离子掺杂对Li_3V_2(PO_4)_3/C电化学性能的影响

采用溶胶-碳热还原法制备了Li3V2-xMx(PO4)3/C(M=Ti,Fe,Ce;x=0.06)复合正极材料,通过XRD、SEM、恒流充放电和电化学阻抗等测试方法研究了Ti4+、Fe3+和Ce3+适量掺杂对材料结构、形貌和电化学性能的影响。结果表明:Ti4+、Fe3+和Ce3+的适量掺杂并未改变材料结构,对材料形貌也未产生明显的影响,但可以在一定程度上降低一次颗粒的尺寸,提高材料的电导率。所有掺杂材料的充放电性能和循环稳定性明显改善,其中Li3V1.94Fe0.06(PO4)3/C表现出最优的电化学性能。     

焙烧条件对Na3V2(PO4)3/C的制备及储锌性能影响

采用喷雾干燥法合成了Na₃V₂(PO₄)₃(NVP)前驱体,然后经过高温煅烧得到水系锌离子电池正极复合材料Na₃V₂(PO₄)₃/C(NVP/C),考察了煅烧温度和煅烧时间对NVP/C性能的影响。通过XRD、SEM和BET对样品结构和形貌进行了表征,通过循环伏安和充放电测试了样品的电化学性能。结果表明,不同煅烧温度和煅烧时间制备样品均为纯相的NVP/C,且并没有改变NVP/C的晶体结构;煅烧温度过高或煅烧时间过长会导致晶粒尺寸增大,性能迅速衰减。NVP/C制备最佳条件为煅烧温度700℃、煅烧时间8 h,在该条件下所制备的NVP/C(记为NVP/C-700-8)形貌更为规整,结晶性良好,具有较小的阻抗以及更好的离子扩散能力,进而表现出最佳的电化学性能。在0.1 A/g电流密度下表现出最佳的放电比容量(122.4 mA·h/g)。在1.0 A/g电流密度下经过200圈循环后放电比容量仍高达103.9 mA·h/g。     

锂离子电池正极材料磷酸钒锂的研究进展

Li3V2(PO4)3因具有优异的电化学性能,成为目前倍受关注的锂离子电池正极材料。介绍了单斜结构磷酸钒锂[α-Li3V2(PO4)3]的结构及充放电机理,概述了几种主要的制备Li3V2(PO4)3方法,包括了固相法、溶胶-凝胶法、微波法。同时阐述了几种主要方法用来对Li3V2(PO4)3电化学性能进行改性研究,对该材料的发展前景进行了展望。     

High performance Na3V2(PO4)3 cathode prepared by a facile solution evaporation method for sodium-ion batteries

Based on its abundance and low cost, sodium based batteries have aroused extensive attention for large scale energy-storage systems. In the current work, Na₃V₂(PO₄)₃ prepared by a facile solution evaporation method (denoted as NVP-SE) is used as cathode materials for sodium ion battery, with a control sample by solid state method. Raman spectrum and TEM are used to study the carbon layer coated on NVP-SE. The results show a highly graphitization and well-coated carbon layer, which is predominant by sp² carbon. Graphitized carbon leads to high electrical conductivity, which can improve the rate performance of Na₃V₂(PO₄)₃ materials. Besides, GITT tests show high Na-ion diffusion coefficient. Even at 30 C, the NVP-SE cathode still delivers a capacity of 70 mAh g⁻¹. Moreover, the material also shows great long term cycling performance. After 500 cycles at 1 C rate and 1000 cycles at 5 C, its discharge capacities are still 103.3 mAh g⁻¹ and 85.4 mAh g⁻¹, which maintain 92.6% and 85.0% of its initial capacity. Thus, simple preparation process and excellent electrochemical performance for Na₃V₂(PO₄)₃/C extend it as a potential material for high power applications.     

