3LiMnPO_4·Li_3V_2(PO_4)_3正极材料的制备及其电化学性能研究

以五氧化二钒干凝胶、碳酸锰、磷酸二氢铵、碳酸锂、乙炔黑为原料,采用固相法在相对较低的温度条件下合成了x Li Mn PO4·y Li3V2(PO4)3锂离子电池复合正极材料。采用X射线衍射(XRD)、扫描电镜(SEM)对其晶体结构和表面形貌进行表征。结果表明,750℃下烧结15 h合成的3Li Mn PO4·Li3V2(PO4)3为结晶良好的两相结构,颗粒粒径较小且分布比较均匀,其在室温、0.2 C倍率下首次充放电容量分别为144.8 m Ah/g和139.8 m Ah/g,循环50次后容量为130.5 m Ah/g。

Ni_2O_3对Ni_(0.5)Zr_2(PO_4)_3红色陶瓷色料性能的影响

本文采用固相法以(NH_4)_2HPO_4、ZrO_2和Ni_2O_3为原料制备了新型Ni_(0.5)Zr_2(PO_4)_3红色陶瓷色料,研究了不同Ni_2O_3的加入量对色料呈色性能的影响。结果表明:Ni_2O_3的添加量为6%时在烧成温度为1400℃、保温时间为1h、色料的红色最好,其色度指数为:L*=68.53,a*=23.20,b*=11.07;通过XRD、TG-DTA和紫外-可见光分光光度法等测试的分析说明,色料呈现红色可能是因为合成了Ni_(0.5)Zr_2(PO_4)_3而Ni^(2+)在磷酸锆中呈现红色所致。

Ultrahigh rate binder-free Na_3V_2(PO_4)_3/carbon cathode for sodium-ion battery

Sodium ion batteries （SIBs） are very promising for large-scale energy storage in virtue of its high energy density, abundant sodium resources and low environmental impact, etc. However, it is still a big chal- lenge to develop high-performance and durable cathode materials for SIBs. Among different candidate materials, Na_3V_2（PO_4）_3 has attracted great attentions due to its high theoretical capacity （117 mAh/g）, stable framework structure and excellent ionic conductivity. However, Na_3V_2（PO_4）_3 delivers inferior rate capability and cycling stability due to its poor electronic conductivity. In this work, free-standing Na_3V_2（PO_4）_3/carbon nanofiber membranes are synthesized by an electrospinning-sintering mute. The sample could deliver excellent cycling capability with specific capacity of 112 mAh/g at 1 C after 250 cycles and ultrahigh rate capability with 76.9 mAh/g even at 100 C, which is superior to many state-of- the-art SIB cathode materials. This can be attributed to the hierarchically distributed Na_3V_2（PO_4）_3 crystals in carbon nanofiber network, which possesses outstanding electronicfionic conductivity and thus leads to an ultrahigh rate capabilitY.

Matrix Induced Synthesis of Eu^(3+) Doped Zn_3(PO_4)_2 and LaPO_4 Phosphors by in-Situ Composing Hybrid Precursors

Using rare earth and zinc coordination polymers with aromatic carboxylic acids as the precursors, composing with the polyethylene glycol (PEG) as the dispersing media, micro crystalline phosphors Zn_3(PO_4)_2∶Eu 3+ and LaPO_4∶Eu 3+ were synthesized by in-situ co-precipitation method. X-ray diffraction and scanning electronic micrograph were used to characterize the resultant samples, whose particle size are in the range of micrometer. The emission spectra of Zn_3(PO_4)_2∶Eu 3+ (λ_ ex=245 nm) and LaPO_4∶Eu 3+ (λ_ ex=390 nm) shows that the emission for Eu 3+ in Zn_3(PO_4)_2 is dominated by the 5D_0→7F_1 (592 nm) magnetic-dipole transition,While the dominant emission for Eu 3+ in LaPO_4 is the typical hypersensitive transition 5D_0→7F_2 (618 nm).

