Materials

Chapter 1. Introduction

1.3. Nanocatalyst

1.3.4. Materials

and corresponding high wettability. To control the wettability, there are some factors as follows

◼ Concentration of solution

◼ A kind of solvent

◼ A kind of solute

◼ Atmospheric condition

◼ Processing temperature

1.3.3.3.2.

Pore structure of Backbone

Another significant factor to control morphology in the infiltration is the pore-morphology of scaffold. Küngas et al. ^[75] and Sarikaya et al. ^[76,77] studied the morphological effect of scaffold on the microstructure of electrode and the performances by using HF treatments and various pore former, respectively. As a result, for the HF treatment, they found significant increases in the surface areas, even after calcination of the treated scaffold. For the pore former effect, the uniformly distributed pores and percolation of the constituent phases minimize the slow anode activation process by using activated reactive sites, while large pores provide a major pathway for gas transport.

, where 𝑟_𝐴, 𝑟_𝐵 and 𝑟_𝑂 are the ionic radius of A, B, and O ions, respectively.

Another perovskite derived by intensive distortion has close-packing type of AO3 layers with the B cations in octahedral holes: the hexagonal (AB) sequence with octahedral B cations sharing faces into infinite one-dimensional chains within the hh (=2H) hexagonal polytype, e.g. BaCoO3. In particular, the alkali earth manganates, such as SrMnO3 and BaMnO3, has so-called hexagonal perovskite layer due to the high oxidation number of Mn.^[78–83]

Between these two extreme forms, the perovskite structure can possess mixed phases with various proportions of cubic and hexagonal layers, such as the material Pr0.5Ba0.5MnO3 and Pr0.5Ba0.5Mn0.85Co0.15O3).^[78–83]

Figure 1-19 Crystal structure of simple perovskite (ABO3)

Layered Perovskite (AA’B2

O

5

)

The layered perovskite structure is named because the unit cell of is twice that of perovskite. It has the same architecture of 12 coordinate A sites and 6 coordinate B site, while two cations are ordered on the B site. This family of compounds can be theoretically described with a stacking sequence of BaO-CoO2-LnOx-CoO2 long the c-axis as shown in Figure 1-20. All mobile oxygen is located only the Ln-O plane, providing oxygen transport channel.

Figure 1-20 Crystal structure of a layered perovskite

This layered structure reduces the oxygen bonding strength in the [AO] layer and provides a disorder-free channel for ion motion, which enhances oxygen diffusivity.^[84] Layered perovskite oxides have received tremendous interest because of its high chemical diffusion and a high surface exchange coefficient.

Ruddlesden-popper (An+1

B

n

O

3n+1

)

This oxide has a K2NiF4-type structure formulated as A2BO4+, which can be described as ABO3

perovskite and AO rock-salt layers arranged along the c-axis with the enough space in the AO layer.

This structure allows for the accommodation of oxygen over stoichiometry as oxygen interstitial species with negative charge, which are balanced through the oxidation of the B-site cations.^[85–89]

These materials show good property in terms of electronic conductivity, oxygen ionic transport property, electrocatalysis for oxygen reduction reaction, and moderate thermal expansion.

Figure 1-21 Crystal structure of a Ruddlesden-Popper

Spinel (AB2

O

4

)

Figure 1-22 Crystal structure of a Spinel

The spinel structure has the formula AB2O4. It is essentially cubic, and the O ion forms an fcc lattice.

Cations (usually metals) occupy 1/8 of the tetrahedral position and 1/2 of the octahedral site, and there are 32 O-ions in the unit cell. The spinel structure is very flexible for the cations that can be incorporated and can mix A and B cations. Basically, the spinel structure is composed of divalent and trivalent cations, and the spinel structure of tetrahedral interstices and octahedral interstices,

respectively. It is also interesting because they can each contain voids as a regular part of the crystal.^[90–92]

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Chapter 2. Energy Conversion: Scale-down and Sr-doping