Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries

A composite anode material of silicon/graphite/multi-walled carbon nanotubes (MWNTs) for Li-ion batteries was prepared by ball milling. This composite anode material showed a discharge capacity of 2274 mAh/g in the first cycle, and after 20 charge-discharge cycles, a reversible capacity of 584 mAh/g was retained, much higher than 218 mAh/g for silicon/graphite composite. It was observed that silicon particles were homogeneously embedded into the “lamellar structures” of flaked graphite particles, and the silicon/graphite composite particles were further wrapped by a MWNTs network. The improvement in the electrochemical properties of the composite anode material was mainly attributed to the excellent resiliency and good electric conductivity of the MWNTs network.     

Electrochemical intercalation of lithium into a natural graphite anode in quaternary ammonium-based ionic liquid electrolytes

Electrochemical intercalation of lithium into a natural graphite anode was investigated in electrolytes based on a room temperature ionic liquid consisting of trimethyl-n-hexylammonium (TMHA) cation and bis(trifluoromethanesulfone) imide (TFSI) anion. Graphite electrode was less prone to forming effective passivation film in 1 M LiTFSI/TMHA-TFSI ionic electrolyte. Reversible intercalation/de-intercalation of TMHA cations into/from the graphene interlayer was confirmed by using cyclic voltammetry, galvanostatic measurements, and ex situ X-ray diffraction technique. Addition of 20 vol% chloroethylenene carbonate (Cl-EC), ethylene carbonate (EC), vinyl carbonate (VC), or ethylene sulfite (ES) into the ionic electrolyte resulted in the formation of solid electrolyte interface (SEI) film prior to TMHA intercalation and allowed the formation of Li-C₆ graphite interlayer compound. In the ionic electrolyte containing 20 vol% Cl-EC, the natural graphite anode exhibited excellent electrochemical behavior with 352.9 mAh/g discharge capacity and 87.1% coulombic efficiency at the first cycle. A stable reversible capacity of around 360 mAh/g was obtained in the initial 20 cycles without any noticeable capacity loss. Mechanisms concerning the significant electrochemical improvement of the graphite anode were discussed. Ac impedance and SEM studies demonstrated the formation of a thin, homogenous, compact and more conductive SEI layer on the graphite electrode surface.     

Enhanced electrochemical properties of SnO2 anode by AlPO4 coating

A SnO₂ anode material undergoes severe capacity loss, which is mainly associated with cracking/crumbling of the material by the large volume change between the Li_xSn and Sn phases, and the intensive reactions with the electrolyte solution. However, AlPO₄ nanoparticle coating showed drastically improved electrochemical properties with decreased surface cracks. The AlPO₄-coated SnO₂ exhibited a capacity of 781 mAh/g, approaching its theoretical capacity at the first cycle, with 44% capacity retention after 15 cycles between 2.5 and 0 V at a relatively high C rate of 105 mA/g. In contrast, the bare SnO₂ showed an initial capacity of 680 mAh/g, with only 8% capacity retention after 15 cycles.     

Improving room-temperature electrochemical performance of solid-state lithium battery by using electrospun La2Zr2O7 fibers-filled composite solid electrolyte

Low ionic conductivity at room temperature and poor interfacial compatibility are the main obstacles to restrain the practical application of polymer solid electrolytes. In this work, lanthanum zirconate (LZO) fibers were prepared by electrospinning method and used for the first time as fillers in sandwich polypropylene carbonate (PPC)-based solid electrolyte. Meanwhile, a graphite coating was applied on one surface of the composite solid electrolyte (CSE) membrane. The results show that the LZO fibers significantly increases the room-temperature electrochemical performance of the CSE, and the graphite coating enhances the interfacial compatibility between electrolyte and lithium anode. Furthermore, an ultra-thin PPC-LZO CSE with a total thickness of 22 μm was prepared and used in NCM622/CSE/Li solid-state cell, which shows an initial discharge capacity of 165.6 mAh/g at the current density of 0.5C and a remaining capacity of 113.0 mAh/g after 250 cycles at room temperature. Rise to 1C, the cell shows an initial discharge capacity of 154.2 mAh/g with a remaining capacity of 95.6 mAh/g after 250 cycles. This ultra-thin CSE is expected to be widely applied in high energy-density solid-state battery with excellent room-temperature electrochemical performances.     