SYNTHESIS AND CHARACTERIZATION OF THE LAMELLAR MICROCRYSTALLINE ZINC PHOSPHATE α-Zn_3(PO_4)_2·4H_2O

Objective To study the structural and anticorrosive property of microcrystalline α-Zn_3(PO_4)_2·4H_2O. Methods Zinc phosphate was prepared from zinc acetate and orthophosphate acid in aqueous solution. Structural characteristics of products were investigated by XRD, RAMAN, FTIR, TG-DTA, SEM, surface area, particle size distribution, and density measurements. Results The title compound, a highly crystalline, micronized and lamellar α-Zn_3(PO_4)_2·4H_2O, has an orthorhombic monoclinic system, space group a_0=10.597(),b_ 0 =18.308(), c_ 0 =5.0304(), V=975.86 3. Its specific area is 0.701m2/g, density 3.1612g/m3, and average size 4.75μm . Conclusion Comparing with commercial Zinc phosphate, the synthesized lamellar microcrystalline zinc phosphate had excellent anticorrosive property and dispersibility.

绿色荧光粉Zn_2Ca(PO_4)_2:Tb^(3+)的制备及发光性能研究

采用高温固相法合成了绿色荧光粉Zn2Ca(PO4)2:Tb3+,测定了该荧光粉的XRD图谱、激发光谱及发射光谱。XRD图谱表明在高温还原气氛下合成了纯相的荧光粉Zn2Ca(PO4)2:Tb3+。该荧光粉的激发谱位于340～400nm。在紫外激发下主要发射峰位于490、544、584、622nm,对应于Tb3+的5D4→7F6、5D4→7F5、5D4→7F4、5D4→7F3的特征发射。考察了Tb3+的掺杂浓度对样品发光效率的影响,分析了Tb3+的544nm发射的自身浓度猝灭机理并探讨了敏化剂Ce3+离子的加入对荧光粉发光的影响。此绿色荧光粉Zn2Ca(PO4)2:Tb3+是一种很有潜力的适于UVLED管芯激发的发光粉。

乙腈-水系混合电解液对Zn-Na_(3)V_(2)(PO_(4))_(3)电池电化学稳定性的影响

Na_(3)V_(2)(PO_(4))_(3)正极材料具有稳定的三维框架结构、较高的工作电压和相对成熟的制备工艺,近年来也逐渐用于水系锌离子电池中。然而,二价Zn^(2+)的脱嵌和活泼的水系反应环境会加速磷酸盐晶格的破坏。本文在Zn-Na_(3)V_(2)(PO_(4))_(3)电池体系的水系电解液中加入适量的乙腈(AN),研究电解液中AN与水的比例对离子溶剂化结构和电化学行为的影响规律,并通过非原位XRD探究Na_(3)V_(2)(PO_(4))_(3)晶体结构的演变。结果表明:过少的AN会加快正极材料晶格框架的破坏,而过多的AN会减缓电极反应动力学;在含有适量AN的电解液中,Zn-Na_(3)V_(2)(PO_(4))_(3)电池不但在50 mA/g的电流密度下具有91.4 mA·h/g的较高比容量,同时在500 mA/g的电流密度下可以稳定循环1000次且无明显容量衰退。

固态电解质Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)中Li+的迁移特性

Li_(1+x)Al_(x)Ti_(2-x)(PO_(4))_(3)(LATP)是一种颇具前景的NASICON型锂离子固态电解质.本文通过第一性原理计算研究了不同Al掺杂浓度(x=0.00,0.16,0.33,0.50)对LATP的结构特性、电学特性以及Li^(+)迁移特性的影响.结果表明,Al能够稳定掺杂进入LiTi2(PO4)3(LTP)的晶体结构当中.当Al掺杂浓度x=0.16时,Li—O键的平均键长最长,成键强度最弱,而Ti—O键强度随Al掺杂浓度变化不大.Al掺杂浓度对LATP带隙的影响不大,但Al附近的O原子聚集了更多的负电荷,形成AlO6极化中心.Li^(+)不同的迁移方式(空位迁移、间隙位迁移和协同迁移)在Al掺杂浓度不同时展现出复杂的能垒变化,Li^(+)在空位迁移中迁移势垒随Al掺杂浓度的增大而升高,而在间隙位迁移中Li^(+)的迁移势垒变化相反,由于协同迁移中涉及空位和间隙位两种位点,Li^(+)的迁移势垒表现为随Al掺杂浓度的升高先降低后升高的复杂变化.当x=0.50时,LATP具有最低的Li^(+)迁移势垒0.342 eV,这个势垒值是间隙位迁移的结果.因此,通过改变Al掺杂浓度,可改变间隙Li^(+)浓度及迁移通道结构,进而调节Li^(+)的迁移性能,提高LATP中的Li^(+)导电性能.

