One-step hydrothermal synthesis of LiMn2O4 cathode materials for rechargeable lithium batteries

LiMn₂O₄ cathode materials with high discharge capacity and good cyclic stability were prepared by a simple one-step hydrothermal treatment of KMnO₄, aniline and LiOH solutions at 120–180 °C for 24 h. The aniline/KMnO₄ molar ratio (R) and hydrothermal temperature exhibited an obvious influence on the component and phase structures of the resulting product. The precursor KMnO₄ was firstly reduced to birnessite when R was less than 0.2:1 at 120–150 °C. Pure-phased LiMn₂O₄ was formed when R was 0.2:1, and the LiMn₂O₄ was further reduced to Mn₃O₄ when R was kept in the range of 0.2–0.3 at 120–150 °C. Moreover, LiMn₂O₄ was fabricated when R was 0.15:1 at 180 °C. Octahedron-like LiMn₂O₄ about 300 nm was prepared at 120 °C, and particle size decreased with an increase in hydrothermal temperature. Especially, LiMn₂O₄ synthesized at 150 °C exhibited the best electrochemical performance with the highest initial discharge capacity of 127.4 mAh g⁻¹ and cycling capacity of 106.1 mAh g⁻¹ after 100 cycles. The high discharge capacity and cycling stability of the as-prepared LiMn₂O₄ cathode for rechargeable lithium batteries were ascribed to the appropriate particle size and larger cell volume.     

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery.In this paper,sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon,which is characterized as high specific surface area and microporous structure.The composite,contained 70%sulfur,as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature....     

Crosslinked polyacrylonitrile precursor for S@pPAN composite cathode materials for rechargeable lithium batteries

S@pPAN has become promising cathode materials in rechargeable batteries due to its high compressed density,low E/S ratio,no polysulfide dissolution,no self-discharge,and stable cycling.However,it is a big challenge to enhance its sulfur content which determines its practical specific capacity.Herein,we prepare crosslinked PAN as precursor,leading to effective enhancement of sulfur content up to 55 wt%and a reversible specific capacity of 838 mAh g _composites^-1 at 0.2C.Because of the microporous structure and high specific area,crosslinked PAN provides more space to accommodate sulfur molecule and improve the interfacial reaction of S@pPAN as well.This work provides a promising direction to design S@pPAN for lithium sulfur batteries with high energy density.     

Soft mechanochemical synthesis: Preparation of cathode materials for rechargeable lithium batteries

To prepare intercalation lithium — transition metal oxide cathode materials for rechargeable lithium batteries, the reactions in the mixtures of the correspondent hydroxides in highly energetic planetary activators, so called ‘soft mechanochemical synthesis’ were studied. The method can be used for direct preparation of final products in a high dispersed and disordered state, as well as for obtaining high reactive precursors yielding final products by the subsequent brief heating at considerably lower temperatures as compared to conventional ceramic method. The as prepared products were analyzed using X-ray diffraction, TG, IRS, XPS, ⁷Li NMR, EPR, diffuse reflectance spectroscopy, electron microscopy, BET, and electrochemical measurements. The peculiarities of crystal structure, electronic state of transition metal ions and cycling behaviour of materials are discussed. The method as proposed is concluded to be economically effective and ecologically clean.     

High capacity and cycling stability of poly(diaminoanthraquinone) as an organic cathode for rechargeable lithium batteries

Poly(1,5‐diaminoanthraquinone) is synthesized by oxidative polymerization of diaminoanthraquinone monomers and investigated as an organic host for Li‐storage reaction. Benefiting from its high density of redox‐active, Li⁺‐associable benzoquinone groups attached to conducting polyaniline backbones, this polymer undergoes its cathodic reaction predominately through Li⁺‐insertion/extraction processes, delivering a very high reversible capacity of 285 mAh g^?1. In addition, the PDAQ polymer cathode exhibits an excellent rate capability (125 mAh g^?1 at 800 mA g^?1) and a considerable cyclability with a capacity retention of ～160 mAh g^?1 over 200 cycles, possibly serving as a sustainable, high capacity Li⁺ host cathode for Li‐ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 235–238     

Synthesis of tetrahedral LiFeO2 and its behavior as a cathode in rechargeable lithium batteries

Synthesis and structural characterization of the first LiFeO2 compound with tetrahedrally coordinated Fe3+ is reported. When used as a positive intercalation electrode in a lithium cell, it can store charge of up to 120 mAhg(-1) at a rate of 100 mAg(-1). However, it converts to the defect spinel LiFe5O8 on cycling. By combining results from powder X-ray diffraction, differential electrochemical mass spectrometry, electrochemical cycling, and TG-MS, it is shown that such conversion, which involved oxygen loss, is not associated with direct O2 gas evolution but instead reaction with the electrolyte. We suggest that intercalation/deintercalation is accompanied by the exchange of Li+ by H+ in the material and subsequent loss of H2O, thus converting LiFeO2 to the defect spinel LiFe5O8 on cycling.     

