Journal of Solid State Chemistry最新文献

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The role of crystallographic orientation on surface properties and ion transport in lithium germanate (Li2GeO3) anodes: A computational approach 结晶取向对锗酸锂（Li2GeO3）阳极表面性质和离子传输的作用：计算方法

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-27 DOI: 10.1016/j.jssc.2024.125032

The performance of lithium-ion batteries (LIBs) hinges on the surface properties of their anodes. Compared to the bulk material, the anode surface is more susceptible to environmental changes during lithium (Li) intake and release, directly impacting factors like capacity, cycling stability, and charge/discharge rates. Lithium germanate (Li₂GeO₃, LGO) has emerged as a promising anode material due to its fast Li-ion conduction. While numerous studies have explored performance improvements through various methods, including defect engineering. However, there is currently a lack of atomistic-level understanding of the surface structure. Consequently, despite the importance of precisely understanding the surface to manipulate its different properties, specific surface details of LGO remain unclear. This knowledge gap hinders precise manipulation of surface properties for optimal performance.This study addresses this critical need by employing theoretical calculations to predict the structural, electrochemical characteristics, and Li-ion transport behavior in LGO surfaces. Our results indicate that polar surfaces exhibit lower formation energies compared to non-polar surfaces. Further investigation revealed that Li-terminated surfaces possess the lowest surface energy among various surface terminations. Interestingly, the work function calculations displayed an opposite trend to surface formation energy, with polar surfaces exhibiting the lowest work function values.To explore Li-ion transport, we employed ab initio molecular dynamics simulations. Notably, the (003) surface displayed the highest Li-ion diffusion rate among all considered surfaces.Further analysis of the (001) surface, which exhibited similar diffusion pathways to the (003) surface, revealed a lower diffusion rate.To understand this disparity, nudged elastic band (NEB) simulations were used to estimate the energy barriers for Li-ion migration along each pathway in both structures. Despite sharing similar pathways, the energy barriers in the (003) surface were significantly lower than those in the (001) surface. This finding suggests that the intrinsic energy landscape of the surface plays a crucial role in dictating Li-ion transport behavior.

锂离子电池（LIB）的性能取决于其阳极的表面特性。与块体材料相比，阳极表面在锂（Li）吸收和释放过程中更容易受到环境变化的影响，从而直接影响容量、循环稳定性和充放电率等因素。锗酸锂（Li2GeO3，LGO）因其锂离子传导速度快而成为一种前景广阔的负极材料。虽然许多研究都在探索通过各种方法（包括缺陷工程）来提高性能。然而，目前还缺乏对表面结构的原子级理解。因此，尽管精确了解表面对操纵其不同性能非常重要，但 LGO 的具体表面细节仍不清楚。本研究利用理论计算来预测 LGO 表面的结构、电化学特性和锂离子传输行为，从而满足了这一关键需求。我们的研究结果表明，与非极性表面相比，极性表面的形成能更低。进一步研究发现，在各种表面端接中，锂端接表面的表面能最低。有趣的是，功函数计算显示出与表面形成能相反的趋势，极性表面的功函数值最低。值得注意的是，在所有考虑过的表面中，(003) 表面的锂离子扩散速率最高。进一步分析(001) 表面，发现其扩散途径与 (003) 表面相似，但扩散速率较低。尽管路径相似，(003) 表面的能垒明显低于(001) 表面。这一发现表明，表面的内在能谱在决定锂离子迁移行为方面起着至关重要的作用。

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引用次数: 0

Structural features of the products based on potassium polytitanate modified in aqueous solutions of ferric sulfate 基于聚钛酸钾在硫酸铁水溶液中改性的产品的结构特征

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-27 DOI: 10.1016/j.jssc.2024.125035