以溶液法制备的钠掺杂锂离子电池正极材料Li3-xNaxV2(PO4)3/C

以溶液法为制备方法、以葡萄糖为碳源合成了一种钠离子掺杂的锂离子电池正极材料Li_3-xNa_xV₂（PO₄）₃/C（x=0、0.01、0.03、0.05、0.07）。XRD结果显示组成相为单斜晶型,与标准Li₃V₂（PO₄）₃衍射峰完全一致。微量钠掺杂并未改变产物的相组成与晶体结构,但使得晶胞参数有所变化,这种变化有利于提高锂离子的扩散系数。SEM与TEM谱图显示材料颗粒基本为近似椭圆形,粒径分布均匀,碳包覆层完整。充放电测试显示Li_2.97Na_0.03V₂（PO₄）₃/C试样的倍率性能最好,在12C倍率下放电比容量约为100mAh/g,循环伏安测试也证明该试样的锂离子扩散系数较高,比纯相Li₃V₂（PO₄）₃提高了约2个数量级。     

锂离子电池正极材料Li3V2（PO4）3研究进展

锂离子电池正极材料Li3V2（PO4）3具有环保、安全性能好、成本低廉、结构稳定、电化学性能较好等特点,吸引了研究者的广泛关注.本文对Li3V2（PO4）5的结构、制备方法和电化学性能的研究现状进行了综述,并对其进行了展望.Li3V2（PO4）5很有希望产业化,进而取代目前市场上的主流材料LiCoO2。     

锂离子电池正极材料磷酸钒锂制备方法研究进展

单斜结构的磷酸钒锂[Li₃V₂（PO₄）₃]材料与其他锂离子电池正极材料相比具有较高的工作电压（3.0~4.8 V）、良好的离子迁移率和优良的热稳定性,是一种具有竞争优势和发展前景的大功率锂离子电池正极材料,成为了近年来研究的热点。综述了锂离子电池正极材料磷酸钒锂的结构特点及其充放电机理。磷酸钒锂的常用合成方法有碳热还原法、水热法、溶胶-凝胶法及流变相法等,着重阐述了磷酸钒锂的不同合成方法对所制备样品的形貌和电化学性能的影响。分析总结了不同合成方法的改进方法,以改善磷酸钒锂正极材料电子导电性和锂离子扩散系数较低的问题。最后,针对磷酸钒锂正极材料在锂离子电池的应用中所存在的问题展望了该材料未来可能的发展方向和研究热点。指出需要优化材料的制备方法以改善材料的颗粒形貌、提高电子导电率和扩散系数等,进而改善材料的循环性能、倍率性能和充放电性能等;需要改进制备流程、提高实验的安全性、简化反应流程和减少制备成本等,以实现磷酸钒锂正极材料的工业化应用。     

Effects of nitrogen and sulfur atom regulation on electrochemical properties of Na3V2(PO4)2F3 cathode material for Na-ion batteries

The cathode material Na₃V₂(PO₄)₂F₃ of sodium-ion battery is well-known for its large number of ion migration channels and high working voltage. However, the electrochemical performance of Na₃V₂(PO₄)₂F₃ is not very outstanding. Thus, in the present study, Na₃V₂(PO₄)₂F₃ cathode materials were successfully synthesized by using the sol-gel method and mechanical milling method to enhance the electrochemical performance. The physicochemical properties of synthesized Na₃V₂(PO₄)₂F₃ were investigated by using X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transition electron microscopy. X-ray diffraction spectroscopy indicates that the doping of nitrogen and sulfur did not alter the crystal form of Na₃V₂(PO₄)₂F₃. Transition electron microscopy image shows that Na₃V₂(PO₄)₂F₃ has a thin carbon layer, and x-ray photoelectron spectroscopy illustrates the successful doping of nitrogen and sulfur into the carbon layer. The cyclic voltammetry curves show that the nitrogen and sulfur co-doped Na₃V₂(PO₄)₂F₃ samples have good reversibility and low polarization. Materials with 15% thiourea has a high discharge specific capacity (126.9 mA h g^?1 at 0.2 C) at the first cycle and excellent cycle stability (126.3 mA h g^?1 after 100 cycles, a capacity retention of 99.5%) among the synthesized cathode materials. In the present study, the electrochemical performance of the Na₃V₂(PO₄)₂F₃ cathode material was enhanced by regulation of co-doping of nitrogen and sulfur atoms.     

