固态电解质锂镧锆氧(Li_7La_3Zr_2O_(12))制备及第一性原理研究

固态电解质(SSE)是锂离子电池(LIB)的关键材料.Li_7La_3Zr_2O_(12)(LLZO)固体电解质是全固态锂离子电池开发中的关键部分.采用高温固相法制备了不同烧结温度后的四方Li_7La_3Zr_2O_(12)(t-LLZO)和立方Li_7La_3Zr_2O_(12)(c-LLZO),分析了两种样品的结构性能.800℃下烧结12小时的t-LLZO呈四方相,晶格尺寸为a=b=13.13064?,c=12.66024?,离子电导率为3.42×10~(-8)S·cm~(-1);1000℃下烧结12小时的c-LLZO呈立方相,晶格尺寸为a=b=c=13.03544?,离子电导率为8.48×10~(-5)S·cm~(-1).另基于密度泛函理论(DFT)的第一性原理计算了四方相和立方相的LLZO固体电解质材料的能带结构、晶格参数、态密度和键布居.通过理论计算解释了四方相LLZO离子电导率低于立方相LLZO的原因.     

Y_(3-x)Bi_xFe_5O_(12)的晶体生长

本文讨论了Y_2O_3-Fe_2O_3-Bi_2O_3-PbO·0.2B_2O_3赝四元系相图的得出与运用;用Bi_2O_3-PbO-B_2O_3做助熔剂,获得了磁性石榴石Y_(3-x)Bi_xFe_5O_(12)单晶(0≤x≤1.2);还论述了Bi-YIG晶体内Bi含量与助熔剂熔液成份的关系。     

Zn_(1-x)Mo_(1-y)Si_yO_4∶Eu_x~(3+)红色荧光粉的合成及发光性能研究

通过固相法合成LED用Zn-Mo1-ySiyO4:Eu3+x红色荧光粉(0.05≤x≤0.30,0≤y≤0.09),讨论了助熔剂、温度等合成条件对Zn1-xMo1-ySiyO4:Eux3+荧光粉发光性质的影响.当烧结温度为800℃时,可以生成ZnMoO4纯相目标产物.由于荧光粉的结晶度和粒径随烧结温度的升高而增大,所以随着烧结温度的升高,样品的发光强度有所提高;当助熔剂Na2CO3的用量约为4%时的样品发射光的强度比未使用助熔剂时明显增强,说明在此体系中,当Eu3+取代Zn2+时,Na2CO3充当助熔剂的同时,Na+起到了电荷补偿作用.荧光光谱实验显示Zn1-xMo1-ySOyO4:Eux3+能够被393和464 nm的紫外光激发,在616 nm处发出强烈的红色荧光.当Eu3+掺杂量约为20%mol时,Zn1-xMo0.97Si0.03O4:Eux3+荧光粉在616 nm处的发光强度达到最大.在引入Si4+离子后能显著增强Zn1-xMoO4:Eux3+的发光强度,组成为Zn0.80 Mo0.97Si0.03O4:Eu0.203+.样品(激发峰值为393 nm)的荧光强度要比Y2O2S:Eu0.053+荧光粉的发光强度强2倍.所以这种荧光物质能够更好地适用于白光LED.     

Bi_2O_3-Y_2O_3系高氧离子导体的离子电导和电子电导的研究

用交流电桥法研究了Bi_2O_3 Y_2O_3体系含22.5—30mol％Y_2O_3烧结试样在po_2值由1至10~(-21)atm范围内氧离子的电导率,实验证明该种材料的氧离子电导率比同温度下ZrO_2基固体电解质高若干倍;用这种材料作为固体电解质组成氧浓差电池,电池电动势和理论电动势的比值E/E_0等于1或接近1,说明这种材料几乎为纯氧离子导体,p型电子空穴导电性很小;用库伦滴定抽氧法测定了含Y_2O_3 27.5mol％样品的电子导电特征氧分压,其值为lgpe＇=(-767000/T)+655,电子导电性极小。可期望为一种新型氧离子导体材料。     