The structure and electronic composition of potassium polytitanate (PPT) powders and the product of their chemical treatment (modification) in the aqueous solution of ferric sulfate (PPT/Fe) have been studied. It has been shown that PPT and PPT/Fe powders consist of X-ray amorphous conglomerates of nano- and submicrosized particles. Further heat treatment of PPT/Fe at 900 °C leads to the formation of a solid solution K_1.5Fe_1.5Ti_6.5O₁₆, which has a hollandite-like crystalline structure. Quantitative characteristics of the local atomic structure of iron ions in the structure of the obtained compounds have been established. Based on the data of Mössbauer spectroscopy, X-ray photoelectron spectroscopy, XANES and EXAFS analyses of Fe K-edge spectra, the mechanism of physico-chemical processes accompanying the PPT particles modification with aqueous solutions of iron (III) salts and their subsequent heat treatment in order to obtain desired functional compounds has been proposed. It has been established that iron and titanium ions consistently change their valence state during the chemical and thermal treatment. The mechanism of structural transformations in the investigated system has been analyzed.

研究了聚钛酸钾（PPT）粉末及其在硫酸铁水溶液中的化学处理（改性）产物（PPT/Fe）的结构和电子组成。研究表明，PPT 和 PPT/Fe 粉末由纳米级和亚微米级颗粒组成的 X 射线无定形团块。在 900 °C 下对 PPT/Fe 进一步热处理后，会形成固溶体 K1.5Fe1.5Ti6.5O16，这种固溶体具有类似于荷兰石的晶体结构。已确定了所获化合物结构中铁离子局部原子结构的定量特征。根据莫斯鲍尔光谱、X 射线光电子能谱、XANES 和 EXAFS 分析铁 K-edge 光谱的数据，提出了用铁（III）盐水溶液对 PPT 粒子进行改性并随后进行热处理以获得所需功能化合物的物理化学过程的机理。研究证实，在化学和热处理过程中，铁离子和钛离子的价态不断发生变化。分析了所研究体系中结构转变的机理。

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引用次数: 0

Stability under electron irradiation of some layered hydrated minerals 一些层状水合矿物在电子辐照下的稳定性

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-26 DOI: 10.1016/j.jssc.2024.125033

The structural damages caused to some layered hydrated minerals by 2.5 MeV electron irradiation using the SIRIUS platform were studied by powder X-Ray diffraction and, in some cases, by ¹H MAS-NMR spectroscopy. It is clearly demonstrated that the radiation damages are distinguishable from the heating effects. It is shown that: i) in all cases electron irradiation leads to distortions of the unit cell and very limited volume expansion, compared to heating; ii) radiation damages increase with increasing the structural complexity of the mineral; iii) portlandite Ca(OH)₂ and brucite Mg(OH)₂ remain crystalline up to high doses (a few GGy), with appearance of stacking fault disorder especially in brucite; iv) brushite CaHPO₄.2H₂O and gypsum CaSO₄.2H₂O undergo a phase transformation of type amorphization for brushite involving the strongest intralayer H bond between the acidic proton and the phosphate tetrahedral, and decomposition for gypsum involving interlayer H bonds between water molecules.

利用 SIRIUS 平台，通过粉末 X 射线衍射和 1H MAS-NMR 光谱研究了 2.5 MeV 电子辐照对一些层状水合矿物造成的结构破坏。研究清楚地表明，辐射损伤与加热效应是可以区分的。研究表明：i) 与加热相比，电子辐照在所有情况下都会导致单胞畸变和非常有限的体积膨胀；ii) 辐射损伤随着矿物结构复杂程度的增加而增加；iii) 波长石 Ca(OH)2 和青金石 Mg(OH)2 在高剂量（几个 GGy）下仍保持结晶状态，特别是在青金石中出现堆叠断层紊乱；iv) 刷石 CaHPO4.2H2O 和石膏 CaSO4.2H2O 会发生相变，其中刷石涉及酸性质子和磷酸盐四面体之间最强的层内 H 键，而石膏则涉及水分子之间的层间 H 键。