Na3V2(PO4)3 with specially designed carbon framework as high performance cathode for sodium-ion batteries

The structures of materials have great influence on their properties. For materials with low electron conductivity, fast electron transport pathway can be constructed through carbon structure design. Here we report a simple but effective method to improve the electrochemical performances of Na₃V₂(PO₄)₃. Polyvinyl Pyrrolidone (PVP) can improve the viscosity of the precursor solution, thus forming aggregate structured material. In Na₃V₂(PO₄)₃, primary particles with a diameter of approximately 300?nm are aggregated through a special carbon network to form micro-sized secondary particles. This kind of structure will provide easy access for electron transportation, thereby improving electrochemical performance of the material. As a cathode material for sodium-ion batteries, Na₃V₂(PO₄)₃ delivers excellent rate (86.6 mAh g^?1 at 30?C) and cycling performance (capacity retention of 88.4% after 2000 cycles at 10?C). The material also exhibits a specific capacity of 100.2 mAh g^?1 at 5?C under 55?°C. The above-mentioned performance is far better than the control sample without PVP. The special carbon network provides electron transport channels which improves the electrochemical performance of the material. This method may provide new ideas for the preparation of phosphate materials.     

High tap density of Ni3(PO4)2 coated LiNi1/3Co1/3Mn1/3O2 with enhanced cycling performance at high cut-off voltage

The LiNi1/3Co1/3Mn1/3O2 is first obtained by the control ed crystallization method and then coated with Ni3(PO4)2 particles. The effects of the coating on rate capability and cycle life at high cut-off voltage are investigated by elec-trochemical impedance spectroscopy and galvanostatic measurements. The element ratio of Ni:Mn:Co is tested by inductively-coupled plasma spectrometer (ICP) analysis and it testified to be 1:1:1. It is indicated that Ni3(PO4)2-coated LiNi1/3Co1/3Mn1/3O2 has an outstanding capacity retention, where 99%capacity retention is maintained after 10 cycles at 5C discharge rate between 2.7 V and 4.6 V. The electrochemical impedance spectroscopy (EIS) results show that the current exchange density i0 of the coated sample is higher than that of LiNi1/3Co1/3Mn1/3O2, which is beneficial to its electrochemical performances. All the conclusions show that the Ni3(PO4)2 coating can prominently enhance the high rate performance of the LiNi1/3Co1/3Mn1/3O2, especially at high cut-off voltage.     

NaTi2(PO4)3纳米晶的室温固相合成及表征

以Ti(SO4)2和Na3PO4·12H2O为原料,在表面活性剂聚乙二醇(PEG)-400的存在下,进行固相反应,然后将混合物在60 ℃下保温4 h, 接着用水洗去混合物中的可溶性无机盐并于100 ℃下干燥,即得纳米晶NaTi2(PO4)3 的前驱体,将前驱体煅烧可得NaTi2(PO4)3纳米晶.前驱体和它的煅烧产物通过TG/DTA,IR,XRD和UV-vis表征.结果表明,500 ℃下煅烧2 h得到的产物为无定形结构,700 ℃下煅烧2 h得到具有高结晶度的斜方NaTi2-(PO4)3[空间群R-3c(167)],其平均一次粒径为47 nm.前驱体及煅烧产物均具有强的紫外吸收能力.     

Mg2+-doped Na3V2(PO4)3/C decorated with graphene sheets: An ultrafast Na-storage cathode for advanced energy storage

NASICON-type Na₃V₂(PO₄)₃ is one of the most promising cathode materials for sodium-ion batteries, delivering about two Na⁺-ions extraction/insertion from/into the unit structure. However, the low electronic conductivity which leads to bad rate capability and poor cycle performance, limits its practical application for sodium-ion batteries. To overcome the kinetic problem, we attempt to prepare the carbon-coated Na₃V₂(PO₄)₃ nanocrystals further decorated by graphene sheets and doped with Mg²⁺ ion via the two steps of sol-gel process and solid-state treatment for the first time. Such architecture synergistically combines the advantages of two-dimensional graphene sheets and 0-dimensional Mg²⁺-doped Na₃V₂(PO₄)₃/C nanoparticles. It greatly increases the electron/Na⁺-ion transport kinetics and assures the electrode structure integrity, leading to attractive electrochemical performance. When used as sodium-ion batteries cathode, the hybrid composite delivers an initial discharge capacity of 115.2 mAh g⁻¹ at 0.2 C rate, and retains stable discharge capacities of 113.1, 109.0, 102.4, 94.0 and 85.2 mAh g⁻¹ at high current rates of 1, 2, 5, 10 and 20 C rate, respectively. Thus, this nanostructure design provides a promising pathway for developing high-performance Na₃V₂(PO₄)₃ material for sodium-ion batteries.     