钠离子电池正极材料Na_(4)Fe_(3-x)Cr_(x)(PO_(4))_(2)P_(2)O_(7)/C@CNT的制备及电化学性能研究

为改善钠离子电池正极材料Na_(4)Fe_(3)(PO_(4))_(2)P_(2)O_(7)的导电性,提高其充放电性能,采用Cr^(3+)掺杂提高正极材料本征导电性,采用包覆碳和复合碳纳米管(CNT)构筑高效导电网络以加快纳米活性物颗粒间的电子传导,制备并探究了Na_(4)Fe_(3-x)Cr_(x)(PO_(4))_(2)P_(2)O_(7)/C@CNT复合材料的结构与电化学性能。结果表明,当Cr^(3+)掺杂量x为0.075、CNT添加质量分数为3%时,所制备材料表现出较小的电荷传递阻抗和优异的高倍率充放电性能。其0.1 C和20 C倍率下的放电比容量分别达到120.64 mAh/g和87.11 mAh/g,10 C倍率下循环500次后容量保持率高达92.37%。

Sr_(0.5)Zr_(2)(PO_(4))_(3)-(Ce,Sm)PO_(4)复相陶瓷核废物固化体的制备及化学稳定性

为同时固化高放废物中的模拟放射性核素Sr、Ce和Sm,采用一步微波烧结工艺成功制备了Sr_(0.5)Zr_(2)(PO_(4))_(3)-(Ce,Sm)PO_(4)复相磷酸盐陶瓷固化体,采用XRD、Raman、SEM-EDS和密度表征研究了其物相组成、微观结构以及致密性,并利用PCT法评估了化学稳定性。结果表明:Sr_(0.5)Zr_(2)(PO_(4))_(3)相和(Ce,Sm)PO_(4)独居石相兼容性好,两相间不发生相互反应;所制备的复相陶瓷固化体晶粒尺寸小,相对密度高于96%,改变Sm/Ce比对固化体的微观结构和致密性无明显影响;PCT测试结果表明Sr、Ce和Sm的元素归一化元素浸出率都较低,与单相磷酸盐陶瓷固化体相比,复相磷酸盐陶瓷固化体具有较为优异的化学稳定性。

焦磷酸磷酸铁钠基钠离子电池日历老化容量衰减机理研究

随着钠离子电池技术的不断发展,深入探索其存储过程中的容量损失机理对提高电池系统日历寿命具有重要意义。本文对焦磷酸磷酸铁钠[Na_(4)Fe_(3)(PO_(4))_(2)P_(2)O_(7)]基钠离子电池的高温存储性能进行了详细研究,通过透射电子显微镜(TEM)、电感耦合等离子体发射光谱(ICP)、拉曼光谱、傅里叶变换红外光谱(FT-IR)及X射线光电子能谱(XPS)等多维度分析技术,全面剖析了正负极活性材料在高温存储过程中的容量损失率、结构、形貌及界面组分的变化。研究结果表明,高温存储后电极活性材料的比容量仅出现轻微衰减,正负极活性材料结构也未见受损,且正极铁元素溶出串扰并不显著。然而,负极侧固体电解质界面(SEI)膜增厚现象十分显著,表明存储期间负极SEI膜会不断溶解生长,且新生成的SEI膜以有机物为主。这一发现揭示了负极侧界面副反应是钠离子电池存储容量损失的主要因素。本研究不仅深化了对钠离子电池日历老化机制的理解,也为后续提升电池性能提供了重要的科学依据。

PVDF-HFP与LATP不同配比对固态电解质膜的影响

液态电解质锂离子电池因其潜在的安全性问题,发展新的固态电解质锂离子电池是目前所研究的热点。磷酸铝钛锂(Li_(1.5)Al_(0.5)Ti_(1.5)(PO_(4))_(3),LATP)是一种NASICON型陶瓷材料,由于其空气稳定性和较好的Li^(+)导电性而备受关注。然而,为了达到良好的离子导电性并降低晶界阻抗,LATP需要950℃以上的高温来实现致密化,这对于大规模应用来说耗时且昂贵。本文使用简单的溶液浇铸法,通过将LATP嵌入共聚物PVDF-HFP(聚偏氟乙烯-六氟丙烯)基体,合成新的复合固态电解质膜。在此基础上,以磷酸铁锂(LiFePO_(4))为正极,使用PVDF-HFP/LATP复合固态电解质膜进行电池组装。在室温下,利用X射线衍射仪(X-ray diffractometer,XRD)、扫描电子显微镜(scanning electron microscope,SEM)对不同质量比的固态电解质膜进行物理特性研究,并进行相关电化学测试。结果表明,PVDF-HFP/LATP质量比为5∶1的复合固态电解质膜,其LATP的NASICON型晶体结构得到了很好的保持;制备的聚合物固态电解质膜具有阻燃性;组装的半电池在常温条件下锂离子迁移数达到0.70。全电池在20次充放电循环下,放电比容量保持率为85%。

