锂离子电池正极材料Li3V2（PO4）3存在的问题及改性研究进展

指出了Li3V2(PO4)3存在的主要问题及其改性办法,综述了包覆改性、掺杂改性以及控制样品的形貌和粒径3种改性手段近年来在Li3V2(PO4)3电化学改性上所取得的研究成果,评价了3种方式的优缺点,并展望了Li3V2(PO4)3今后的研究方向。     

锂离子电池复合正极材料xLiFePO4·yLi3V2(PO4)3的制备与性能研究

以FePO4·xH2O、V2O5、NH4H2PO4和Li2CO3为原料,以乙二酸为还原剂,在常温常压下经机械活化并还原嵌锂,形成无定形的5LiFePO4·Li3V2(PO4)3前驱体混合物,然后低温热处理合成出晶态的复合正极材料5LiFePO4·Li3V2(PO4)3.分别研究了复合材料的物相结构、形貌、电化学性能.SEM图像表明合成的材料粒径小、分布均匀,一次粒径为100～200nm.充放电测试结果表明,650℃烧结12h制得的复合正极材料5LiFePO4·Li3V2(PO4)3电化学性能优良,1C放电比容量高达158mAh/g,达到该复合材料的理论比容量(156.8mAh/g).复合材料具有良好的倍率性能和循环性能,在10C放电比容量高达114mAh/g,100次循环后容量几乎无衰减.循环伏安测试表明,复合材料的脱嵌锂性能优良,且明显优于单一的LiFePO4和Li3V2(PO4)3.     

Mn掺杂Li3Fe2(PO4)3正极材料的制备与表征

通过固相反应法合成出Li3+xFe2-xMnxn(Po4)3(x-0～O.1)、Li3Fel.ω5Mn0.05(PO4)3和Li2.95Fe1.ωMnoN.05(PO4)3正极材料.采用行星式球磨方法,均匀混合正极材料和导电乙炔黑以提高活性材料的电子导电率和降低颗粒尺寸.Mn掺杂的Li3Fe2(PO4)3样品的恒电流充放电测试和伏安循环测试(2～4V)发现,所有样品中Fe3+/Fe2+氧化还原电对均有两个稳定的充放电平台(2.8、2.7V)、Li3+,Fe2-xMnxII(PO4)3和Li3Fe1.95Mn0.05(PO4)3中Mn3+/Mn2+电对的充放平台位于3.5V左右.不同价态Mn的掺杂均可明显提高正极材料的电化学性能,其中Mn掺杂样品的电化学性能最好,其中Li3.05Fel.95MnⅡ0.05(PO4)3/C的C/20和C/2恒流放电比容量分别可达11O和66mAh/g.     

聚乙二醇为碳源合成0.7LiFePO_4·0.3Li_3V_2(PO_4)_3/C复合正极材料及性能研究

以Li OH·H2O、Fe C2O4·2H2O、NH4VO3和NH4H2PO4为原料,分别以不同聚合度的聚乙二醇(PEG-200、PEG-600、PEG-1000、PEG-2000、PEG-6000)为碳源,通过高温固相法合成0.7Li Fe PO4·0.3Li3V2(PO4)3/C复合正极材料(LFVP/C)。用X射线衍射、拉曼光谱和扫描电镜对材料的结构和形貌进行了表征。充放电测试表明,在电压范围为2.0~4.3 V时,PEG-200为碳源的LFVP/C的复合正极材料具有较高的比容量、优良的循环性能和倍率特性。10C条件下其放电容量可以保持120 m Ah/g。     

Na+掺杂对Li3V2（PO4）3/C晶体结构及性能的影响

利用一步碳热还原法制备了Li3-xNaxV2(PO4)3/C(x=0、0.01、0.02、0.03、0.05、0.08、0.10、0.15)复合正极材料,并用X射线衍射、扫描电镜、红外光谱、循环伏安法、电化学阻抗谱和恒电流充放电技术研究了掺杂对材料结构、微观形貌、充放电性能和Li+脱出嵌入过程的影响。研究表明掺杂少量Na+不影响材料Li3V2(PO4)3的基本结构,但可在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。与Li3V2(PO4)3/C相比,Li2.98 Na0.02 V2(PO4)3/C在倍率为15C下的第50次放电容量提高12.1mAh/g,具有较好的倍率性能和循环性能。     

