0.52Ni0.13Co0.13Mo0.02O2表现出更低的阳离子混排和优异的电化学性能。经过Mo6+掺杂后的正极,由于Li+高速的迁移速率,使得首次不可逆容量损失降低,并展现出更好的高倍率性能和优异的循环稳定性。在0.5C倍率下循环100周后,Li1.20Mn0.52Ni0.13Co0.13Mo0.02O2的容量保持率达到92.2%,远远大于Li1.20Mn0.54Ni0.13Co0.13O2的87.5%。另外,当放电倍率增大到5C时,Li1.20Mn0.54Ni0.13Co0.13O2的放电比容量要比Li1.20Mn0.52Ni0.13Co0.13Mo0.02O2低21.0 mA·h/g。因此,采用Mo6+掺杂改性Li1.20Mn0.54Ni0.13Co0.13O2正极材料,可以有效提高锂电池的循环保持率和高倍率放电性能。  相似文献   

19.
In the material of xLi2MnO3 ·(1-x) LiMO2 (0 < x < 1), the Li2MnO3 component is used to stabilize the layered LiMO2 structure. However, the electrochemical inactive Li2MnO3 makes Li-ion diffusion difficult, leading to a sluggish rate capability. In this work, Li1.3Ti1.7Al0.3(PO4)3 (LTA0.3), a NASICON-type Li-ion conductor, is applied to modified Li1.2Mn0.54Ni0.13Co0.13O2 to overcome the above shortcoming. Additionally, the Li-ion conductivity of LiTi2(PO4)3 can be improved effectively by replacing tetravalent cation Ti4+ with trivalent Al3+ at the optimal ratio. At 1C rate, the LR cathode with 3 wt% LTA0.3 delivers 200 mAh g?1 after 170 cycles and maintains 140 mAh g?1 after 500 cycles. Moreover, the modified cathode shows an enhanced rate performance of 169.7 mAh g?1 at 5C. Enhanced cycle durability and rate capability are aroused by the 3D skeletal framework of LTA0.3, which is suitable for Li-ion diffusion. The LTA0.3 coating layer displays a robust shell which not only avoids the corrosion of electrode materials but also effectively facilitates Li-ion diffusion.  相似文献   

20.
《Ceramics International》2016,42(16):18620-18630
The development of Li-rich layer cathode materials has been limited by poor cycle, rate performance, phase transformation and voltage decay. To improve these properties, a facile and low-cost wet method is employed to fabricate Pr6O11 coating layer on Li[Li0.2Mn0.54Co0.13Ni0.13]O2 nanoparticles. The 3–6 nm Pr6O11 coating layer is observed on the surface of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 by HRTEM. Interestingly, HAADF-STEM and EDS analyses show that the transition metal ions and the praseodymium ions mutually infiltrate in the Pr6O11 coating layer and Li[Li0.2Mn0.54Co0.13Ni0.13]O2 nanoparticles during calcination. A combination of HAADF-STEM with EDS and XPS studies reveals that Pr6O11 coating layer is bridged to Li[Li0.2Mn0.54Co0.13Ni0.13]O2 nanoparticles by the chemical bonds of transition phase Li1.2MXPr1−xO2. XRD patterns show that all samples are indexed to the layered structure α-NaFeO2, but the lattice parameters are influenced lightly after Pr6O11 coating. HRTEM and SAED analyses elucidate that the super large Pr ions surface-doping and the Pr6O11 coating are verified to suppress the transformation of layer to spinel structure in the bulk nanoparticles after cycles. The sample coated with 3 wt% Pr6O11 exhibits wonderful electrochemical performance with the first coulomb efficiency of 85.6%, the capacity retention ratio of 97.9% after 50 cycles and the discharge capacity of 162.2 mAh g−1 at 5 C. The resistant of charge transfer and the electrodes polarization are reduced by Pr6O11 coating according to EIS. Therefore, Pr6O11, which contains the super large Pr ions, plays two roles: the first one, it is coated on the Li[Li0.2Mn0.54Co0.13Ni0.13]O2 nanoparticles to optimize the environment of the interface reaction between electrodes and electrolyte; the other one, its Pr ions surface-doping stabilizes the structure in the superficial region of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 nanoparticles and suppresses the voltage decay. The multifunctional Pr6O11 can play a significant role in accelerating development of new materials with excellent stabilization and high capacity.  相似文献   

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