A simple and novel effective strategy using mechanical treatment to improve the oxygen uptake/release rate of YBaCo4O7+δ for thermochemical cycles

doi:10.1016/j.jmst.2020.06.043

Abstract

Abstract:

In recent years, oxygen storage materials (OSMs) have been widely used in many fields. It would be particularly important for researchers to design high-oxygen-uptake/release-rate materials. In this study, various synthesis processes were used to successfully synthesize YBaCo₄O_7+δ and comprehensively investigate their potential applications. Compared with traditional solid-state reaction method and co-precipitation method, the results demonstrated that the utilization of mechanical ball milling treatment on co-precipitated precursors could lead to samples with reversible oxygen uptake/release under an oxidative atmosphere at low temperatures. The resultant materials exhibited fast oxygen absorption/desorption rate that could uptake/release oxygen directly to the equilibrium state within 9 min and 20 min, respectively. The mechanochemically ball-milled sample possessed outstanding oxygen storage performance, which could be attributed to their small particle size, the active outer surface of particles, large specific surface area, and relatively low activation energy. Moreover, the ball-milled sample also exhibited excellent cycling stability during relatively short time spacing. TG results also demonstrated that the ball-milled samples could reversibly uptake/release 2.90 wt.% of excess oxygen (while only 0.70 wt.% for solid-state samples) by adjusting the ambient temperature under pure O₂ atmosphere, which would make them promising candidates in various applications. This research demonstrated that mechanical treatment could be an effective strategy to tune the properties and oxygen storage capacity(OSC) performances of YBaCo₄O_7+δ.

Key words: Oxygen storage materials, Mechanical treatment, YBaCo₄O₇, Thermochemical cycles

Tingru Chen, Yusuke Asakura, Takuya Hasegawa, Teruki Motohashi, Shu Yin. A simple and novel effective strategy using mechanical treatment to improve the oxygen uptake/release rate of YBaCo₄O_7+δ for thermochemical cycles[J]. J. Mater. Sci. Technol., 2021, 68: 8-15.

Figures/Tables 12

Fig. 1. XRD patterns together with Rietveld results for YBaCo4O7+δ synthesized by the three routes: (a) SS sample, (b) CP sample, and (c) BM sample. (d) Schematic illustration of the crystal structure of YBaCo4O7+δ.

Table 1 Structure parameters of the as-obtained samples.

Sample name	a [Å]	c [Å]	V [Å³]	Rwp [%]	Rp [%]	S
Solid state SS	6.2963(3)	10.2491(4)	351.88(3)	2.3	1.6	1.9
Coprecipitation CP	6.2988(2)	10.2623(3)	352.14(3)	2.3	1.6	1.6
Ball milling BM	6.2978(2)	10.2720(2)	352.82(3)	1.6	1.3	1.3

Fig. 2. SEM images of YBaCo4O7+δ synthesized by the three routes. (a) SS sample, (b) CP sample, and (c) BM sample.

Fig. 3. EDS mapping images of YBaCo4O7+δ synthesized by ball-milling treatment.

Fig. 4. (a) TEM image and (b) HRTEM image of the BM sample (inset: SAED pattern).

Fig. 5. TG curves of YBaCo4O7+δ in flowing O2 gas: (a) from room temperature to 1000 °C with a heating rate of 5 °C/min and (b) up to 500 °C with heating/cooling rates of 5 °C/min. (i) SS sample, (ii) CP sample, and (iii) BM sample.

Table 2 The maximum weight change (ΔW), OSC, oxygen content, and specific surface area for the SS, CP, and BM samples.

As prepared sample	Maxium ΔW	OSC μmol-O₂/g	Oxygen content δ	Specific surface area/(m²/g)
SS	1.79 wt%	558	0.64	0.4
CP	2.60 wt%	811	0.93	1.1
BM	2.89 wt%	905	1.04	3.2

Fig. 6. TG curves of YBaCo4O7+δ with heating/cooling rates of ±5 °C/min and ±1 °C/min. (a) CP sample and (b) BM sample.

Fig. 7. (a) Isothermal TG curves in flowing N2 and O2 at 350 °C for YBaCo4O7+δ synthesized by the three routes (i) SS sample, (ii) CP sample, and (iii) BM sample. (b) Oxygen uptake/release time of the three samples. (c) Isothermal TG curves and related (d) uptake/release time of the BM sample at different operation temperatures.

Fig. 8. (a) Isothermal TG curves recorded for YBaCo4O7+δ synthesized by the three routes (i) SS sample, (ii) CP sample, and (iii) BM sample at 350 °C upon switching the gas flow between N2 and O2 (time interval: 60 min). (b) uptake/release time required for the first cycle; (c) uptake/release time in the fifth cycle for the three samples.

Fig. 9. (a) Isothermal TG curves recorded for YBaCo4O7+δ at 350 °C upon switching the gas flow between N2 and O2 with a time interval of 30 min. (b) the cyclic performance of oxygen release. Solid line: BM sample; Line-symbol: CP sample).

Fig. 10. (a) TG curves of the three YBaCo4O7+δ samples upon temperature swing between 350 °C and 500 °C in flowing O2 gas: (i) SS sample, (ii) CP sample, and (iii) BM sample. (b) Temperature profile.

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A simple and novel effective strategy using mechanical treatment to improve the oxygen uptake/release rate of YBaCo₄O_7+δ for thermochemical cycles

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