快速测定磷酸(氢)钙中磷含量

本方法适合于pH4．2时水溶性的磷酸盐中磷含量的测定、磷酸（氢）钙中磷含量的测定。     

HPW/Ti_3(PO_4)_4的制备及其催化酯化性能

制备了系列磷酸钛原位负载不同含量x(wt%)磷钨酸H3PW12O40(HPW)的酯化催化剂HPW-x/Ti3(PO4)4,通过催化丙酸与正戊醇的酯化反应考察了其催化酯化性能,并采用IR分析对催化剂进行了表征。结果表明,300℃焙烧2h条件下,磷钨酸含量15%的催化剂HPW-15/Ti3(PO4)4具有最佳的催化活性,催化合成低碳链羧酸酯丙酸戊酯的适宜条件为:0.2mol丙酸,催化剂用量0.4g,n(正戊醇)∶n(丙酸)=1.6∶1,反应时间4h,酯化率达97.7%。该催化剂循环利用6次酯化率减小幅度不足7.5%。该催化剂对长碳链羧酸酯庚酸戊酯的合成循环利用6次酯化率为93.2%～83.5%。     

Electrochemical performance of nanocrystalline Li3V2(PO4)3/carbon composite material synthesized by a novel sol–gel method

A novel sol–gel method based on V₂O₅·nH₂O hydro-gel was developed to synthesize nanocrystalline Li₃V₂(PO₄)₃/carbon composite material. In this route, V₂O₅·nH₂O hydro-gel, NH₄H₂PO₄, Li₂CO₃ and high-surface-area carbon were used as starting materials to prepare precursor, and the Li₃V₂(PO₄)₃/carbon was obtained by sintering precursor at 750 °C for 4 h in flowing argon. The sol–gel synthesis ensures homogeneity of the precursors and improved reactivity. The sample was characterized by XRD, SEM and TEM. X-ray diffraction results show Li₃V₂(PO₄)₃ sample is monoclinic structure with the space group of P2₁/n. The TEM image indicates that the Li₃V₂(PO₄)₃ particles modified by conductive carbon are about 70 nm in diameter. The Li₃V₂(PO₄)₃/carbon system showed that the discharge capacities in the first and 50th cycle are about 155.3 and 143.6 mAh/g, respectively, in the range of 3.0–4.8 V. The sol–gel method is fit for the preparation of Li₃V₂(PO₄)₃/carbon composite material which may offer some favorable properties for commercial application.     

VO(H_2PO_4)_2热分析研究

运用ＴＧ、ＤＴＡ,研究了ＶＯ（Ｈ２ＰＯ４）２在流动空气气氛中的热反应行为、非等温反应动力学和热效应。ＶＯ（Ｈ２ＰＯ４）２从６０９Ｋ开始失重,到６９５Ｋ失重完毕,失重率为１４．０１％,失重后的产物为ＶＯ（ＰＯ３）２。运用Ｓｈａｒｐ法、Ｃｏａｔｓ－Ｒｅｄｆｅｒｎ法和Ｄｏｙｌｅ－Ｚｓａｋｏ法对基础实验数据进行分析,推断出该热分解反应机理为成核和生长（ｎ＝１）,动力学函数为Ａｖｒａｍｉ－Ｅｒｏｆｅｅｖ方程;非等温热分解反应动力学方程：ｄα／ｄＴ＝Ａ／βｅ－Ｅ／ＲＴ（１－α）;动力学补偿方程：ｌｎＡ＝０．１８１Ｅ－４．６８ｂ;热分解反应转变热为０．２９１ｋＪ·ｇ－１。     

Modification of the morphology of Na3V2(PO4)2F3 as cathode material for sodium-ion batteries by polyvinylpyrrolidone