Nano-LiCoO2 as cathode material of large capacity and high rate capability for aqueous rechargeable lithium batteries

Crystalline nanoparticles of LiCoO₂ are prepared by a sol–gel method at 550 °C and characterized by X-ray diffraction. Their electrochemical behaviors were characterized by cyclic voltammograms, capacity measurement and cycling performance. Results show that the reversible capacity of the nano-LiCoO₂ can be up to 143 mAh/g at 1000 mA/g and still be 133 mAh/g at 10,000 mA/g (about 70C) in 0.5 mol/l Li₂SO₄ aqueous electrolyte. In addition, their cycling behavior is also very satisfactory, no evident capacity fading during the initial 40 cycles. These data present great promise for the application of aqueous rechargeable lithium batteries.     

Porous V2O5-SnO2/CNTs composites as high performance cathode materials for lithium-ion batteries

Vanadium pentoxide (V₂O₅) exhibits high theoretical capacities when used as a cathode in lithium ion batteries (LIBs), but its application is limited by its structural instability as well as its low lithium and electronic conductivities. A porous composite of V₂O₅-SnO₂/carbon nanotubes (CNTs) was prepared by a hydrothermal method and followed by thermal treatment. The small particles of V₂O₅, their porous structure and the coexistence of SnO₂ and CNTs can all facilitate the diffusion rates of the electrons and lithium ions. Electrochemical impedance spectra indicated higher ionic and electric conductivities, as compared to commercial V₂O₅. The V₂O₅-SnO₂/CNTs composite gave a reversible discharge capacity of 198 mAh·g^?1 at the voltage range of 2.05–4.0 V, measured at a current rate of 200 mA·g^?1, while that of the commercial V₂O₅ was only 88 mAh·g^?1, demonstrating that the porous V₂O₅-SnO₂/CNTs composite is a promising candidate for high-performance lithium secondary batteries.     

Partially substituted lithium manganese oxides as 3 V cathode materials for secondary lithium batteries

Low temperature synthesis and electrochemical properties of partially substituted lithium manganese oxides are reported. We demonstrate various metallic cations (Cu²⁺, Ni²⁺, Fe³⁺, Co³⁺) can be incorporated in the 3 V layered cathodic material Li_0.45MnO_2.1. New compounds Li_0.45Mn_0.88Fe_0.12O_2.1, Li_0.45Mn_0.84Ni_0.16O_2.05, Li_0.45Mn_0.79Cu_0.21O_2.3, Li_0.45Mn_0.85Co_0.15O_2.3 are prepared. These 3 V cathode materials are characterized by the same shape of discharge-charge profiles but different values of the specific capacity, between 90 mAh g⁻¹ and 180 mAh g⁻¹. The best results in terms of capacity and cycle life are obtained with the selected content of 0.15 Co per mole of oxide, as the optimum composition. The high kinetics of Li⁺ transport in Li_0.45Mn_0.85Co_0.15O_2.3 compared to that in the Co-free material is consistent with a substitution of Mn(III) by Co(III) in MnO₂ sheets.     

Poly(3,4-ethylenedioxythiophene)V2O5 hybrids for lithium batteries

A series of hybrid electrode materials, poly(3,4-ethylenedioxythiophene)/V₂O₅, has been synthesized using an oxidative insertion and polymerization reaction. FTIR, X-ray diffraction and transmission electron microscopy studies have shown that the incorporation of polymer between V₂O₅ slabs leads to an enhanced bidimensionality. The electrochemical lithium capacity has been increased up to ∼330 mAh/g at the second discharge in the range of 2.0–4.4 V vs. Li. This improvement of electrochemical performance compared to pristine V₂O₅ is attributed to the higher electric conductivity and enhanced bidimensionality.     

Morphology-controllable synthesis of LiMn2O4 particles as cathode materials of lithium batteries

We reported a new method for the preparation of morphology-controllable LiMn₂O₄ particles. In this method, dimension-different MnO₂ nanowires synthesized hydrothermally by adjusting the reaction temperature were used as the precursor. The morphology and structure of the resulting products were characterized with scanning electron microscope and X-ray diffraction, and the performances of the prepared LiMn₂O₄ samples as cathode material of lithium batteries were investigated by cyclic voltammetry and galvanostatic charge/discharge test. The results indicate that the morphology of LiMn₂O₄ transforms from tridimensional particle (TP) to unidimensional rod (UR) through quadrate lamina (QL) with increasing the diameter and length of MnO₂ nanowires. Although the cyclic stabilities of LiMn₂O₄-TP, LiMn₂O₄-QL, and LiMn₂O₄-UR are very close (the 0.1 C capacity after 50 cycles is 101, 93, and 99 mAh g^?1 at 25 °C, and 84, 78, and 82 mAh g^?1 at 50 °C, respectively), LiMn₂O₄-QL delivers much higher rate capacity (about 70 mAh g^?1 at 5 C and 30 mAh g^?1 at 10 C) than LiMn₂O₄-TP and LiMn₂O₄-UR (about 20 mAh g^?1 at 5 C, 3 mAh g^?1 at 10 C, 25 mAh g^?1 at 5 C, and 3 mAh g^?1 at 10 C).     