新型AB5型氧化合金/碳复合材料作为锂离子电池负极性能研究

对回收的废旧镍氢(MH-Ni)电池负极材料AB5型储氢合金进行改性再利用,经过高温氧化处理和添加改性石墨制成复合材料后,用于高性能锂离子电池负极材料.通过X射线衍射(XBD)和电子显微镜(SEM)对材料进行了简单表征,采用恒电流充放电仪对材料进行电化学性能测试.实验结果表明,所制得的AB5型氧化合金/碳复合材料的首次充...     

Synthesis of Zn2SnO4 anode material by using supercritical water in a batch reactor

Zn₂SnO₄ anode powders were successfully synthesized using supercritical water (SCW) and metal salt solutions with 10 min reaction time. Effect of NaOH concentration, Zn to Sn ratio, and synthesis temperature were studied with a SCW batch reactor. X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge/discharge cycling tests were employed to characterize the physical properties and electrochemical performance of the as-prepared samples. Alkaline solution concentration and synthesis temperature played a key role in the production of single-phase Zn₂SnO₄ powders. At a solution concentration of 0.3 M NaOH and a molar ratio of Zn:Sn = 2:1 at 400 °C and 30 MPa, the average size range of the pure Zn₂SnO₄ powders was 0.5-1.0 μm, and the morphology was nearly uniform and cubic-like in shape. The initial specific discharge capacity of the Zn₂SnO₄ powders prepared at this condition was 1526 mAh/g at a current density of 0.75 mA/cm² in 0.05-3.0 V, and their irreversible capacity loss was 433 mAh/g. The discharge capacities of the Zn₂SnO₄ powders decreased with cycling and remained at 856 mAh/g after 50 cycles, which was 56% of the initial capacity.     

Synthesis and electrochemical properties of submicron LiNi0.8Co0.2O2 by a polymer-pyrolysis method

A polymer-pyrolysis method was used to synthesize LiNi_0.8Co_0.2O₂, which has potential application in lithium ion batteries. The effect of calcination temperature and time on the structure and electrochemical performance of the material was investigated. XRD analysis showed that the powders obtained by calcination at 750 °C for 3 h had the best-ordered hexagonal layer structure. SEM image showed these powders were fine, narrowly distributed with platelet morphology. The charge-discharge tests demonstrated these powders had the best electrochemical properties, with an initial discharge capacity of 189 mAh/g and capacity retention of 95.2% after 50 cycles when cycled at 50 mA/g between 3.0 and 4.3 V. Besides, these powders also had exhibited excellent rate capability.     

A novel approach to explore Zn based anodes for lithium-ion battery applications

As an approach to investigate upon the electrochemical property of Zn as a possible lithium battery anode material, an ever first attempt to explore two types of Zn based alloy anodes, viz., Zn_0.9Ni_0.075In_0.025 (nickel rich) and Zn_0.9Ni_0.025In_0.075 (indium rich) was made. Citric acid assisted modified sol-gel method [CAM sol-gel] has been adopted to synthesize the anode materials at 500 °C and characterized further by XRD and SEM for phase purity and preferred surface morphology, respectively. An average crystallite size of 800 nm-1.2 μm has been calculated from the PXRD pattern and the compounds were found to exist in the cubic phase. A discharge capacity of 936 and 1155 mAh/g were exhibited by Zn_0.9Ni_0.075In_0.025 and Zn_0.9Ni_0.025In_0.075 anodes respectively, with an excellent capacity retention (>85%) and enhanced coulombic efficiency (95-98%). It is further understood that the Zn_0.9Ni_0.025In_0.075 anode with increased In content has exhibited promising electrochemical property with a steady state reversible capacity of ∼490 mAh/g even after 25 cycles, compared to the corresponding nickel rich counterpart, viz., Zn_0.9Ni_0.075In_0.025.     

Nano-porous Si/C composites for anode material of lithium-ion batteries

Nano-porous silicon composite incorporated with graphite and pyrolyzed carbon was synthesized and investigated as a promising anode material for lithium-ion batteries. The nano-porous Si/graphite composite was prepared via two-step ball-milling followed by etching process. Then carbon was incorporated by using different approaches. The nano-porous Si/graphite/C composite exhibits a reversible capacity of about 700 mAh/g with no capacity loss up to the 120th cycle at a constant current density of 0.2 mA/cm². The superior electrochemical characteristics are attributed to the nanosized pores in Si particles, which suppress the volume effect, and buffering action as well as excellent electronic and ionic conductivity of carbon materials.     