非晶态锂离子导体B_2O_3-0.7Li_2O-0.7LiCl-xAl_2O_3-0.1V_2O_5的电学性质和电子自旋共振研究

对两种非晶态B_2O_3-0.7Li_2O-0.7LiCl-xAl_2O_3-0.1V_2O_5(x=0.05和0.15),用差热分析、电导率测量、X射线衍射和电子自旋共振进行研究,发现:1)V_2O_5不仅作非晶网络形成剂,而且改变了晶化过程;2)对B_2O_3-Li_2O-LiCl-Al_2O_3-V_2O_5玻璃,与P_2O_5-Li_2O-LiCl-Al_2O_3玻璃类似,粉末压片的离子电导率比60目粉末大26倍,而整片非晶的离子电导率又比粉末压片大近二个数量级,而且激活能明显减小,更适合离子传输;3)添加少于3.9mol%的V_2O_5,对非晶态锂离子导体B_2O_3-0.7Li_2O-0.7LiCl-xAl_2O_3,未引起电子电导率显著增大,又可应用电子自旋共振(ESR)技术研究其微观结构和电子运动状态。     

流延法制备高锂离子电导Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3固态电解质及其环氧树脂改性

以溶胶凝胶法合成的高纯Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3(LATP)纳米晶体粉末为原料,通过流延法成膜,在950℃下煅烧5 h合成LATP固态电解质片;对其进行环氧树脂改性后,能量色散X射线光谱元素图像表明环氧树脂完全浸入LATP内部,可以有效防止水渗透.研究发现流延法合成的LATP固态电解质在25℃?C时电导率高达8.70×10~(-4)S·cm~(-1)、活化能为0.36 eV、相对密度为89.5%.经过环氧树脂改性后电导率仍高达3.35×10-4S·cm-1、活化能为0.34 e V、相对密度为93.0%.高电导隔水的环氧树脂改性LATP固态电解质可作为锂金属保护薄膜用于新型高比容量电池.     

锌掺杂固态电解质材料磷酸钛铝锂的制备及第一性原理研究

高安全性的固体锂离子电池是目前研究的热点之一,固态电解质是研究全固态电池的关键.磷酸钛铝锂固体电解质(LATP)具有良好的发展空间,因此采用高温固相法,制备锌掺杂LATP(LAZTP)固体电解质,通过XRD、SEM分析对比其物象和形貌特征,并对这两种材料压片进行阻抗分析,研究材料的电化学性能.基于密度泛函理论的第一性原理,研究LAZTP的能带结构和态密度与材料电化学性能的关系.结果表明:所掺杂锌的LATP材料,在球磨工艺下,与LATP相比衍射峰尖锐,材料结晶度良好,都为R-3C结构,LAZTP微观尺度下材料颗粒清晰,呈块状,孔隙均匀致密度较好,离子电导率相比较高,为1.9×10^-3S/cm,而制作的LATP的电导率为4.02x10^-4 S/cm,掺杂后的电导率明显高出一个数量级.计算得出的LATP能带带隙为0.163 eV和LAZTP能带带隙为0.05 eV,分态密度中Ti-s、Li-s、Al-s峰值尖锐,变化明显,表明掺杂锌后,材料明显提高了导电率和结构稳定性.     

多晶Li_(3+x)V_(1-x)T_xO_4(T=Ge,Si)离子导电性能的改善

本文用阻抗谱方法研究了Li_(3+x)V_(1-x)T_xO_4(T=Si,Ge)多晶的离子导电性,发现一些工艺条件如成型压强、烧结时间和烧结程序对电导率有很大影响。注意分析了这些影响的物理起因。最佳工艺条件是:在大约8t/cm~2压强下成型样品。在1000℃连续烧结5至6天,烧结过程中,应尽量避免温度波动。在此条件下制备的Li_(3.5)V_(0.5)Ge_(0.5)O_4和Li_(3.3)V_(0.7)Si_(0.3)O_4多晶样品在25℃的离子电导率分别为2.2×10~(-5)Q~(-1)cm~(-1)和1.9×10~(-5)Q~(-1)cm~(-1)。     