引用次数: 0

Synthesis of spherical amorphous metal‒organic frameworks via an in situ hydrolysis strategy for chiral HPLC separation 通过原位水解策略合成球形无定形金属有机框架，用于手性 HPLC 分离

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-22 DOI: 10.1016/j.jssc.2024.125028

To obtain metal-organic frameworks (MOFs) that are more suitable for applications in liquid chromatography separation, the synthesis of spherical MOF particles of micrometer size is of great importance. Herein, by using an in situ hydrolysis strategy, the reactions of zirconium tetrachloride with terephthalonitrile under optimized water content and temperature give rise to Zr(IV)-carboxylic amorphous metal-organic frameworks (aMOFs) with spherical shapes at the micrometer scale. The aMOF particles can be used as a matrix to fabricate a chiral stationary phase (CSP) after coating cellulose derivative, cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC), on it. The resulting CSP, namely, CDMPC@aMOF, was further applied to separate enantiomers under high-performance liquid chromatography (HPLC). The results showed that six racemic compounds, including metalaxyl, prothioconazole, trans-stilbene oxide, 1-(1-naphthalenyl)ethanol, 1-phenylethanol and atropine sulfate, were well separated by a CDMPC@aMOF packed column.

为了获得更适合液相色谱分离应用的金属有机框架（MOFs），合成微米级的球形 MOF 颗粒非常重要。本文采用原位水解策略，在优化的含水量和温度条件下，将四氯化锆与对苯二甲腈进行反应，得到了具有微米级球形形状的锆(IV)-羧基无定形金属有机框架（aMOF）。在 aMOF 颗粒上涂覆纤维素衍生物--纤维素-三（3,5-二甲基苯基氨基甲酸酯）（CDMPC）后，可将其用作基质来制造手性固定相（CSP）。得到的 CSP（即 CDMPC@aMOF）被进一步用于在高效液相色谱法（HPLC）下分离对映体。结果表明，CDMPC@aMOF填料柱能很好地分离6种外消旋化合物，包括金属硫醇、丙硫咪唑、反式氧化二苯乙烯、1-(1-萘基)乙醇、1-苯乙醇和硫酸阿托品。

引用次数: 0

A fluorinated star-shaped covalent organic framework for efficient iodine adsorption 高效吸附碘的氟化星形共价有机框架

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-21 DOI: 10.1016/j.jssc.2024.125025

Covalent organic frameworks (COFs) are widely used for gaseous radioiodine capture through distinctive properties. Herein, 2D fluorinated imine COF (JLNU-316) was designed and constructed in this study. JLNU-316 exhibited large BET surface area of 596.25 mg²/g and pore size (2.74 and 3.78 nm), excellent thermal and chemical stability. The adsorption of iodine by JLNU-316 reached 4.08 g/g, which exceeded most of the current fluorine-containing porous iodine adsorption materials. Furthermore, the iodine adsorption capacity remains at 99 % after seven days of exposure to air conditions, and JLNU-316 maintains stable performance following ten cycles. The introduction of heteroatoms enhanced the stability of JLNU-316 and enriched the adsorption sites, thereby increasing the iodine adsorption capacity. This study guides for the design and preparation of novel iodine adsorbents.

共价有机框架（COF）具有独特的性能，被广泛用于气态放射性碘捕获。本研究设计并构建了二维氟化亚胺 COF（JLNU-316）。JLNU-316 的 BET 表面积为 596.25 mg2/g，孔径为 2.74 和 3.78 nm，具有良好的热稳定性和化学稳定性。JLNU-316 的碘吸附量达到 4.08 g/g，超过了目前大多数含氟多孔碘吸附材料。此外，JLNU-316 在空气中暴露七天后，碘吸附容量仍能保持在 99%，并且在十次循环后仍能保持稳定的性能。杂原子的引入增强了 JLNU-316 的稳定性，丰富了吸附位点，从而提高了碘的吸附能力。这项研究为设计和制备新型碘吸附剂提供了指导。

