In our preceding paper (Y. Fukui et al., Phys. Chem. Chem. Phys., 2023, 25, 25594–25602), we reported a systematic study of the Ag⁺-ion conducting behaviour of silver iodide (AgI)-loaded mesoporous aluminas (MPAs) with different pore diameters and AgI-loading ratios. By optimising the control parameters, the Ag⁺-ion conductivity has reached 7.2 × 10⁻⁴ S cm⁻¹ at room temperature, which is more than three orders of magnitude higher than that of bulk AgI. In the present study, the effect of silver bromide (AgBr)-doping in the AgI/MPA composites on Ag⁺-ion conductivity is systematically investigated for the first time, using variable-temperature powder X-ray diffraction, differential scanning calorimetry, and electrochemical impedance spectroscopy measurements. The AgBr-doped AgI/MPA composites, AgI-AgBr/MPA, formed a homogeneous β/γ-AgI-structured solid solution (β/γ-AgI_ss) for the composites with AgBr ≤ 10 mol%, above which the composites underwent a phase separation into β/γ-AgI_ss and face-centred cubic AgBr solid solutions (AgBr_ss). The onset temperature of the exothermic peaks attributed to the transition from α-AgI-structured solid-solution phase to β/γ-AgI_ss or AgBr_ss decreased with increasing the AgBr-doping ratio. The room-temperature ionic conductivity of the AgI–AgBr/MPA composites exhibited a volcano-type dependence on the AgBr-doping ratio with the highest value (1.6 × 10⁻³ S cm⁻¹) when the AgBr content was 10 mol%. This value is more than twice as high as that of the highest conducting AgI/MPA found in our previous study.

中文翻译：

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碘化银/介孔氧化铝复合材料离子传导的系统研究2：溴化银掺杂的影响

在我们之前的论文 (Y. Fukui et al. , Phys. Chem. Chem. Phys. , 2023, 25 , 25594–25602) 中，我们报道了对碘化银 (AgI)- 的Ag ⁺离子传导行为的系统研究。具有不同孔径和 AgI 负载比的负载介孔氧化铝 (MPA)。通过优化控制参数，室温下Ag ⁺离子电导率达到7.2 × 10 ^-4 S cm ^-1，比块体AgI高三个数量级以上。在本研究中，首次系统地研究了AgI/MPA 复合材料中溴化银 (AgBr) 掺杂对 Ag ⁺离子电导率的影响，采用变温粉末 X 射线衍射、差示扫描量热法和电化学阻抗谱测量。 AgBr 掺杂的 AgI/MPA 复合材料 AgI-AgBr/MPA 形成均匀的 β/γ-AgI 结构固溶体 (β/γ-AgI _ss )，其中 AgBr ≤ 10 mol%，复合材料在该固溶体之上经历了相分离为 β/γ-AgI _ss和面心立方 AgBr 固溶体 (AgBr _ss )。随着AgBr掺杂比例的增加，由α-AgI结构固溶体相转变为β/γ-AgI _ss或AgBr _ss的放热峰的起始温度降低。 AgI-AgBr/MPA复合材料的室温离子电导率对AgBr掺杂比例表现出火山型依赖性，当AgBr含量为10 mol%时，离子电导率达到最高值（1.6 × 10 ^-3 S cm ^-1 ）。该值比我们之前研究中发现的最高导电 AgI/MPA 的值高出两倍多。