The crystal structures of synthetic 7 .~ and 10 Jk manganates, synthetic birnessite and buserite, substituted by mono- and divalent cations were investigated by X-ray and electron diffractions. The monoclinic unit cell parameters of the subcell of lithium 7 A manganate, which is one of the best ordered manganates, were obtained by computing the X-ray powder diffraction data: a = 5.152 A, b = 2.845 A, c = 7.196 A, 13 = 103.08 ~ On the basis of the indices obtained by computing the X-ray diffraction data of Li 7 A manganate, monovalent Na, K and Cs and divalent Be, Sr and Ba 7 A manganates were interpreted as the same monoclinic structure with 13 = 100-103 ~ as that of Li 7 A manganate, from their X-ray diffraction data. In addition, divalent Mg, Ca and Ni 10 A manganates were also interpreted as the same monoclinic crystal system with 13 = 90-94 ~ The unit cell parameters, especially a, c and 13, change possibly with the type of substituent cation probably because of the different ionic radius, hydration energy and molar ratio of substituent cation to manganese. However, these diffraction data, except for those of Sr and Ba 7 A and Ca and Ni 10 A manganates, reveal only some parts of the host manganese structure with the edge-shared [MnO6] octahedral layer. On the other hand, one of the superlattice reflections observed in the electron diffractions was found in the X-ray diffraction lines for heavier divalent cations Sr and Ba 7 A and Ca and Ni 10 A manganates. The reflection presumably results from the substituent cation position in the interlayer which is associated with the vacancies in the edge-shared [MnO6] layer and indicates that the essential vacancies are linearly arranged parallel to the b-axis. Furthermore, the characteristic superlattice reflection patterns for several cations, Li, Mg, Ca, Sr, Ba and Ni, manganates were interpreted that the substituent cations are regularly distributed in the interlayer according to the exchange percentage of substituent cation to Na + . In contrast, the streaking in the a-direction observed strongly in the electron diffractions for heavier monovalent cations, K and Cs, manganates probably results from the disordering of their cations in the a-direction in the interlayer.

中文翻译：

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单价和二价阳离子取代的合成 7 Å 和 10 Å 锰酸盐的晶体结构

通过 X 射线和电子衍射研究了被单价和二价阳离子取代的合成 7 .- 和 10 Jk 锰酸盐、合成水钠锰矿和布氏石的晶体结构。通过计算 X 射线粉末衍射数据得到 7 A 锰酸锂子电池的单斜晶胞参数，它是最好的有序锰酸盐之一：a = 5.152 A，b = 2.845 A，c = 7.196 A， 13 = 103.08 ~ 根据计算 Li 7 A 锰酸盐的 X 射线衍射数据得到的指数，单价 Na、K 和 Cs 和二价 Be、Sr 和 Ba 7 A 锰酸盐被解释为与 13 相同的单斜结构= 100-103 ~ 与 Li 7 A 锰酸盐的 X 射线衍射数据相同。此外，二价镁、Ca 和 Ni 10 A 锰酸盐也被解释为相同的单斜晶系，13 = 90-94 ~ 晶胞参数，尤其是 a、c 和 13，可能随着取代阳离子的类型而变化，可能是因为离子半径不同，水合能和取代基阳离子与锰的摩尔比。然而，除了 Sr 和 Ba 7 A 以及 Ca 和 Ni 10 A 锰酸盐的衍射数据外，这些衍射数据仅揭示了具有边缘共享 [MnO6] 八面体层的主体锰结构的某些部分。另一方面，在较重的二价阳离子 Sr 和 Ba 7 A 以及 Ca 和 Ni 10 A 锰酸盐的 X 射线衍射线中发现了在电子衍射中观察到的一个超晶格反射。反射可能是由夹层中的取代阳离子位置引起的，该位置与共享边缘的 [MnO6] 层中的空位相关，并表明基本空位平行于 b 轴线性排列。此外，Li、Mg、Ca、Sr、Ba 和 Ni、锰酸盐等几种阳离子的特征超晶格反射模式被解释为根据取代基阳离子与 Na + 的交换百分比，取代基阳离子在层间有规律地分布。相比之下，在较重的单价阳离子 K 和 Cs 的电子衍射中强烈观察到 a 方向的条纹，锰酸盐可能是由于它们的阳离子在中间层中的 a 方向无序。