掺杂磷酸钒锂材料的合成及改性研究

采用球磨喷雾辅助碳热还原法制备锂离子正极材料Li3V2(PO4)3,并通过金属离子掺杂技术对Li3V2(PO4)3进行改性.采用SEM、CV对掺杂Cr、Ti、Mg的材料(Li3V2(PO4)3(LVP-1)、Li3V1.8Cr0.2(PO4)3 (LVP-2)、Li3V1.8Ti0.2(PO4)3(LVP-3)、Li3V1.8Mg0.2(PO4)3(LVP-4))进行了形貌分析和电化学性能研究.结果表明:掺杂少量的Cr离子不影响材料的形貌,掺杂Ti、Mg离子改变了晶体材料的粒径;在充放电测试分析中,纯相材料的放电容量较高,但纯相材料的容量保持率比其他3种材料低;倍率性能测试同样表明Li3V1.8Mg0.2(PO4)3材料放电容量大且循环性能好.     

锂离子电池正极材料Li3V2-2x/3Mnx（PO4）3的溶胶凝胶法合成和电化学性能

以CH3COOLi·2H2O、V2O5、Mn(CH3COO)2·4H2O、(NH4)2HPO4和蔗糖为原料,采用溶胶–凝胶法合成了掺锰磷酸钒锂/碳(Li3V2-2x/3Mnx(PO4)3/C)复合正极材料,用XRD、XPS、SEM、电化学性能对样品进行了表征.测试结果表明,少量锰的掺杂并未改变Li3V2(PO4)3/C的单斜结构,Li3V1.94Mn0.09(PO4)3中的Mn和V分别以+2和+3价存在,其颗粒类似球形,直径比较均匀且小于200 nm,并表现出良好的电化学性能.在0.1C倍率和3.0～4.8 V电压内,该样品的首次充、放电容量分别为182.1和168.8 mAh/g,放电效率高达92.69%,而且100次循环后,其放电比容量仍是首次放电容量的77.4%.     

锂离子电池复合正极材料xLiFePO4·yLi3V2（PO4）3的制备与性能研究

以FePO4·xH2O、V2O5、NH4H2PO4和Li2CO3为原料,以乙二酸为还原剂,在常温常压下经机械活化并还原嵌锂,形成无定形的5LiFePO4·Li3V2（PO4）3前驱体混合物,然后低温热处理合成出晶态的复合正极材料5LiFePO4·Li3V2（PO4）3.分别研究了复合材料的物相结构、形貌、电化学性能.SEM图像表明合成的材料粒径小、分布均匀,一次粒径为100～200nm.充放电测试结果表明,650℃烧结12h制得的复合正极材料5LiFePO4·Li3V2（PO4）3电化学性能优良,1C放电比容量高达158mAh/g,达到该复合材料的理论比容量（156.8mAh/g）.复合材料具有良好的倍率性能和循环性能,在10C放电比容量高达114mAh/g,100次循环后容量几乎无衰减.循环伏安测试表明,复合材料的脱嵌锂性能优良,且明显优于单一的LiFePO4和Li3V2（PO4）3.     

碳源对液相法制备Li3V2（PO4）3/C的影响

以4种不同种类的有机物(柠檬酸、水杨酸、聚丙烯酸、蔗糖)为碳源,通过液相反应合成Li3V2(PO4)3/C复合材料。研究了不同碳源对复合材料的晶型结构、形貌及电化学性能的影响。结果表明,碳源对Li3V2(PO4)3/C材料的晶型结构没有影响,但对电化学性能影响较明显,其中采用柠檬酸为碳源制得的Li3V2(PO4)3/C复合材料电化学性能最好。进一步研究了柠檬酸的加入量对复合材料的电化学性能的影响,发现当柠檬酸加入量为钒与碳的物质的量比为1∶4时,样品的平均粒径较小,电化学性能最好,0.1C首次放电比容量为123.59mAhg-1,0.5C首次放电比容量也高达117.27mAhg-1,循环10次后,仍保持在117.19mAhg-1,容量几乎没有衰减,10C时比容量仍有105.43mAhg-1。     

金属元素掺杂Li_3V_2(PO_4)_3正极材料的研究进展

金属元素掺杂能从本质上改善Li3V2(PO4)3的电子电导率和锂离子扩散速率,从而提高材料的电化学性能。概述了近年来金属元素掺杂Li3V2(PO4)3的研究进展,分别从掺杂元素和表征技术两方面进行综述,介绍了Mg2+、Ni 2+、Cr3+、Co2+等金属离子掺杂对Li3V2(PO4)3的结构以及电化学性能的影响,并对进一步的研究方向和发展趋势提出了见解。     

Dielectric properties of Bi4(GeO4)3 and Bi4(SiO4)3

Dielectric constant, dielectric loss and conductivity of Bi₄(GeO₄)₃ and Bi₄(SiO₄)₃ single crystals have been measured as a function of frequency and in the temperature range from liquid nitrogen temperature to 400° C. The values of the static dielectric constant at room temperature are 16·4 and 13·7 for Bi₄(GeO₄)₃ and Bi₄(SiO₄)₃ respectively. The plots of log (σ) against reciprocal temperature at different frequencies of these crystals merge into a straight line beyond 250°C and the activation energies calculated in this region are found to be 0·95 eV and 1·2 eV for Bi₄(GeO₄)₃ and Bi₄(SiO₄)₃ respectively.     

