Supercritical-hydrothermal accelerated solid state reaction route for synthesis of LiMn2O4 cathode material for high-power Li-ion batteries

Synthesis of the spinel structure lithium manganese oxide (LiMn₂O₄) by supercritical hydrothermal (SH) accelerated solid state reaction (SSR) route was studied. The impacts of the reaction pressure, reaction temperature and reaction time of SH route, and the calcination temperature of SSR route on the purity, particle morphology and electrochemical properties of the prepared LiMn₂O₄ materials were studied. The experimental results show that after 15 min reaction in SH route at 400 °C and 30 MPa, the reaction time of SSR could be significantly decreased, e.g. down to 3 h with the formation temperature of 800 °C, compared with the conventional solid state reaction method. The prepared LiMn₂O₄ material exhibits good crystallinity, uniform size distribution and good electrochemical performance, and has an initial specific capacity of 120 mA·h/g at a rate of 0.1C (1C=148 mA/g) and a good rate capability at high rates, even up to 50C.     

模拟废旧锂离子电池湿法冶金浸出液再生铝掺杂LiNi0.5Co0.2Mn0.3O2正极材料

采用共沉淀法制备均相Al掺杂的LiNi0.5Co0.2Mn0.3O2正极材料,以利用Al对再生镍钴锰(NCM)正极材料的正面改性作用,并改善锂离子电池回收过程中繁琐和高成本的除杂过程.当浸出液中的Al3+含量为过渡金属(Ni、Co和Mn)总量的1％(摩尔分数)时,制备的Al掺杂NCM正极材料中晶格氧和Ni2+的浓度增加...     

喷墨打印制备LFP/Mxene阴极锂电池及其电化学性能

制备了MXene含量2%、3%、4%、5%、6%（质量分数）的磷酸铁锂(LFP)/Ti₃AlC₂(MXene)复合材料并将其制备成墨水,通过喷墨打印方法得到锂离子阴极电池,并研究MXene含量对LFP电化学性能的影响。结果表明,随着MXene含量的增加,LFP/MXene 复合材料的电化学性能先升高后降低。以4%MXene的添加剂制备得到的LFP/MXene 复合材料电化学性能测试最佳,其电容量达到181.2 mAh·g^-1,100次循环后其库仑效率为99.4%。MXene材料具有手风琴层状结构,使得磷酸铁锂的接触比增加,此外,MXene材料比石墨烯材料具有更多的官能团结构,有助于LFP的电化学性能改进。但如果MXene加入过多,MXene材料发生结块,会降低LFP/MXene 复合材料电化学性能。     

耐久型高倍率性能锰酸锂微球的合成(英文)

以Mn2+和NH4HCO3为原料,通过控制结晶法合成球形MnCO3前驱体模板。以LiNO3和MnCO3为原料,按照一定的摩尔比机械混合,在700°C下煅烧8h,合成高倍率性能和长循环性能的球形尖晶石LiMn2O4材料。分别考查原料的摩尔比、反应时间以及反应温度对前驱体MnCO3形貌和产率的影响。采用X射线粉末衍射和扫描电镜对合成的MnCO3和LiMn2O4进行表征,对LiMn2O4样品进行室温条件下的充放电性能测试。电化学测试结果表明:尖晶石锰酸锂微球在10C的放电倍率下的首次放电容量达90mA·h/g(1C放电容量为148mA/g),800次循环后容量保持率达到75%。该方法合成的LiMn2O4微球作为高功率型锂离子电池的正极材料有着较好的应用前景。     

Synthesis and characterization of cobalt-free Ba0.5Sr0.5Fe0.8Cu0.2O3−δ perovskite oxide cathode nanofibers

