Synthesis of Precursors

LaSrMnO4: Stoichiometric amounts of SrCO3 (Sigma Aldrich, ≥ 98%), Mn2O3 (Sigma Aldrich,

99%), and La2O3 (Alfa Aesar, 99.9%) were ground with a mortar and pestle. La2O3 was dried

at 1150 °C prior to use. The mixture was heated under a flow of pure argon (99.996%) with a flow rate of 0.5 standard liter per minute (SLM) at 1100 °C for 6 hours followed by heating at 1450 °C for 48 hours with one intermediate grinding.

La2CoO4+d: Stoichiometric ratios of La2O3 (Alfa Aesar, 99.9%, pre-dried at 1200 °C before use)

and Co3O4 (Alfa Aesar, 99.7%) were mixed using a ball mill made from ZrO2 for 1 hour with a

rotational speed of 600 RPM. For the milling process, a small fraction of isopropanol as the dispersing agent has been used. Then the mixture was heated at 1300 °C for 12 hours under Ar flowing (purity 99.999%, 0.4 SLM flow).

La2NiO4+d: A variety of La2NiO4+d compounds were synthesized by solid-state reactions

according to previous reports [74, 75]: Stoichiometric ratios of La2O3 (Alfa Aesar, 99.9%, pre-

dried at 1200 °C for 12 h before use) and NiO (Sigma Aldrich, +99.99%, pre-dried at 700 °C for 12 h before use) were mixed and heated under different atmospheres at 800 °C for 10 h. Then the mixture was hand-ground and re-heated under Air, oxygen or Ar at 1400 °C and kept for 4 h. The heating/cooling rates were 2 °C/min and 3 °C/ min, respectively. La2NiO4.13 has

been used to make the electrode composite, while the other La2NiO4+d compounds have been

used as references for XAS measurements. The treatment conditions and the respective lattice parameters for each La2NiO4+d compound are summarized in Table 4-1. The XRD

measurements of each phase can be found in Figure 4-1.

Table 4-1. Heating atmosphere under which the La2NiO4+d compounds were made. The composition of the

compounds were determined according to obtained lattice parameters in accordance with ref [76].

Compound Heating atmosphere Lattice parameters (Fmmm) Ni oxidation state a (Å) b (Å) c (Å) wt% La2NiO4.030§ purified Ar (in presence of Mn as O2 getter)* 5.483(1) 5.473(2) 12.599(1) 67 +2.06 5.512(1) 5.466(1) 12.566(1) 33 La2NiO4.055 Ar 5.475(1) 5.469(1) 12.618(1) 100 +2.22 La2NiO4.13 Air 5.466(1) 5.463(1) 12.676(1) 100 +2.26 La2NiO4.17 O2 5.466(1) 5.458(1) 12.697(1) 100 +2.34

* After heating at 800 °C for 12 h and 1400 °C for 4 h, the sample was heated once more at 900 °C for 4 h under presence of Mn.

Figure 4-1. XRD patterns of La2NiO4+d (0.03 ≤ d ≤ 0.17) that were also used as standards for XAS measurements.

LaSrCoO4: Stoichiometric amounts (according to literature [77]) of La2O3 (Alfa Aesar, 99.9%,

pre-dried at 1200 °C for 12 h before use), Co3O4 (Alfa Aesar, 99.7%) and SrCO3 (Sigma Aldrich

≥ 98%) are mixed and heated at 750 °C for 3 h under air (total weight of the batch = 0.5 g). The powders then hand ground and heated again at 1300 °C for 24 h under air.

LaSrFeO4: To synthesize pure LaSrFeO4, stoichiometric amounts of dry La2O3 (Alfa Aesar,

99.9%, pre-dried at 1200 °C for 12 h before use), SrCO3 (Sigma Aldrich ≥ 98%) and Fe2O3

(Sigma Aldrich ≥ 99%) have been ball milled for 1 h at a rotational speed of 600 RPM, using isopropanol as a dispersing agent. The mixture then heated at 700 °C for 12 h and 1200 °C for 48 h with intermediate hand grinding. Heating/cooling rates were considered to be 2 °C/min.

SrFeO2: To prepare SrFeO2, first SrFeO3 was made by ball milling of stoichiometric amounts of

SrCO3 (Sigma Aldrich ≥ 98%) and Fe2O3 for 5 min at 400 RPM using isopropanol as a dispersing

agent. The powders then heated at 1100 °C for 10 h followed by the second heat treatment at 1100 °C for 8 h with intermediate hand grinding. The synthesized SrFeO3 was further reduced

using CaH2 as the reducing agent (CaH2 was used in excess). The mixture of oxide and reducing

agent were loaded (inside an Ar-filled glovebox) in an air tight reactor and heated at 300 °C for 48 h (the sealed reactor was kept outside the glovebox during the heating operation, however, it was loaded/unloaded inside the glovebox). To remove the unreacted CaH2, the obtained

powders were washed (outside of the glovebox) with a mixture of methanol (400 ml, dried for 6 days with granular molecular sieve) and NH4Cl. The powders were further re-washed with

pure dried methanol and finally filtered.

(Co/Mg)0.5Fe0.5Sb2O4: Schafarzikite-type compounds with composition Mg0.5Fe0.5Sb2O4 and

Co0.5Fe0.5Sb2O4 have been prepared in collaboration with School of Chemistry, University of

Birmingham according to the preparation procedure described by de Laune et al. [78]: stoichiometric amounts of dried mixture of the metal oxides and antimony metal (CoO, 325 mesh Sigma-Aldrich; Fe2O3 ≥ 99.9% Sigma-Aldrich; Sb2O3, Reagent Plus, Sigma-Aldrich; Sb,

BDH; MgO, ≥ 99% 325 mesh Sigma-Aldrich) were heated in evacuated sealed quartz tubes between 6 hours to 36 hours at 700 °C with intermittent grinding.

La0.9Ba0.1F2.9 Electrolyte material: Preparation of the La0.9Ba0.1F2.9 was done according to

literature [24]: Stoichiometric ratios of BaF2 (STREM Chemicals, 99%) and LaF3 (STREM

balls (10 balls in total). The precursors were dried inside the glovebox at 190 °C for 4 h, prior to milling. All the milling operations within this thesis were performed by a RETSCH PM 100 or 100 CM planetary ball mill. The weight of each electrolyte batch was considered to be 10 g, resulting in a ball to powder ratio of 3.2:1.