Biomimetic mineralization can lead to advanced crystalline composites with common chemicals under ambient conditions. An exceptional example is biomimetic nacre with its superior fracture toughness. The synthesis of the prismatic layer with stiffness and wear resistance nonetheless remains an elusive goal. Herein, we apply a biomimetic mineralization method to grow prismatic-type CaCO3 thin films, mimicking their biogenic counterparts found in mollusk shells with a three-step pathway: coating a polymer substrate, deposition of a granular transition layer, and mineralization of a prismatic overlayer. The synthetic prismatic overlayers exhibit structural similarity and comparable hardness and Young’s modulus to their biogenic counterparts. Furthermore, employment of a biomacromolecular soluble additive, silk fibroin, in fabrication of the prismatic thin films leads to micro-/nano-textures with enhanced toughness and emerging under-water superoleophobicity. This study highlights the crucial role of the granular transition layer in promoting competition growth of the prismatic layer.

The profiles of the decisive thermodynamic potentials in a battery are analyzed with emphasis on the solid electrolyte interphase (SEI) passivation layers that form. Consequences for growth and chemical stability are discussed. The extreme cases of an artificial SEI and a thermodynamically fully defined in situ SEI are distinguished. The analysis also includes the open-circuit voltage drop over the combination SEI/electrolyte. The treatment is rigorous for the assumed simplified conditions (constant transport coefficients, pseudo-1D geometry, and absence of space charge zones and structural complications). In the last section, more realistic situations are addressed on a less quantitative level. The results can also be applied to fuel cells or electrolyzers.

In biomineralization and bioinspired mineralization, substrates and additives function synergistically in providing structural control of the mineralized layers including their orientation, polymorph, morphology, hierarchical architecture, etc. Herein, a novel type of granular aragonitic CaCO-poly(acrylic acid) substrate guides the mineralization of prismatic CaCO thin films of distinct morphology and polymorph in the presence of different additives including organic compounds and polymers. For instance, weakly charged amino acids lead to columnar aragonite overlayers, while their charged counterparts and organic acids/bases inhibit the overgrowth. Employment of several specific soluble polymer additives in overgrowth instead results in calcitic overlayers with distinct hierarchical architecture, good hardness/Young's modulus, and under-water superoleophobicity. Interestingly, self-organized patterns in the CaCO-poly(l-glutamic acid) overlayer are obtained under proper mineralization conditions. We demonstrate that the granular seed comprised of mineralized and polymeric constituents is a versatile platform for obtaining prismatic CaCO thin films, where structural control can be realized by the employment of different types of additives in overgrowth. We expect the methodology to be applied to a broad spectrum of bioinspired, prismatic-type crystalline products, aiming for the development of high-performance hybrids.

Our study shows that in bioinspired mineralization, the crystal shape and lateral orientation are highly correlated instead of being independent.

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