The cobalt-free perovskite-oxide, Ba_0.5Sr_0.5Fe_0.8Cu_0.2O_3−δ (BSFC) is a very important cathode material for intermediate-temperature proton-conducting solid oxide fuel cells. Ba_0.5Sr_0.5Fe_0.8Cu_0.2O_3−δ nanofibers were synthesized for the first time by a sol-gel electrospinning. Process wherein a combination of polyvinylpyrrolidone and acetic acid was used as the spinning aid and barium, strontium, iron and copper nitrates were used as precursors for the synthesis of BSFC nanofibers. X-ray diffraction studies on products prepared at different calcination temperatures revealed a cubic perovskite structure at 900 °C. The temperature of calcination has a direct effect on the crystallization and surface morphology of the nanofibers. High porosity, and surface area, in addition to an electrical conductivity of 69.54 S cm⁻¹ at 600 °C demonstrate the capability of BSFC nanofibers to serve as effective cathode materials for intermediate-temperature solid oxide fuel cells.     

介孔Li3V2（PO4）3正极材料的研磨溶胶凝胶法合成和电化学性能（英文）

以V2O5·nH2O、LiOH·H2O、NH4H2PO4和蔗糖为原料,采用研磨溶胶凝胶技术制备了无定形Li3V2(PO4)3前驱体,再经过焙烧获得具有单斜结构的介孔Li3V2(PO4)3正极材料,并用XRD、SEM、TEM、比表面积和电化学性能测试来表征材料的性能。研究表明,在700°C下焙烧的样品具有良好的介孔结构、最大的比表面积(188cm2/g)和最小的孔径(9.3nm)。在0.2C倍率下,该介孔样品的首次放电容量达155.9mA·h/g,经过50次循环后其容量仍然可达154mA·h/g,表现出非常稳定的放电性能。     

Synthesis of LiNi1/3CO1/3Mn1/3O2 cathode material via oxalate precursor

Using oxalic acid and stoichiometrically mixed solution of NiCl2, CoCl2, and MnCl2 as starting materials, the triple oxalate precursor of nickel, cobalt, and manganese was synthesized by liquid-phase co-precipitation method. And then the LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery were prepared from the precursor and LiOH-H2O by solid-state reaction. The precursor and LiNi1/3Co1/3Mn1/3O2 were characterized by chemical analysis, XRD, EDX, SEM and TG-DTA. The results show that the composition of precursor is Ni1/3Co1/3Mn1/3C2O4·2H2O. The product LiNi1/3Co1/3Mn1/3O2, in which nickel, cobalt and manganese are uniformly distributed, is well crystallized with a-NaFeO2 layered structure. Sintering temperature has a remarkable influence on the electrochemical performance of obtained samples. LiNi1/3Co1/3Mn1/3O2 synthesized at 900 ℃ has the best electrochemical properties. At 0.1C rate, its first specific discharge capacity is 159.7 mA·h/g in the voltage range of 2.75-4.30 V and 196.9 mA·h/g in the voltage range of 2.75-4.50 V; at 2C rate, its specific discharge capacity is 121.8 mA·h/g and still 119.7 mA·h/g after 40 cycles. The capacity retention ratio is 98.27%.     

改进溶剂热法制备锂离子电池负极材料用多级孔Co3O4微球

将溶剂热法与高温煅烧法相结合制备多级孔Co3O4微球,采用XRD、SEM、TEM和电化学测试等技术研究该多级孔Co3O4微球的结构和性能.结果表明:当煅烧温度为700℃时,所合成的Co3O4(Co3O4-700)是由丰富的纳米颗粒(50～200 nm)和大量孔洞(～100 nm)构成的微米级微球(1～2μm);该Co3...     