Phase formation in ScPO4–Na3PO4–Li3PO4 ternary system

Phase formation in ternary system of complex Sc, Na and Li phosphates was studied at 950 °C and synthesis of new phases of definite composition was carried out. Obtained specimens were investigated with X-ray powder diffraction and infrared spectroscopy. Compositions of fields of homogeneity with NASICON-like structure were discovered.     

The elastic behaviour of Ce3S4 and La3S4

The hydrostatic pressure and temperature dependences of the elastic stiffnesses of the cubic, Th₃P₄ structure compounds Ce₃S₄ and La₃S₄ have been measured using the ultrasonic pulse echo overlap technique. Although Ce₃S₄, unlike La₃S₄ (T _c = 103 K), does not undergo a phase transition when its temperature is lowered to 16 K, its elastic stiffnesses (C₁₁-C₁₂)/2 and C₁₁ soften with decreasing temperature (in a similar manner but less markedly than those of La₃S₄); this lattice instability indicates an incipient phase transition. In both compounds the elastic constants increase under pressure: the long-wavelength acoustic-mode Grüneisen parameters are all positive, and the application of pressure does not induce acoustic phonon-mode softening.     

Novel magnetically separable g-C3N4/Fe3O4/Ag3PO4/Co3O4 nanocomposites: Visible-light-driven photocatalysts with highly enhanced activity

In this study, a series of novel quaternary g-C₃N₄/Fe₃O₄/Ag₃PO₄/Co₃O₄ nanocomposites were fabricated. The prepared nanocomposites were characterized by XRD, EDX, SEM, TEM, UV-DRS, FT-IR, PL, TG, and VSM methods to gain insight about structure, purity, morphology, optical, thermal, and magnetic properties. Photocatalytic activity of the samples was investigated under visible-light irradiation by degradations of rhodamine B, methylene blue, methyl orange, and phenol as four organic pollutants. The highest photocatalytic degradation efficiency was observed when the sample calcined at 300 °C for 2 h with 20 wt% of Co₃O₄. The photocatalytic activity of this nanocomposite is almost 16.8, 15.7, 4.6, and 5.1 times higher than those of the g-C₃N₄, g-C₃N₄/Fe₃O₄, g-C₃N₄/Fe₃O₄/Ag₃PO₄ (20%), and g-C₃N₄/Fe₃O₄/Co₃O₄ (20%) samples in photodegradation of rhodamine B, respectively. Finally, on the basis of the energy band positions, the mechanism of enhanced photocatalytic activity was discussed.     

The heat capacities of U3As4 and Th3As4

The heat capacities of the arsenides of uranium (U₃As₄) and thorium (Th₃As₄) have been measured in the temperature range 5–300 K. A sharp -shaped anomaly at 195.8 K, associated with the ferromagnetic transition, was observed in U₃As₄. The smooth specific heat curve C _p(T) for nonmagnetic analog Th₃As₄ has been used to determine the lattice contribution to the heat capacity of U₃As₄. The resulting magnetic entropy at 290 K has been estimated as 10.67 J/K mole of U atom, which is close to the theoretical R ln 4 value. This fact is interpreted in terms of crystal field interactions in the crystal lattice with S₄ point symmetry. Critical entropy and enegy parameters are compared with the theoretical predictions for 3d Ising and Heisenberg models. The critical coefficients are also considered.     

Eu4As3, a new trigonal anti-Th3P4-type compound

Eu₄As₃ = Eu²⁺₃Eu³⁺As₃ crystallizes in a rhombohedrally distorted anti-Th₃P₄ structure with $\text{a}\text{= 9.176(1)}\text{A}\text{?}$, α = 90.855(8)°. It is ferromagnetic below T_C ≈ 20 K. If the distortion is a consequence of charge ordering, then trigonal modifications should be expected also for Eu₃LnX₃ and Yb₃LnX₃ (X = As, Sb, Bi).