Optimization Strategies of Na_(3)V_(2)(PO_(4))_(3) Cathode Materials for Sodium‑Ion Batteries

Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.

动态缺陷导致Na_(3)Sc_(2)(PO_(4))_(3):Yb^(3+),Er^(3+)材料上转换和下转移发光不同热猝灭行为研究

掺Eu^(2+)的离子导体Na_(3)Sc_(2)(PO_(4))_(3)具有优异的抗热猝灭性能,是一种很有前景的大功率照明用发光材料。然而,其负热猝灭机理仍有待深入研究。本文以Yb^(3+)/Er^(3+)的f-f跃迁上转换和下转移窄带发射而非更易受干扰的Eu^(2+)d-f跃迁发射为研究对象,旨在获得更清晰的机理。结果表明,热致缺陷/离子的动态迁移能促进高温下辐射跃迁和抑制非辐射跃迁,导致上转换发光具有显著的负热猝灭,下转移发光热猝灭较小。其中,布居速率较慢的上转换过程更容易受到时间尺度与之相当的Na^(+)/空位迁移过程的影响。本研究可为理解发光材料热猝灭机制提供另一种视角。

A high-entropy-designed cathode with V^(5+)-V^(2+) multi-redox for high energy density sodium-ion batteries

Na_(3)V_(2)(PO_(4))_(3)(NVP)is gifted with fast Na^(+)conductive NASICON structure.But it still suffers from low electronic conductivity and inadequate energy density.Herein,a high-entropy modification strategy is realized by doping V^(3+)site with Ga^(3+)/Cr^(3+)/Al^(3+)/Fe^(3+)/In^(3+)simultaneously(i.e.Na_(3)V_(2-x)(GaCrAlFeIn)_x(PO_(4))_(3);x=0,0.04,0.06,and 0.08)to stimulate the V^(5+)■V^(2+)reversible multi-electron redox.Such configuration high-entropy can effectively suppress the structural collapse,enhance the redox reversibility in high working voltage(4.0 V),and optimize the electronic induced effect.The in-situ X-ray powder diffraction and in-situ electrochemical impedance spectroscopy tests efficaciously confirm the robust structu ral recovery and far lower polarization throughout an entire charge-discharge cycle during 1.6-4.3 V,respectively.Moreover,the density functional theory calculations clarify the stronger metallicity of high-entropy electrode than the bare that is derived from the more mobile free electrons surrounding the vicinity of Fermi level.By grace of high-entropy design and multi-electron transfer reactions,the optimal Na_(3)V_(1.7)(GaCrAlFeIn)_(0.06)(PO_(4))_(3)can exhibit perfect cycling/rate performances(90.97%@5000 cycles@30 C;112 mA h g^(-1)@10 C and 109 mA h g^(-1)@30 C,2.0-4.3 V).Furthermore,it can supply ultra-high185 mA h g^(-1)capacity with fa ntastic energy density(522 W h kg^(-1))in half-cells(1.4-4.3 V),and competitive capacity(121 mA h g^(-1))as well as energy density(402 W h kg^(-1))in full-cells(1.6-4.1 V),demonstrating enormous application potential for sodium-ion batteries.

Cathode nanoarchitectonics with Na_(3)VFe_(0.5)Ti_(0.5)(PO_(4))_(3): Overcoming the energy barriers of multielectron reactions for sodium-ion batteries