The enhanced anodic performance of highly crimped and crystalline nanofibrillar carbon in lithium-ion batteries

To find a novel high-performance anode material for lithium-ion batteries, a new form of carbon characterized by highly crimped and crystalline nanofibrillar microtextures was produced by heat treating polyacrylonitrile/FeCl₃ hybrid precursor and subsequent thermal annealing under hydrogen gas. This form of carbon exhibits a rechargeable capacity of ∼630 mAh/g, which is superior to that of graphite, with a Coulomb efficiency of ∼70%. Further, the new form of carbon was found to exhibit an efficiency of lithium ion insertion/extraction of ∼100% in the voltage range from 0.06 to 0.80 V, with a capacity of ∼400 mAh/g. We speculate that this excellent capacity is due to the characteristic structure of this form of carbon, i.e. its highly entangled web-like hyperstructure consisting of highly crimped and crystalline nanofibrillar microtextures, which enables good permeation and has high resilience to volume deformation during the insertion/extraction of Li ions.     

Electrochemical properties of heat-treated polymer-derived SiCN anode for lithium ion batteries

Silicon-carbon-nitrogen material (SiCN) is pyrolyzed from polysilylethylenediamine (PSEDA) derivation, followed by a heat-treating process at 1000 °C in Ar atmosphere. This heat-treated SiCN material has an excellent electrochemical performance as an anode for lithium ion batteries. Charge-discharge cycle measurements show that the heat-treated SiCN material exhibits a high first cycle discharge capacity of 829.0 mAh g⁻¹ and stays between 400 and 370 mAh g⁻¹ after 30 cycles. The discharge capacity remains above 300 mAh g⁻¹ at the high current density of 80 and 160 mA g⁻¹. These values are higher than untreated SiCN and commercial graphite anodes, which indicates that the heat-treating process improves the charge-discharge capacity, cycle stability and high-rate ability of SiCN anode. It is seemed that changes of SiCN structure, the formation of loose nano-holes on material surface and the formation of graphitic carbon phase in heat-treating process contribute to the improvement of electrochemical properties for SiCN anode.     

Electrochemical characteristics and intercalation mechanism of ZnS/C composite as anode active material for lithium-ion batteries

ZnS/C composites were synthesized by a combined precipitation with carbon coating method. Morphology and structure of the as-prepared ZnS/C composite materials with carbon content of 4.6 wt%, 9.3 wt% and 11.4 wt% were characterized using TEM and XRD technique. TEM observation demonstrated that the ZnS/C (9.3 wt% C) composite showed excellent microstructure with 20–30 nm ZnS nanoparticles uniformly dispersed in conductive carbon network. Electrochemical tests showed that the ZnS/C (9.3 wt% C) composite presented superior performance with initial charge and discharge capacity of 1021.1 and 481.6 mAh/g at a high specific current of 400 mA/g, after 300 cycles, the discharge capacity of ZnS/C electrode still maintained at 304.4 mAh/g, with 63.2% of its initial capacity. The rate capability and low temperature performance of the ZnS/C (9.3 wt% C) composite were compared with commercial MCMB anode. The results showed that the ZnS/C (9.3 wt%) composite exhibited much better cycle capability and low temperature performance than MCMB anode. ZnS/C composite seems to be a promising anode active material for lithium ion batteries. Intercalation mechanism of the ZnS/C composites for lithium ion insertion–extraction is proposed based on the ex situ X-ray diffraction analysis incorporating with its electrochemical characteristics.     

Synthesis of confinement structure of Sn/C-C (MWCNTs) composite anode materials for lithium ion battery by carbothermal reduction

A composite anode material was prepared with confined tin into multiwall carbon nanotube by carbothermal reduction. The morphology and structure of Sn/C (nature graphite) and Sn/C-C (nature graphite + multiwall carbon nanotube) were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was revealed that the additive of MWCNT was a crucial factor to improve Sn /C composite anodes for cyclability and reversible capacity. Volume changes and morphological changes in Sn can be reduced by encasing MWCNT in a carbonaceous material that has sufficient flexibility to act as a buffer. Electrochemical performance test shows that the charge capacity of the Sn/C-C (NG + MWCNT) electrode in the fiftieth cycle was 400 mAh/g, which was higher than that of the Sn/C (NG) electrode. After 50 cycles, the retention of the Sn/C-C electrode and the Sn/C electrode was 80% and 63%, respectively.     

