Recently, nanoparticle organic hybrid materials (NOHMs) have been considered promising electrolytes for energy storage applications due to their unique combination of properties, which include high thermal stability, negligible vapor pressure, and easy synthesis. However, the structural features of NOHMs in electrochemical systems are not well understood. Hence, we investigate the impact of grafting type (ionic vs covalent) on the structure and performance of NOHMs that consist of a silica core and grafted HPE polymer (Jeffamine M2070) in aqueous solution with and without the presence of the supporting electrolyte (0.1 M KHCO₃) using small-angle neutron scattering. Careful analyses of the results indicate that even at low grafting density (0.8 chains nm^–2) and concentration (1–3 wt %), ionic NOHMs solutions contain a free polymer that may interact with the grafted polymer, altering the assembly of NOHMs in solution. Our investigation also elucidates that the covalent NOHM solutions consist of both aggregated and dispersed NOHMs in the solution. Moreover, the addition of the supporting electrolyte affects the assembly and structure of the polymer in the ionic NOHMs solution significantly, whereas only a slight change in the conformation of the grafted polymer is observed for covalent NOHMs. These conformational changes alter the performance of the NOHMs solution, resulting in a dramatic change in viscosity. Careful analysis shows that this significant alteration of solution viscosity in the ionic NOHMs can be traced back to the presence of the free polymer that interacts with the grafted layer and the attenuation of this interaction between the free and grafted polymers with the addition of salt. Thus, these studies elucidate the impact of grafting type on the overall structure, assembly, and performance of functionalized NOHMs in aqueous solution and explicitly correlate the structure and assembly of NOHMs to their transport properties and must be considered when designing functional systems that incorporate NOHMs.

中文翻译：

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深入了解不同接枝类型溶液中纳米颗粒有机杂化材料 (NOHM) 的组装和构象

最近，纳米颗粒有机杂化材料（NOHM）因其独特的性能组合（包括高热稳定性、可忽略的蒸气压和易于合成）而被认为是用于储能应用的有前途的电解质。然而，电化学系统中 NOHM 的结构特征尚不清楚。因此，我们研究了接枝类型（离子与共价）对 NOHM 结构和性能的影响，NOHM 由二氧化硅核和接枝 HPE 聚合物（Jeffamine M2070）组成，在水溶液中存在和不存在支持电解质（0.1 M KHCO ₃ ) 使用小角中子散射。对结果的仔细分析表明，即使在低接枝密度（0.8 链 nm ^–2）和浓度（1–3 wt%）下，离子 NOHM 溶液也含有可能与接枝聚合物相互作用的游离聚合物，从而改变 NOHM 的组装解决方案。我们的研究还阐明，共价 NOHM 溶液由溶液中聚集的和分散的 NOHM 组成。此外，支持电解质的添加显着影响离子NOHMs溶液中聚合物的组装和结构，而对于共价NOHMs，仅观察到接枝聚合物的构象发生轻微变化。这些构象变化改变了 NOHM 溶液的性能，导致粘度发生巨大变化。仔细分析表明，离子 NOHM 中溶液粘度的这种显着变化可以追溯到与接枝层相互作用的游离聚合物的存在，以及通过添加盐来减弱游离聚合物和接枝聚合物之间的这种相互作用。因此，这些研究阐明了接枝类型对水溶液中功能化 NOHM 的整体结构、组装和性能的影响，并明确将 NOHM 的结构和组装与其传输特性相关联，并且在设计包含 NOHM 的功能系统时必须考虑这一点。