引用次数: 0

Homochiral Zn(Ⅱ) coordination polymers with helixes constructed from semirigid lactate deriatives for circular polarization luminescence and fluorescent prober 用于圆偏振发光和荧光探针的具有半刚性乳酸二聚体螺旋结构的同手性 Zn（Ⅱ）配位聚合物

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jssc.2024.125024

In the presence of nitrogen heterocyclic compound 2,5-di(1H-imidazole-1 -yl)pyridine (2,5-DIP), luminescent chiral synthons (R)-H₃CTA and (S)–H₃CTA assembled with Zn²⁺ ions to obtain enantiomers [Zn((R)-HCTA) (2,5-DIP)]_n (HU14-R) and [Zn((S)-HCTA) (2,5-DIP)]_n (HU14–S)) under hydrothermal condition, respectively. Partially deprotonated (R)-HCTA^2- anions were bridged by Zn²⁺ ions to form small left-handed (R)-HCTA-Zn chain in HU14-R, while (S)-HCTA^2- anions and Zn²⁺ ions were connected together resulting in enantiomeric right-handed chain in HU14–S. Moreover, larger left-handed (R)-HCTA-Zn-2,5-DIP chain and right-handed (S)-HCTA-Zn-2,5-DIP chain were found in HU14-R and HU14–S, respectively. These helical building blocks were joined together to create a pair of 3D frameworks with dia net, which show strong fluorescent characteristic and circular dichroism response. Further tests proved that HU14-R and HU14–S have circularly polarized light (CPL) activity and their luminescence anisotropy factors (g_1um) at 358 nm are +0.00346 and −0.00157, respectively. Moreover, as fluorescent probes, they have high stability, reliability and interference detection rate, and detection limits are up to 2.80 × 10⁻⁶ M for Cr₂O₇²⁻ and 6.19 × 10⁻⁶ M for MnO₄⁻.

在氮杂环化合物 2,5-二（1H-咪唑-1-基）吡啶（2,5-DIP）的存在下，发光手性合成物 (R)-H3CTA 和 (S)-H3CTA 与 Zn2+ 离子结合，在水热条件下分别得到对映体 [Zn((R)-HCTA) (2、5-DIP)]n (HU14-R) 和 [Zn((S)-HCTA) (2,5-DIP)]n (HU14-S)) 对映体。在 HU14-R 中，部分去质子化的 (R)-HCTA2- 阴离子与 Zn2+ 离子桥接，形成小的左手 (R)-HCTA-Zn 链；而在 HU14-S 中，(S)-HCTA2- 阴离子和 Zn2+ 离子连接在一起，形成对映体右手链。此外，在 HU14-R 和 HU14-S 中分别发现了较大的左手（R）-HCTA-Zn-2,5-DIP 链和右手（S）-HCTA-Zn-2,5-DIP 链。这些螺旋结构单元连接在一起，形成了一对直径为网状的三维框架，显示出强烈的荧光特性和圆二色性响应。进一步的测试证明，HU14-R 和 HU14-S 具有圆偏振光（CPL）活性，它们在 358 纳米波长处的发光各向异性系数（g1um）分别为 +0.00346 和 -0.00157。此外，作为荧光探针，它们具有较高的稳定性、可靠性和干扰检测率，Cr2O72- 和 MnO4- 的检测限分别高达 2.80 × 10-6 M 和 6.19 × 10-6 M。

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引用次数: 0

Analyzing structural changes and variable range hopping conduction in Na0.5Bi0.5TiO3 perovskite: Effect of Sr2+ doping at Bi-site 分析 Na0.5Bi0.5TiO3 包晶的结构变化和变程跳变传导：在铋位掺杂 Sr2+ 的影响

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jssc.2024.125023

In this present investigation, we explored the impact of Sr²⁺ doping at the Bi-site on the structural, electrical, and optical characteristics of

{Na}_{0.5} {Bi}_{0.5} Ti O_{3}

(NBT) nanomaterial. By employing the citrate auto-combustion method, we synthesized pure