Interfacial structural stabilization on amorphous silicon anode for improved cycling performance in lithium-ion batteries

Interfacial structures of electrode-current collector and electrode-electrolyte have been designed to be stabilized for improved cycling performance of amorphous silicon (Si) that is considered as an alternative anode material to graphite for lithium-ion batteries. Interfacial structural stabilization involves the interdigitation of Si electrode-Cu current collector substrate by anodic Cu etching with thiol-induced self-assembly, and the formation of self-assembled siloxane on the surface of Si electrode using silane. The novel interfacial architecture possesses promoted interfacial contact area between Si and Cu, and a surface protective layer of siloxane that suppresses interfacial reactions with the electrolyte of 1 M LiPF₆/ethylene carbonate (EC):diethylene carbondate (DEC). FTIR spectroscopic analyses revealed that a stable solid electrolyte interphase (SEI) layer composed of lithium carbonate, organic compounds with carboxylate metal salt and ester functionalities, and PF-containing species formed when having siloxane on Si electrode. Interfacially stabilized Si electrode exhibited a high capacity retention 80% of the maximum discharge capacity after 200 cycles between 0.1 and 1.5 V vs. Li/Li⁺. The data contribute to a basic understanding of interfacial structural causes responsible for the cycling performance of Si-based alloy anodes in lithium-ion batteries.     

钇掺杂钛酸锂/石墨烯纳米复合材料的合成与电化学性能

以氧化石墨烯（GO）为基底，钛酸四丁酯、一水合氢氧化锂、六水合硝酸钇为原料，十六烷基三甲基溴化铵为表面活性剂，采用溶剂热法合成前驱体，在N2气氛保护下高温煅烧合成了钇掺杂钛酸锂/氧化石墨烯纳米复合材料。采用SEM、XRD、EDS、Raman对复合材料进行了形貌、结构和成分表征。将复合材料用作锂离子电池负极材料，采用循环伏安法、恒流充放电循环法研究了其电化学性能。结果表明，片状钛酸锂包覆在氧化石墨烯片上形成了钇掺杂钛酸锂/氧化石墨烯纳米复合材料。在100 mA/g的电流密度下，钇掺杂量为8%（以钛酸锂的物质的量为基准，下同）的纳米复合材料的首次放电比容量为145.5mA·h/g，经过100圈充放电循环后容量衰减几乎为0，经过200圈循环后容量衰减1.59%，经过300圈循环后容量衰减3.24%，与目前容量保持率只有80%左右的石墨负极相比有明显的改进。钇元素的掺杂和钛酸锂包覆氧化石墨烯形式的复合材料可以减小钛酸锂电极在充放电循环中的极化程度，从而改善了材料的循环性能。     

High performance Li3V2(PO4)3/C composite cathode material for lithium ion batteries studied in pilot scale test

Li₃V₂(PO₄)₃/C composite cathode material was synthesized via carbothermal reduction process in a pilot scale production test using battery grade raw materials with the aim of studying the feasibility for their practical applications. XRD, FT-IR, XPS, CV, EIS and battery charge-discharge tests were used to characterize the as-prepared material. The XRD and FT-IR data suggested that the as-prepared Li₃V₂(PO₄)₃/C material exhibits an orderly monoclinic structure based on the connectivity of PO₄ tetrahedra and VO₆ octahedra. Half cell tests indicated that an excellent high-rate cyclic performance was achieved on the Li₃V₂(PO₄)₃/C cathodes in the voltage range of 3.0-4.3 V, retaining a capacity of 95% (96 mAh/g) after 100 cycles at 20C discharge rate. The low-temperature performance of the cathode was further evaluated, showing 0.5C discharge capacity of 122 and 119 mAh/g at −25 and −40 °C, respectively. The discharge capacity of graphite//Li₃V₂(PO₄)₃ batteries with a designed battery capacity of 14 Ah is as high as 109 mAh/g with a capacity retention of 92% after 224 cycles at 2C discharge rates. The promising high-rate and low-temperature performance observed in this work suggests that Li₃V₂(PO₄)₃/C is a very strong candidate to be a cathode in a next-generation Li-ion battery for electric vehicle applications.     