Nanometer Cr2O3-doped MnO2 spheres for rechargeable lithium batteries

Nanometer manganese dioxide spheres were prepared by water/oil microemulsion technology using sodium pyrosulfite and potassium permanganate as the raw materials. The scanning electron microscopy and the transmission electron microscopy images showed that the as-prepared MnO₂ particles aggregated with many nanosize spheres with an average diameter about 100 nm. From the X-ray diffraction patterns, it suggested that the achieved materials had the crystal structure of α-MnO₂. The electrochemical properties of the nanometer MnO₂ spheres doped with various amounts of Cr₂O₃ were studied in detail in this paper. The results revealed that the MnO₂ particles doped with 4 wt.% Cr₂O₃ can maintain more than 150 mAh g⁻¹, which is about 84% of the initial specific capacity, even after 50 cycles indicating a promising application in the rechargeable lithium batteries.     

Synthesis and performance of carbon-coated Li3V2(PO4)3 cathode materials for lithium-ion batteries

The carbon-coated monoclinic Li₃V₂(PO₄)₃ (LVP/C) cathode materials can be synthesized by one-step heat treatment from a sucrose-containing precursor. Properties of the prepared composite material were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), pore size distribution and specific surface area analyzer, optical particle size analyzer and electrochemical methods. X-ray diffraction results show that LVP sample is monoclinic structure. The sample presents initial discharge capacity of 127.2 mA h/g (at 0.2 C rate), and exhibits better cycling stability (115.1 mA h/g at 30th cycle at 0.2 C rate) and better rate capability (83.1 mA h/g at 50th cycle under 6 C rate) in the voltage range of 3.0–4.3 V. In the voltage range of 3.0–4.8 V, it exhibits a initial discharge capacity of 169.1 mA h/g and good cycling stability (104.9 mA h/g at 20th cycle at 0.5 C rate).     

Enhancing LiNiO2 cathode materials by concentration-gradient yttrium modification for rechargeable lithium-ion batteries

Lithium nickel oxide (LiNiO2) cathode materials are featured with high capacity and low cost for rechargeable lithium-ion batteries but suffer from severe inter...     

A series of spinel phase cathode materials prepared by a simple hydrothermal process for rechargeable lithium batteries

A series of spinel-structured materials have been prepared by a simple hydrothermal procedure in an aqueous medium. The new synthetic method is time and energy saving i.e., no further thermal treatment and extended grinding. The main experimental process involved the insertion of lithium into electrolytic manganese dioxide with glucose as a mild reductant in an autoclave. Both the hydrothermal temperature and the presence of glucose play the critical roles in determining the final spinel integrity. Particular electrochemical performance has also been systematically explored, and the results show that Al³⁺, F⁻ co-substituted spinels have the best combination of initial capacity and capacity retention among all these samples, exhibited the initial capacity of 115 mAh/g and maintained more than 90% of the initial value at the 50th cycle.     

锂离子电池正极材料LiNi_0.5Mn_1.5O_4表面包覆CuO的研究

本文首先通过共沉淀法和固相球磨法制备了纳米级的LiNi0.5Mn1.5O4高电压正极材料,然后通过溶胶-凝胶法制备了表面包覆CuO的CuO-LiNi0.5Mn1.5O4复合材料.通过对CuO包覆量为1%,3%和5%的复合材料的电化学性能对比,发现当包覆量为1%时,材料的性能最佳.在1 C下,材料的放电比容量高达126.1 mA h g?1,循环100次后容量保持率在99.5%.CuO包覆在纳米LiNi0.5Mn1.5O4材料表面,阻止电解液与活性颗粒的直接接触,削弱了电解液与LiNi0.5Mn1.5O4的相互作用,进而在一定程度上减缓了电解液的分解;CuO的包覆同时还缓解了电解液中HF对材料的攻击,阻止了锰的溶解和由此带来的结构改变,进而提高了材料的循环稳定性.     

Charge storage mechanisms of cathode materials in rechargeable aluminum batteries

Science China Chemistry - Rechargeable aluminum batteries (RABs) have attracted great interest as one of the most promising candidates for large-scale energy storage because of their high...     

Electrochemical properties of PABTH as cathode materials for rechargeable lithium battery

The electrochemical properties of polyanthra [1′,9′,8′-b,c,d,e] [4′,10′,5′-b′,c′,d′,e′]bis-[1,6,6a(6a-S^IV)trithia]pentalene (PABTH) were studied. It is found that PABTH exhibits a good cyclability and high capacity of 290 mAh/g in 1 M LiTFSI/DXL–DME (2:1 by weight) electrolyte. Detailed electrochemical characterization reveals that the capacity fading of PABTH within the first several cycles is due to the loss of ABTH monomer or its oligomer that is contained in PABTH in the form of soluble discharging products. It also needs to be noted that PABTH and ABTH has much higher charge–discharge efficiency (up to 95%) than that of sulfur (below 85%) because the S–S bond is fixed to the backbone.