{Na}_{0.5} {Bi}_{0.5} Ti O_{3}

nano-perovskites, as well as various Sr-doped counterparts. Analysis of the observed X-ray diffraction patterns through Rietveld refinement revealed a rhombohedral phase with space group R3c, although the composition doped with 10 % Sr exhibited impurity phases. The introduction of Sr²⁺ ions had a discernible influence on diverse microstructural parameters, including lattice parameters (a and c), microstrain, X-ray density, and particle size. Detailed morphological and elemental assessments were conducted utilizing TEM, FE-SEM, and EDX spectroscopy. The analysis of UV–Vis absorption spectra yielded a reduction in the optical band gap with increasing Sr addition up to 8 % doping, followed by an increase. Random Free-Energy Barrier Model (RBM) was employed to analyze complex AC conductivity. The three-dimensional Godet's Variable Range Hopping (3D G-VRH) model was also applied to elucidate the electrical transport properties.

在本研究中，我们探讨了在铋位掺杂 Sr2+ 对 Na0.5Bi0.5TiO3（NBT）纳米材料的结构、电学和光学特性的影响。我们采用柠檬酸盐自动燃烧法合成了纯净的 Na0.5Bi0.5TiO3 纳米超晶石以及各种掺杂 Sr 的对应物。通过里特维尔德精炼法分析观察到的 X 射线衍射图样显示出空间群为 R3c 的斜方体相，尽管掺杂 10% Sr 的成分显示出杂质相。Sr2+ 离子的引入对不同的微观结构参数有明显的影响，包括晶格参数（a 和 c）、微应变、X 射线密度和粒度。利用 TEM、FE-SEM 和 EDX 光谱进行了详细的形态和元素评估。紫外-可见吸收光谱分析表明，随着 Sr 掺杂量的增加，光带隙减小到 8%，随后又增大。随机自由能垒模型（RBM）被用来分析复合交流电导率。此外，还采用了三维戈德变程跳变（3D G-VRH）模型来阐明电传输特性。

{"title":"Analyzing structural changes and variable range hopping conduction in Na0.5Bi0.5TiO3 perovskite: Effect of Sr2+ doping at Bi-site","authors":"","doi":"10.1016/j.jssc.2024.125023","DOIUrl":"10.1016/j.jssc.2024.125023","url":null,"abstract":"<div><div>In this present investigation, we explored the impact of Sr2+ doping at the Bi-site on the structural, electrical, and optical characteristics of <math><mrow><msub><mtext>Na</mtext><mn>0.5</mn></msub><msub><mtext>Bi</mtext><mn>0.5</mn></msub><mtext>Ti</mtext><msub><mi>O</mi><mn>3</mn></msub></mrow></math> (NBT) nanomaterial. By employing the citrate auto-combustion method, we synthesized pure <math><mrow><msub><mtext>Na</mtext><mn>0.5</mn></msub><msub><mtext>Bi</mtext><mn>0.5</mn></msub><mtext>Ti</mtext><msub><mi>O</mi><mn>3</mn></msub></mrow></math> nano-perovskites, as well as various Sr-doped counterparts. Analysis of the observed X-ray diffraction patterns through Rietveld refinement revealed a rhombohedral phase with space group R3c, although the composition doped with 10 % Sr exhibited impurity phases. The introduction of Sr2+ ions had a discernible influence on diverse microstructural parameters, including lattice parameters (a and c), microstrain, X-ray density, and particle size. Detailed morphological and elemental assessments were conducted utilizing TEM, FE-SEM, and EDX spectroscopy. The analysis of UV–Vis absorption spectra yielded a reduction in the optical band gap with increasing Sr addition up to 8 % doping, followed by an increase. Random Free-Energy Barrier Model (RBM) was employed to analyze complex AC conductivity. The three-dimensional Godet's Variable Range Hopping (3D G-VRH) model was also applied to elucidate the electrical transport properties.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142310854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-pressure synthesis, crystal structure and anisotropic thermal/compressive behaviors of pseudo-ternary (V,Cr,Mo)P4 伪三元(V,Cr,Mo)P4 的高压合成、晶体结构和各向异性热/压缩行为