Ca_xSi合金前驱物常压氮化制备Ca_(1-x)AlSiN_3∶xEu~(2+)红色荧光粉及发光性能研究

采用CaxSi合金前驱物和Eu B6常压氮化制备了Ca Al Si N3∶Eu2+氮化物红色荧光粉。研究了不同烧结温度、添加助熔剂及二次烧结对发光性能的影响。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、荧光分光光度计对发光材料的形貌、晶体结构、发光性能与热稳定性进行了研究。分析结果表明:通过合金前驱物常压氮化法得到的氮化物荧光粉具有Ca Al Si N3结构,空间群为Cmc21。Ca Al Si N3∶Eu2+红色荧光粉的最佳烧结温度为1 550℃。添加质量分数为6%的Sr F2助熔剂后,荧光粉发光强度的提升效果最好。添加6%Sr F2助熔剂及二次烧结后得到的荧光粉的晶粒生长更加完整,颗粒度明显改善,发射光谱的相对强度也明显提高,比未加助熔剂单次烧结的荧光粉相对强度提高了近一倍。将发射峰位在640 nm的Ca0.98Al Si N3∶0.02Eu2+红色荧光粉应用在白光LED的封装中,获得了色温为3 109 K、显色指数为92.5以及色温为4 989K、显色指数为95.8的高显色白光LED,说明本文合成的氮化物红色荧光粉可以实现暖白光和正白光高显色的白LED发光器件。     

助熔剂对无机质子导体BaZrO_3结构及形貌的影响

利用高温固相法制备了无机质子导体BaZrO3。研究了助熔剂的添加对材料的合成温度及微观形貌的影响。通过添加LiF及Li2CO3为助熔剂,可以在1500℃,保温8h合成很好的单相样品。且LiF为助熔剂制备样品的结晶性明显高于Li2CO3为助熔剂制备的样品。XRD精修表明所合成的样品为很好的单相样品。能带计算分析样品的带隙为3.236eV。通过加入LiF及Li2CO3为助熔剂,明显改善了样品的微观形貌,其中LiF为助熔剂样品的颗粒尺寸较小、团聚少,分散性好。当LiF及Li2CO3添加量为8%时,晶界处有小颗粒析出,这种小颗粒为提高材料的质子导电性提供了潜在的可能性。     

The role of Bi2O3 as a network modifier and a network former in xBi2O3 · (1 − x)LiBO2 glass system

The effect of Bi₂O₃ on the glass transition temperature, electrical conductivity and structure of LiBO₂ glass has been investigated. T_g vs. composition curve shows three different linear regions, while there is an overall decrease in T_g with the increase in Bi₂O₃ content. The slope of these three straight lines is in a decreasing order. These results are interpreted in terms of the increase in the number of non-bridging oxygen atoms, substitution of Bi-O bond in place of B-O bond and change in Li⁺ ion concentration. The conductivity vs. composition curve exhibits two maxima which are interpreted in terms of the structural modification effect of Bi₂O₃ on LiBO₂ network and mixed-former effect, respectively. Results obtained from the XPS studies of the samples of composition x 0.005, have shown that the number of non-bridging oxygen atoms from B-O bond increases with the increase in Bi₂O₃ content. It has a maximum value at x = 0.003 where the conductivity has also exhibited a maximum value. Further increase of Bi₂O₃ content causes decrease in it. For higher Bi₂O₃ content (x * > 0.005), O 1s spectra of Bi₂O₃ has been separated out from that of Bi₂O₃. Bismuth ions have been substituted for boron ions as network former ions.     

Synthesis and ionic conductivity of new layered perovskite compound, Ag2La2Ti3O10

A new layered perovskite compound, Ag₂La₂Ti₃O₁₀, was synthesized by an ion-exchange reaction of M₂La₂Ti₃O₁₀ (M = Na,K) with a AgNO₃ molten salt. The crystal structure and the ionic conductivity of the ion-exchanged compound were investigated. The ionic conductivities attributed to the interlayer silver ions were observed at high temperatures. The ionic conductivity of Ag₂La₂Ti₃O₁₀ was much higher than that of Na₂La₂Ti₃O₁₀, while the interlayer sodium ions in Na₂La₂Ti₃O₁₀ and silver ions in Ag₂La₂Ti₃O₁₀ have almost the same rock-salt type coordination. The higher conductivity of Ag₂La₂Ti₃O₁₀ is probably due to the higher polarizability of silver ions.     