NASICON-type Na₃V₂(PO₄)₂F₃ (NVPF) is proposed to be a potential cathode material for sodium-ion battery because of its good structural stability, relatively high capacity and voltage platform. Nonetheless, the poor-rate performance, resulting from its low conductivity, has become a massive obstacle to its practical application. In this work, carbon coating together with morphology controlling were introduced to solve the issue of NVPF. This experiment used a hydrothermal method to prepare Na₃V₂(PO₄)₂F₃@C (NVPF@C) and explored the impact of surfactants (polyvinylpyrrolidone (PVP)) on the positive material performance of sodium-ion battery. Through various characterisation, NVPF@C compared its performance with that of untreated products, and verified that appropriate surfactant modification could enhance the performance of the electron conduction and sodium ion diffusion, thus effectively improved the performance of NVPF. Through comparison, it was found that appropriate surface modification with PVP can achieve the effects of specific crystal surface exposure and clusters of porous micron ball structure, and improve the electrochemical performance of NVPF best. Under the charge and discharge ratio of 0.2C, its initial reversible capacity was 127.8 mA h g^?1. After 100 cycles, its discharge capacity was 106.1 mA h g^?1, and the cycling retention rate reached 82.8%. Compared to the original NVPF, its performance has been dramatically improved.     

铜（Ⅱ）掺杂Li3V2（PO4）3/C的结构与性能

用一步碳热还原法制备了Li3V2-xCux(PO4)3/C(x=0.00、0.02、0.05、0.08、0.10、0.15)复合正极材料,并研究了掺杂对材料结构、微观形貌、充放电性能的影响。结果表明掺杂少量铜(Ⅱ)不会影响材料Li3V2(PO4)3的基本结构,但会在Li3V2(PO4)3中形成电子缺陷,提高晶体内部原子的无序化程度,降低极化和电荷转移电阻。从而改善材料的电化学性能。Li3V1.98Cu0.02(PO4)3/C的10 C放电容量比Li3V2(PO4)3/C提高了20 mA.h/g,具有较好的倍率性能。     

Construction of simultaneous modified Na3V2(PO4)3/C cathode with K/Zr substitution and carbon nanotubes enwrapping for high performance sodium ion battery

Na₃V₂(PO₄)₃ (NVP) has been deemed to be a prospective cathode material due to the unique NASICON-type framework for sodium ion battery (SIB). Nevertheless, the inferior intrinsic conductive property seriously impedes the development of NVP. Herein, the K/Zr co-substituted and carbon nanotubes (CNTs) enwrapped NVP/C composite is successfully synthesized through a facile sol-gel route. Notably, the introduced K⁺ in Na1 site possesses a pillar effect on the crystal structure to efficiently stabilize the framework. Meanwhile, Zr⁴⁺ with larger ionic radius successfully replaces of V³⁺, which is beneficial to expanding the interplanar spacing to facilitate the migration of Na⁺. Moreover, the enwrapped tubular CNTs can restrict the agglomerations of active grains to diminish the pathways for ionic and electronic transportation. Synthetically, the CNTs and amorphous coated carbon layers jointly construct a cross-linked 3D network to provide accelerated channels for electronic transportation. Consequently, the modified Na_2.96K_0.04V_1.93Zr_0.0525(PO₄)₃/C@CNTs composite exhibits superior electrochemical performance with excellent kinetic properties. Accordingly, it delivers a great capacity value of 110.8 mAh g^?1 at 0.1 C. Besides, it exhibits a reversible capacity of 102 mAh g^?1 at 2 C and maintains 89.7% after 300 cycles. As for a higher rate of 5 C, it releases an initial capacity of 99 mAh g^?1 and a high retention of 90.9% can be obtained after 1300 cycles. Significantly, the optimized sample delivers a high capacity of 91.2 mAh g^?1 at an ultra-high rate of 60 C and sustains 78.3% after 3000 cycles. Furthermore, the symmetric full cell is successfully fabricated and reveals superior high-rate capability with excellent stability. Therefore, this modified Na_2.96K_0.04V_1.93Zr_0.0525(PO₄)₃/C@CNTs composite would be a promising cathode material for practical applications in SIB.