The structure and electrochemical performance of LiFeBO3 as a novel Li-battery cathode material

LiFeBO₃ cathode material has been synthesized successfully by solid-state reaction using Li₂CO₃, H₃BO₃ and FeC₂O₄·2H₂O as starting materials. The crystal structure has been determined by the X-ray diffraction. Electrochemical tests show that an initial discharge capacity of about 125.8 mAh/g can be obtained at the discharge current density of 5 mA/g. When the discharge current density is increased to 50 mA/g, the specific capacity of 88.6 mAh/g can still be held. In order to further improve the electrochemical properties, the carbon-coated LiFeBO₃, C-LiFeBO₃, are also prepared. The amount of carbon coated on LiFeBO₃ particles was determined to be around 5% by TG analysis. In comparison with the pure LiFeBO₃, a higher discharge capacity, 158.3 mAh/g at 5 mA/g and 122.9 mAh/g at 50 mA/g, was obtained for C-LiFeBO₃. Based on its low cost and reasonable electrochemical properties obtained in this work, LiFeBO₃ may be an attractive cathode for lithium-ion batteries.     

High rate capability of carbonaceous composites as anode electrodes for lithium-ion secondary battery

Anode materials with high rate capability for Li-ion secondary batteries were investigated by using the mixture of graphite, cokes, and petroleum pitch. Since obvious potential plateaus were obtained at graphite contents above 40 wt.%, which would cause difficulties in perceiving the capacity variations as a function of electrical potential, the graphite content were determined at 20–30 wt.%. The composites with a given content of graphite and remaining content of petroleum pitch/cokes mixtures at 1:4, 1:1, and 4:1 mass ratios were heated at a temperature range of 800–1200 °C. For a given composition of carbonaceous composite, the discharge rate capability improved but the reversible capacity decreased with increasing the heat treatment temperature. Although the reversible capacity increased with increasing content of the petroleum pitch for given graphite content and heat treatment temperature, the discharge rate capability decreased. The carbonaceous composites prepared by the mixture of 30 wt.% graphite and 70 wt.% petroleum pitch/cokes mixture at 1:4 mass ratio with the heat treatment at 800 °C showed relatively high electrochemical properties, of which reversible capacity, initial efficiency, discharge rate capability (retention of discharge capacity in 5 C/0.2 C) and charge capacity at 5 C were 312 mAh/g, 79%, 89% and 78 mAh/g, respectively.     

Effects of cathode fabrication conditions and cycling on the electrochemical performance of LiNiO2 synthesized by combustion and calcination

LiNiO₂ was synthesized by the combustion method with various excess lithium amount z in Li_1 + zNiO₂ (z = 0.04, 0.08, 0.10, 0.12, and 0.15). The sample with z = 0.10 has the largest first discharge capacity of 195 mAh/g at 0.1 C rate and voltage range 2.7-4.4 V with the weight ratio of active material:acetylene black:binder = 85:10:5. The LiNiO₂ cathodes, in which the excess lithium amount z for the synthesis of LiNiO₂ was 0.10, were fabricated with various weight ratios of active material:acetylene black:binder (85:10:5, 85:12:3, and 90:7:3). The cathode with the ratio of active material:acetylene black:binder 85:10:5 has the best electrochemical properties. The variation, with C-rate, of discharge capacity vs. number of cycles curve for the LiNiO₂ cathode with the weight ratio of active material:acetylene black:binder = 85:10:5 was investigated. At 0.1 C rate, the LiNiO₂ cathode has the largest first discharge capacity, the discharge capacity degradation rate of 0.70 mAh/g/cycle and a discharge capacity at n = 50 of 134 mAh/g.     

One-step synthesis and improved electrochemical performance of Li(Ni1/3Co1/3Mn1/3)O2 by a modified radiated polymer gel method

We present the mechanism for the synthesis of a layered Li(Ni_1/3Co_1/3Mn_1/3)O₂ compound by a modified radiated gel method. Pure-phase Li(Ni_1/3Co_1/3Mn_1/3)O₂ material was achieved when the polymer gel was calcined at 900 °C between 15 and 30 h. The unit cell parameter c decreased, and a varied slightly with increased sintering time. Electrochemical characterization revealed that the optimized sample (25 h) had a high initial discharge capacity of 188 mAh/g (2.8-4.5 V, 20 mA/g), an excellent capacity retention of 90.1% after 30 cycles and a good rate performance.