Synthesis and electrochemical properties of Li[NixCoyMn1-x-y]O2 （x, y= 2/8, 3/8） cathode materials for lithium ion batteries

The uniform layered Li(Ni_2/8Co_3/8Mn_3/8)O₂, Li(Ni_3/8Co_2/8Mn_3/8)O₂, and Li(Ni_3/8Co_3/8Mn_2/8)O₂ cathode materials for lithium ion batteries were prepared using the hydroxide co-precipitation method. The effects of calcination temperature and transition metal contents on the structure and electrochemical properties of the Li-Ni-Co-Mn-O were systemically studied. The results of XRD and electrochemical performance measurement show that the ideal preparation conditions were to prepare the Li(Ni_3/8Co_3/8Mn_2/8)O₂ cathode material calcined at 900°C for 10 h. The well-ordered Li(Ni_3/8Co_3/8Mn_2/8)O₂ synthesized under the optimal conditions has the I ₀₀₃/I ₁₀₄ ratio of 1.25 and the R value of 0.48 and delivers the initial discharge capacity of 172.9 mA·h·g⁻¹, the discharge capacity of 166.2 mA·h·g⁻¹ after 20 cycles at 0.2C rate, and the impedance of 558 Ω after the first cycle. The decrease of Ni content results in the decrease of discharge capacity and the bad cycling performance of the Li-Ni-Co-Mn-O cathode materials, but the decreases of Mn content and Co content to a certain extent can improve the electrochemical properties of the Li-Ni-Co-Mn-O cathode materials.     

Synthesis of LiFePO<Subscript>4</Subscript>/C as cathode material by a novel optimized hydrothermal method

Olivine LiFePO 4 , as a cathode material for lithium ion batteries, was prepared by a novel optimized hydrothermal method; afterwards, the product mixed with glucose was two-step (350℃ and 700℃) calcinated under high-purity N 2 atmosphere to obtain the LiFePO 4 /C composite. The study on the hydrothermal preparation method, which focused on the influences of molar ratios, initial pH value, reaction temperature, and duration, was made to promote the resultant performances and to investigate the relations between the performances and the reaction conditions. The resultant samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical tests, which include charge-discharge, electrochemical impedance spectroscopy, and cyclic voltammetry. The result shows that the optimal hydrothermal condition is to set the Li:Fe:P molar ratio at 3:1:1 and the reaction temperature at 180℃ for 5 h duration with an initial pH value of 7. The optimized sample, with an average particle size of 100 to 300 nm and a discharge capacity of 118.2 mAh·g-1 at 0.1C, exhibits a stable and narrow-gapped charge-discharge platform and small capacity losses after cycles.     

Synthesis and characterization of layered Li（Ni1/3Mn1/3CO1/3）O2 cathode materials by spray-drying method

Spherical Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 was prepared via the homogenous precursors produced by solution spray-drying method. The precursors were sintered at different temperatures between 600 and 1 000 ℃ for 10 h. The impacts of different sintering temperatures on the structure and electrochemical performances of Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 were compared by means of X-ray diffractometry(XRD), scanning electron microscopy(SEM), and charge/discharge test as cathode materials for lithium ion batteries. The experimental results show that the spherical morphology of the spray-dried powers maintains during the subsequent heat treatment and the specific capacity increases with rising sintering temperature. When the sintering temperature rises up to 900 ℃ , Li(Ni_(1/3)Mn_(1/3)Co_(1/3))O_2 attains a reversible capacity of 153 mA·h/g between 3.00 and 4.35 V at 0.2C rate with excellent cyclability.     

Improving electrochemical performance of Ni-rich layered oxide cathodes via one-step dual modification strategy

A one-step overall strategy from surface to bulk was proposed to simultaneously synthesize the Nb-doped and LiNbO₃-coated LiNi_0.83Co_0.12Mn_0.05O₂ cathode materials. The incorporation of LiNbO₃ coating can regulate the interface and facilitate the diffusion of Li-ions. Simultaneously, the stronger Nb—O bond can effectively suppress Li⁺/Ni²⁺ cation mixing and strengthen the stability of crystal structure, which helps to mitigate the anisotropic variations of lattice parameters during Li⁺ de/intercalation. The results showed that the dual-modified materials exhibited good structural stability and distinguished electrochemical performance. The optimal NCM-Nb2 sample showed an excellent capacity retention of 90.78% after 100 cycles at 1C rate between 2.7 and 4.3 V, while only 67.90% for the pristine one. Meanwhile, it displayed a superior rate capability of 149.1 mA·h/g at the 10C rate. These results highlight the feasibility of one-step dual modification strategy to synchronously improve the electrochemical performance of Ni-rich layered oxide cathodes.     