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jssc.2024.125021

Pseudo-ternary CrP₄-type (V,Cr,Mo)P₄ was successfully synthesized at the conditions of 4 GPa and 900 °C by using a large volume multi-anvil-type press. SEM-EDS and STEM analyses revealed that the synthesized pseudo-ternary (V,Cr,Mo)P₄ contains almost equimolar amounts of transition metals. The lattice parameters and unit cell volume of (V,Cr,Mo)P₄ yield the average value of its end-members. The low-temperature (133 K–333 K) in-situ synchrotron XRD measurements demonstrated that the c-axis showed the highest coefficient of thermal expansion, followed by the b-axis and the a-axis. These thermal behaviors are the same as the binary end-members and pseudo-binary (V,Cr)P₄. While from the high-pressure (P < 10 GPa) in-situ synchrotron XRD measurements, it was found that (V,Cr,Mo)P₄ showed no phase transition and compression behaviors in which the c-axis was more compressible than the other two axes (b and a) and the b-axis was slightly compressible more than the a-axis. The zero-pressure bulk modulus of 106 (1) GPa and 122.1 (7) GPa were obtained for (V,Cr)P₄ and (V,Cr,Mo)P₄, respectively. MoP₆ octahedral is highly distorted in comparison with VP₄ and CrP₄, thus the incorporation of MoP₄ greatly yields incompressible behaviors of CrP₄-type phosphides with respect to temperature and pressure.

在 4 GPa 和 900 ℃ 的条件下，利用大容量多安维尔压机成功合成了伪三元 CrP4 型 (V,Cr,Mo)P4。SEM-EDS 和 STEM 分析表明，合成的伪三元 (V,Cr,Mo)P4 几乎含有等摩尔量的过渡金属。(V,Cr,Mo)P4的晶格参数和单胞体积得出了其端部成员的平均值。低温（133 K-333 K）原位同步辐射 XRD 测量表明，c 轴的热膨胀系数最大，其次是 b 轴和 a 轴。这些热行为与二元端分子和伪二元（V,Cr）P4 相同。高压（P < 10 GPa）原位同步辐射 XRD 测量发现，(V,Cr,Mo)P4 没有出现相变和压缩行为，其中 c 轴的可压缩性高于其他两轴（b 轴和 a 轴），b 轴的可压缩性略高于 a 轴。(V,Cr)P4 和 (V,Cr,Mo)P4 的零压体积模量分别为 106 (1) GPa 和 122.1 (7) GPa。与 VP4 和 CrP4 相比，MoP6 的八面体高度畸变，因此，MoP4 的加入大大提高了 CrP4 型磷化物在温度和压力方面的不可压缩性。

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引用次数: 0

Synthesis, spectral, structural and Hirshfeld surface analysis of bis(5-ammonium isophthalic acid) hexabromostannate(IV) tetrahydrate hybrid 双（5-间苯二甲酸铵）六溴锡酸（IV）四水合物的合成、光谱、结构和 Hirshfeld 表面分析

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-19 DOI: 10.1016/j.jssc.2024.125022

A Tin(IV)-5-ammonium isophthalic acid hybrid has been successfully synthesized at room temperature using 5-ammonium isophthalic acid hydrobromide and tin (IV) bromide as precursors. Single-crystal X-ray diffraction analysis reveals that the compound crystallizes in a triclinic system with a centrosymmetric space group Pī, where the asymmetric unit consists of one [C₈H₈NO]⁺ cation, half of a [SnBr₆]²⁻ anion, and two water molecules. The crystal cohesion is reinforced by a network of intermolecular interactions, including N–H⋯Br, O–H⋯Br, N–H⋯O, and O–H⋯O hydrogen bonds, which play a crucial role in stabilizing the crystal structure and ensuring its integrity. BVS calculations performed on SnBr₆²⁻ anion resulted in 3.95, it is conclusively shown that tin's near the formal oxidation state is 4+. At room temperature, diffuse reflectance spectral measurements indicated a band gap of 2.93 eV. The ¹H and ¹³C NMR analyses reveal distinct chemical shifts and broadening due to coupling effects, providing critical insights into the structural arrangement and interactions within the compound. Fingerprint plots have been utilized to identify and quantify the percentage of hydrogen bonding interactions.