A low cost composite quasi-solid electrolyte of LATP,TEGDME,and LiTFSI for rechargeable lithium batteries

The composite quasi solid state electrolytes(CQSE) is firstly synthesized with quasi solid state electrolytes(QSE) and lithium-ion-conducting material Li_(1.4)Al_(0.4)Ti_(1.6)(PO_4)_3(LATP), and the QSE consists of [LiG4][TFSI] with fumed silica nanoparticles. Compared with LATP, CQSE greatly improves the interface conductance of solid electrolytes. In addition,it has lower liquid volume relative to QSE. Although the liquid volume fraction of CQSE is droped to 60%, its conductivity can also reach 1.39 × 10~(-4)S/cm at 20℃. Linear sweep voltammetry(LSV) is conducted on each composite electrolyte.The results show the possibility that CQSE has superior electrochemical stability up to 5.0 V versus Li/Li+. TG curves also show that composite electrolytes have higher thermal stability. In addition, the performance of Li/QSE/Li Mn_2O_4 and Li/CQSE/Li Mn_2O_4 batteries is evaluated and shows good electrochemical characteristics at 60℃.     

B2O3添加宝石级金刚石单晶的生长特性

利用温度梯度法, 在5.3-5.7 GPa压力、1200-1600 ℃的温度条件下, 将B₂O₃粉添加到FeNiMnCo+C合成体系内, 进行B₂O₃添加宝石级金刚石单晶的合成. 研究得到了FeNiMnCo触媒生长B₂O₃添加宝石级金刚石单晶的相图分布规律. 结果表明B₂O₃添加会使晶体生长的“V”形区上移和低温六面体单晶生长区间变宽. 通过晶体生长实验, 研究合成了不同形貌的B₂O₃添加宝石级金刚石单晶. 研究同时证实, B₂O₃的过量添加会对宝石级金刚石单晶生长带来不利影响. 当B₂O₃的添加量高于约3 wt‰、生长时间超过20 h时, 很难实现优质B₂O₃添加宝石级金刚石单晶的生长. 但B₂O₃的适量添加(不超过1 wt‰), 有助于提高低温板状六面体宝石级金刚石单晶的成品率. 通过对晶体生长速度的研究发现, B₂O₃的添加使得优质晶体的生长速度明显降低, 随着晶体生长时间的延长, B₂O₃添加剂对晶体生长的抑制作用会越发明显. 扫描电镜测试结果表明, 合成体系内B₂O₃添加剂的引入, 导致晶体表面的平整度明显下降.     

Ionic conductivity of crystalline and glassy Mg4.5Na7(P2O7)4

In our work single crystals of Mg_4.5Na₇(P₂O₇)₄ were prepared, pulverized, pressed into pellets and sintered in order to measure the electrical conductivity of polycrystalline specimens. The conductivity was also measured on glassy specimens obtained by the melting of previously prepared crystals. The electrical conductivities at 25°C with values of the order of 10⁻¹⁶ Ω⁻¹ cm⁻¹ for polycrystalline samples and a value of the order of 10⁻¹⁴ Ω⁻¹ cm⁻¹ for glass, show that the glassy phase of Mg_4.5Na₇(P₂ because of its greater molar volume and loosely packed structure, is a better matrix for ionic motion.     

用正电子湮没研究纳米碲化铋的缺陷及其对热导率的影响

利用水热法合成了Bi₂Te₃纳米粉末, 并在300–500 ℃的温度范围内对其进行等离子烧结. X射线衍射测试表明制得的Bi₂Te₃粉末是单相的. 对于300–500 ℃范围内烧结的样品, 扫描电子显微镜观察发现随着烧结温度的升高样品颗粒明显增大, 但是根据X射线衍射峰的宽度计算得到的样品晶粒大小并没有明显的变化. 正电子湮没寿命测试结果表明, 所有的样品中均存在空位型缺陷, 而这些缺陷很可能存在于晶界处. 正电子平均寿命随着烧结温度的升高而单调下降, 说明较高的烧结温度导致了空位型缺陷浓度的降低. 另外, 随着烧结温度从300 ℃升高到500 ℃, 样品的热导率从0.3 W·m^-1·K^-1升高到了2.4 W·m^-1·K^-1, 这表明在纳米Bi₂Te₃中, 空位型缺陷和热导率之间存在着密切的联系.     