High temperature oxidation of Ti–46Al–6Nb–0.5W–0.5Cr–0.3Si–0.1C alloy

A newly developed Ti–46Al–6Nb-0.5W-0.5Cr-0.3Si-0.1C alloy was oxidized isothermally and cyclically in air, and its high-temperature oxidation behavior was investigated. When the alloy was isothermally oxidized at 700 °C for 2000 h, the weight gain was only 0.15 mg/cm². The parabolic rate constant, k_p (mg²/cm⁴·h), measured from isothermal oxidation tests was 0.002 at 900 °C and 0.009 at 1000 °C. Such excellent isothermal oxidation resistance resulted from the formation of the dense, continuous Al₂O₃ layer between the outer TiO₂ layer and the inner (TiO₂-rich, Al₂O₃-deficient) layer. The alloy also displayed good cyclic oxidation resistance at 900 °C. Some noticeable scale spallation began to occur after 68 h at 1000 °C during the cyclic oxidation test.     

Effect of annealing temperature on ferroelectric properties of （Bi, Nd）4（Ti, V）3O12 thin films

Thin films of Nd^3＋/V^5＋-cosubstituted bismuth titanate, （Bi3.sNd0.5）（ Ti2.96V0.04）O12 （BNTV）, were fabricated on the Pt（111）/Ti/SiO2/Si（100） substrates by a chemical solution deposition technique and annealed at different temperatures of 650, 700, 750 and 800 ℃. The surface morphology and ferroelectric properties of the samples were studied in detail. The result shows that the film annealed at 800 ℃ indicates excellent ferroelectricity with a remanent polarization of 2Pr=40.9 i.tC/cm^2, a coercive field （Ec） of 114 kV/cm at an applied electrical field of 375 kV/cm. The substitution of Ti-site ion by V^5＋ ions could improve the upper limit of the optimal annealing temperature by decreasing the space charge density in BNT thin film. Additionally, the mechanism concerning the dependence of ferroelectric properties of BNTV thin films on the annealing temperature was discussed.     

Synthesis of Li excess LiFePO4/C using iron chloride extracted from steel scrap pickling

Olivine-type Li rich Li_1+xFePO₄/C composites are synthesized by a solid state reaction process using premilled Li₂CO₃ and pre-synthesized amorphous FePO₄·xH₂O powders. The amorphous FePO₄·xH₂O powders are prepared from an industrial waste liquid (by-product), a FeCl₃ (38%) solution, via a precipitation process. In addition, lithium carbonate is pre-milled using a high energy nano mill to control particle sizes and shape differences for enhancing the reaction activity in the starting materials. The main purpose of this study is to investigate the effect of excess Li on the electrochemical properties of LiFePO₄ cathode materials. The pre-synthesized FePO₄ powders are mixed with pre-milled lithium carbonate and glucose (8 wt%) using a ball-mill process. The structural characteristics of the Li_1+xFePO₄/C composites are examined by XRD and SEM. To investigate the effect of excess Li content on the electrochemical properties in Li_1+xFePO₄/C composites, a Li[LiPF₆ (Ethylene carbonate + Dimethyl carbonate)] Li_1+xFePO₄/C model cell is used. It is demonstrated that the 1% Li rich Li/[Li_1.01FePO₄/C] cell exhibits the best electrochemical performance and delivers an initial discharge capacity of 161 mAhg^?1, which is 25 mAhg^?1 higher than that of the Li/[LiFePO₄/C] cell.     