以 5-间苯二甲酸氢溴酸铵和溴化锡（IV）为前体，在室温下成功合成了锡（IV）-5-间苯二甲酸铵杂化物。单晶 X 射线衍射分析表明，该化合物的结晶呈三菱系，具有中心对称空间群 Pī，其中的不对称单元由一个 [C8H8NO]+ 阳离子、半个 [SnBr6]2- 阴离子和两个水分子组成。晶体的内聚力通过分子间的相互作用网络得到加强，其中包括 N-H⋯Br、O-H⋯Br、N-H⋯O 和 O-H⋯O 氢键，它们在稳定晶体结构和确保其完整性方面起着至关重要的作用。对 SnBr62- 阴离子进行的 BVS 计算结果为 3.95，这最终表明锡的近形式氧化态为 4+。在室温下，漫反射光谱测量结果表明带隙为 2.93 eV。1H 和 13C NMR 分析显示了不同的化学位移和耦合效应导致的展宽，为了解化合物内部的结构排列和相互作用提供了重要依据。指纹图谱被用来识别和量化氢键相互作用的百分比。

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引用次数: 0

Improvement of electrochemical properties of LiFe0.9Zn0.1-xMnxPO4 (x=0, 0.05, 0.075, 0.1) by double doping with Zn2+, Mn2+ 通过 Zn2+、Mn2+ 双掺杂改善 LiFe0.9Zn0.1-xMnxPO4（x=0，0.05，0.075，0.1）的电化学特性

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry

Pub Date : 2024-09-18 DOI: 10.1016/j.jssc.2024.125015

Zn²⁺ and Mn²⁺ co-doped LiFe_0.9Zn_0.1-xMn_xPO₄ (where x = 0, 0.05, 0.075, 0.1) composites are synthesized by a simple one-step hydrothermal method. The composition, structure, morphology and electrochemical properties of the materials are fully characterized using XRD, SEM, TEM, EDS, CV and AC impedance tests. The results show that the co-doping of Zn²⁺ and Mn²⁺ preserves the olivine structure of LiFePO₄ and also stabilizes the crystal structure, reduces the charge transfer resistance and improves the Li⁺ diffusion rate. When the initial specific capacity of the cathode material with the doping ratio of Zn = 0.025 and Mn = 0.075 is 161.8 mAh·g⁻¹, the discharge specific capacity after 200 cycles is still as high as 157.8 mAh·g⁻¹ with a capacity retention of 97.5 %, which is obviously better than the rest of the materials.

通过简单的一步水热法合成了 Zn2+ 和 Mn2+ 共掺杂 LiFe0.9Zn0.1-xMnxPO4（其中 x = 0、0.05、0.075、0.1）复合材料。利用 XRD、SEM、TEM、EDS、CV 和交流阻抗测试对材料的组成、结构、形貌和电化学性能进行了全面表征。结果表明，Zn2+ 和 Mn2+ 的共掺杂不仅保留了 LiFePO4 的橄榄石结构，还稳定了晶体结构，降低了电荷转移电阻，提高了 Li+ 的扩散速率。当 Zn = 0.025 和 Mn = 0.075 掺杂比的正极材料的初始比容量为 161.8 mAh-g-1 时，200 次循环后的放电比容量仍高达 157.8 mAh-g-1，容量保持率为 97.5%，明显优于其他材料。

引用次数: 0

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