溶胶-凝胶法制备Li1.0Nb0.6Ti0.5O3:Eu3+红色荧光粉

采用溶胶-凝胶法制备Li_1.0Nb_0.6Ti_0.5O₃：Eu³⁺红色荧光粉,讨论了煅烧温度、煅烧时间以及Eu³⁺掺杂浓度对样品发光性能的影响。通过XRD、荧光光谱分别对样品的性能进行表征,结果表明：样品的晶相结构为"M-相（M-phase）"。在466 nm蓝光激发下,合成的荧光粉具有橙光（593 nm）和红光（612 nm）发射。发光强度随着煅烧温度的升高先增大后减小,最佳的煅烧温度为850℃。同时,随着煅烧时间的增加,发光强度先增大后减小,最佳煅烧时间为6 h。当Eu₂O₃掺入质量分数为2.5%时,样品的发光强度达到最大。Li_1.0Nb_0.6-Ti_0.5O₃：Eu³⁺红色荧光粉在白光LED的应用中具有潜力。     

A higher conductivity Bi2O3-based electrolyte

We have developed a Bi₂O₃ electrolyte doped with Dy₂O₃ and WO₃ (DyWSB) that exhibits a higher conductivity than that of 20 mol% erbia stabilized bismuth oxide (20ESB), thus, giving it the highest conductivity of any known solid oxide electrolyte. Electrical conductivity results of the Dy–W stabilized bismuth oxide system are presented. The dopants were selected based on their polarizability and its effect on structural stability and conductivity. At 800 °C, the conductivity of (BiO_1.5)_0.88(DyO_1.5)_0.08(WO₃)_0.04 is 0.57 S/cm (1.5 times as high as that of 20ESB), and at 500 °C, the conductivity is 0.043 S/cm (2 times as high as that of 20ESB).     

Ni2O3掺杂对新固相源顶部籽晶熔渗生长法制备单畴GdBCO超导块材超导性能的影响

本文通过在新固相源中添加Ni₂O₃的方法, 采用顶部籽晶熔渗生长工艺(TSIG)制备出组分为(1-x) (Gd₂O₃+1.2BaCuO₂)+x Ni₂O₃、直径为20 mm的单畴GdBCO 超导块材(其中x = 0, 0.02, 0.06, 0.10, 0.14, 0.18, 0.30, 0.50 wt%), 并研究了Ni₂O₃的掺杂量x对样品的表面生长形貌、微观结构、临界温度T_c、磁悬浮力以及俘获磁通密度的影响. 研究结果表明, 当Ni₂O₃的掺杂量x在0–0.50 wt%的范围内时, 均可制备出单畴性良好的样品, 且Ni₂O₃的掺杂对样品中Gd211粒子的分布和粒径没有明显的影响. 在Ni₂O₃的掺杂量x从0增加到0.50 wt%的过程中, 样品的临界温度T_c呈现下降的趋势, 从x=0时的92.5 K下降到x=0.50 wt%时的86.5 K, 这是由于Ni^{3 +}替代GdBCO晶体中Cu^{2 +}所致; 样品磁悬浮力和俘获磁通密度均呈现先增大后减小的变化规律, x=0.14 wt%时, 磁悬浮力达到最大值34.2 N, x=0.10 wt%时, 俘获磁通密度达到最大值0.354 T. 样品磁悬浮力和俘获磁通密度的变化规律与Ni₂O₃的掺杂量x有密切关系, 只有当掺杂量x合适时, Ni³⁺对Cu^{2 +}的替代既不会造成T_c的明显下降, 但又能产生适量的Ni^{3 +}/Cu²⁺ 晶格畸变, 从而达到提高样品磁通钉扎能力和超导性能的效果.