Preparation and electrochemical properties of LiFePO4/C composite with network structure for lithium ion batteries

The bare LiFePO4 and LiFePO4/C composites with network structure were prepared by solid-state reaction. The crystalline structures, morphologies and specific surface areas of the materials were investigated by X-ray diffractometry（XRD）, scanning electron microscopy（SEM） and multi-point brunauer emmett and teller（BET） method. The results show that the LiFePO4/C composite with the best network structure is obtained by adding 10% phenolic resin carbon. Its electronic conductivity increases to 2.86 × 10^-2 S/cm. It possesses the highest specific surface area of 115.65 m^2/g, which exhibits the highest discharge specific capacity of 164.33 mA.h/g at C/IO rate and 149.12 mA.h/g at 1 C rate. The discharge capacity is completely recovered when C/10 rate is applied again.     

共沉淀法制备LiNi0.8Co0.1Mn0.1O2过程中加料速度对其性能的影响

采用共沉淀法制备Ni0.8Co0.1Mn0.1(OH)2前驱体,与LiOH.H2O混合后在氧气气氛中焙烧得到LiNi0.8Co0.1Mn0.1O2正极材料,探讨共沉淀反应过程中快速加料和慢速加料制度对前驱体形貌和LiNi0.8Co0.1Mn0.1O2正极材料性能的影响。通过X射线衍射(XRD)、扫描电镜(SEM)和电化学测试对样品进行表征。结果表明:慢速加料法减小了材料的粒径,合成了平均粒径在0.5μm左右的球形Ni0.8Co0.1Mn0.1(OH)2前驱体,且粒径分布比较集中;所合成LiNi0.8Co0.1-Mn0.1O2正极材料具有良好的层状结构,且无杂相存在;缓慢加料法得到的样品的电化学性能有很大提高,在0.1 C、0.5 C和1 C下首次放电比容量分别达到223.5、194.3和190.7 mA.h/g,循环30次后,容量保持率为80.09%、80.80%和85.84%。     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的制备及性能研究

采用溶胶-凝胶法制备了锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2,并考察了烧结温度对材料结构、表面形貌和电化学性能的影响.XRD和SEM测试结果表明,900℃下烧结得到的样品是粒径在0.3～0.5 μm范围的球形粒子,具有最佳的阳离子有序度;充放电测试结果表明,其在0.1C倍率下首次放电容量达到148.8...     

Accessing the full spectrum of corrosion behaviour of tempered type 420 stainless steel

Bipolar electrochemistry produces a linear potential gradient between two feeder electrodes, providing access to the full spectrum of anodic-to-cathodic electrochemical behaviour. A type 420 martensitic stainless steel has been used to investigate microstructure evolution and corrosion behaviour with application of different tempering heat treatments. Tempering treatments at 250°C, 400°C and 700°C revealed the occurrence of pitting corrosion, with treatments at 550°C resulting in general and intergranular corrosion. Cr₂₃C₆ was present in all tempering conditions, with Cr₇C₃ and CrC only observed for tempering at 550°C. The 250°C tempering treatment had the highest corrosion resistance with a hardness value much higher than 500 HV.     

掺铝氧化锌包覆LiFePO4的合成与性能（英文）

以简单的固相法合成了橄榄石结构LiFePO4,并以导电掺铝氧化锌材料(AZO)对其表面进行包覆。充放电结果显示,表面包覆大幅度改善了LiFePO4材料的倍率和低温性能。在20C高倍率条件下,AZO包覆LiFePO4的放电比容量可达100.9mA·h/g;在低温20°C时进行0.2C充放电,未包覆LiFePO4和AZO包覆LiFePO4的放电比容量分别为50.3mA·h/g和119.4mA·h/g。经分析,这可能是由于采用导电AZO包覆措施而增加了LiFePO4材料的电导率,从而极大地提高了其比容量。另外,导电AZO包覆措施还增加了LiFePO4材料的振实密度。这些结果表明AZO包覆LiFePO4材料是一种很好的适用于锂离子动力电池的正极材料。