High electrochemical stability and safety make Na+superionic conductor(NASICON)-class cathodes highly desirable for Na-ion batteries(SIBs).However,their practical capacity is limited,leading to low specific energy.Furthermore,the low electrical conductivity combined with a decline in capacity upon prolonged cycling(>1000 cycles)related to the loss of active material-carbon conducting contact regions contributes to moderate rate performance and cycling stability.The need for high specific energy cathodes that meet practical electrochemical requirements has prompted a search for new materials.Herein,we introduce a new carbon-coated Na_(3)VFe_(0.5)Ti_(0.5)(PO_(4))_(3)(NVFTP/C)material as a promising candidate in the NASICON family of cathodes for SIBs.With a high specific energy of∼457 Wh kg^(-1) and a high Na+insertion voltage of 3.0 V versus Na^(+)/Na,this cathode can undergo a reversible single-phase solid-solution and two-phase(de)sodiation evolution at 28 C(1 C=174.7 mAh g^(-1))for up to 10,000 cycles.This study highlights the potential of utilizing low-cost and highly efficient cathodes made from Earth-abundant and harmless materials(Fe and Ti)with enriched Na^(+)-storage properties in practical SIBs.

Yb^(3+)/Nd^(3+)掺杂对Sr_(9)Ga(PO_(4))_(7)∶Cr^(3+)发光性能的影响

近红外荧光粉由于其独特的物理特性和广阔的应用前景吸引了人们极大的研究兴趣。本文通过高温固相反应法合成Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+)近红外荧光粉,使用460 nm蓝光激发样品的发射波长位于833 nm,半峰宽为117 nm。随后引入稀土离子合成Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),Yb^(3+)和Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),Nd^(3+)近红外荧光粉。相比Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),460 nm蓝光激发的Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),Yb^(3+)同时出现Cr^(3+)和Yb^(3+)特征发射峰,经过光谱分析和荧光寿命变化证明Cr^(3+)-Yb^(3+)存在能量传递通道,最高使Cr^(3+)-Yb^(3+)能量传递效率达80.2%,得益于Yb^(3+)卓越的热稳定性促使整体荧光光谱热稳定性提高约3.7倍。设计合成的Sr_(9)Ga(PO_(4))_7∶0.8Cr^(3+),Nd^(3+)样品调制出833,876,1 060 nm的多峰发射,显著拓宽了近红外光谱范围。最终,讨论了荧光粉在温度传感和无损检测领域的应用,证明该系列荧光粉具有广阔的应用前景。

Solid-state NMR study on sodium intercalation at low voltage window for Na_(3)V_(2)(PO_(4))_(3) as an anode

In-situ XRD,^(31)P NMR and ^(23)Na NMR were used to analyze the interaction behavior of Na_(3)V_(2)(PO_(4))_(3) at low voltage,and then a new intercalation model was proposed.During the transition from Na_(3)V_(2)(PO_(4))_(3) to Na_(4)V_(2)(PO_(4))_(3),Na ions insert into M1,M2 and M3 sites simultaneously.Afterwards,during the transition of Na_(4)V_(2)(PO_(4))_(3)to Na_(5)V_(2)(PO_(4))_(3),Na ions mainly insert into M3 site.

Robust Cross-Linked Na_(3)V_(2)(PO_(4))_(2)F_(3) Full Sodium-Ion Batteries

Sodium-ion batteries(SIBs)have rapidly risen to the forefront of energy storage systems as a promising supplementary for Lithium-ion batteries(LIBs).Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)as a common cathode of SIBs,features the merits of high operating voltage,small volume change and favorable specific energy density.However,it suffers from poor cycling stability and rate performance induced by its low intrinsic conductivity.Herein,we propose an ingenious strategy targeting superior SIBs through cross-linked NVPF with multi-dimensional nanocarbon frameworks composed of amorphous carbon and carbon nanotubes(NVPF@C@CNTs).This rational design ensures favorable particle size for shortened sodium ion transmission pathway as well as improved electronic transfer network,thus leading to enhanced charge transfer kinetics and superior cycling stability.Benefited from this unique structure,significantly improved electrochemical properties are obtained,including high specific capacity(126.9 mAh g^(-1)at 1 C,1 C=128 mA g^(-1))and remarkably improved long-term cycling stability with 93.9%capacity retention after 1000 cycles at 20 C.The energy density of 286.8 Wh kg^(-1)can be reached for full cells with hard carbon as anode(NVPF@C@CNTs//HC).Additionally,the electrochemical performance of the full cell at high temperature is also investigated(95.3 mAh g^(-1)after 100 cycles at 1 C at 50℃).Such nanoscale dual-carbon networks engineering and thorough discussion of ion diffusion kinetics might make contributions to accelerating the process of phosphate cathodes in SIBs for large-scale energy storages.

Unraveling the incompatibility mechanism of ethylene carbonate-based electrolytes in sodium metal anodes

Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.