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Development of Efficient Electrocatalysts for Metal-Air Batteries

Development of Efficient Electrocatalysts for Metal-Air Batteries
Translated Title
금속 공기전지용 고효율 양극촉매 개발
Hyun, Su Yeon
DGIST Authors
Hyun, Su Yeon; Shanmugam, Sangaraju; Kim, Ha Suck
Shanmugam, Sangaraju
Kim, Ha Suck; 1330
Issue Date
Available Date
Degree Date
2016. 8
Oxygen electrocatalystMetal-air batteryLithium-oxygen (Li-O2) batteryCobalt vanadium oxideCo-CoO/CNR공기 촉매금속 공기전지리튬 공기전지코발트 바나듐 옥사이드
Metal-air batteries have a lot of merits whereas there are still facing various fundamental issues to reach commercial applications such as poor cycleability, low round-trip efficiency and poor rate capability. For instance, the round-trip efficiency of metal-air batteries with bare carbon electrode is below 70% in contrast with that of the conventional LIBs-in case LiCoO2 is around 95%. These challenges are stem from instability of not only Li metal but also binder and electrolyte. Above all, the major challenge is the sluggish kinetics of oxygen reduction and evolution reactions at the oxygen electrode during battery discharge and charge. Therefore, the development of electrochemically active, stable and non-precious bifunctional catalyst is highly required for the commercialization of this technology for practical metal-air batteries. We first focus on designing an inexpensive and highly active OER electrocatalyst, Co3V2O8 with 1D morphology consisting of nanotubes and nanorods which can be used in Zn-air battery. In addition to looking for new cost-effective materials with stable structure and also tuning the morphology of the existing material to improve their catalytic activity which is directly related with battery performance has been considered to improve oxygen evolution reaction. From this point of view, one dimensional (1D) nanostructure materials possess better triple phase boundary to facilitate efficient transport pathways for electrons and ions. Moreover, high surface area of 1D nanostructure expected to provide high performance to suppress sluggish oxygen electrode kinetics. To understand the effect of Co3V2O8 morphology on OER activity, we have synthesized 1D & 0D nanostructures and discussed their performance. The result demonstrates that the 1D-Co3V2O8 cathode exhibits superior OER activity and long term stability to those of 0D-Co3V2O8 and even for commercial precious metal catalysts. The excellent OER performance and long-term durability is attributed to the well-designed one dimensional nanorods and nanotubes like structure, the synergistic effect of different metal ions, and the presence of amorphous nitrogen-doped carbon. In the second part of research, we developed Co-CoO/CNR catalysts as a bifunctional air cathode for the OER and ORR for application of Li-O2 batteries. High power density could be achieved with this system since the Li-O2 batteries possess higher open-circuit voltage of 2.96 V than that of Zn-air batteries (1.65 V). The Co-CoO/CNR cathode achieved a discharge capacity of 10569 mAh gcatalyst-1 at a current density of 100 mA g-1, which is higher than that of CNR electrode (7087 mAh gcatalyst-1). This result demonstrates that Co-CoO/CNR catalyst exhibits good oxygen reduction activity. Moreover, the Co-CoO/CNR cathode shows almost 6 times better cycling performance than CNR electrode with a cutoff capacity of 1000 mAh gcatalyst-1. The poor cycleability of Li-O2 batteries with CNR electrode should be caused by the accumulation of Li2CO3, which is the one of the major products in this oxygen electrode. The enhancement of discharge capacity and voltage observed for Co-CoO/CNR electrode may due to the presence of uniform mesoporous nanostructure with high surface area so that it could diffuse Li+ easily and provide space to accommodate discharge solid products. Furthermore, Co-CoO nanoparticles on CNR electrode might help to minimize the oxidation of carbon structure and form nanosized Li products during the discharge process. ⓒ 2016 DGIST
Table Of Contents
I. Introduction 1 -- 1.1 Forward 1 -- 1.2 Objectives 3 -- II. Theoretical background 4 -- 2.1 Metal-air battery 4 -- 2.1.1 Metal-air battery fundamentals 4 -- 2.2 Aqueous metal-air battery system 6 -- 2.2.1 Zn-air battery 6 -- 2.2.2 Working principle of Zn-air battery 7 -- 2.2.3 Drawbacks of Zn-air battery 8 -- 2.3 Non-aqueous metal-air battery system 10 -- 2.3.1 Li-air battery 10 -- 2.3.2 Working principle of Li-air battery 14 -- 2.3.3 Drawbacks of Li-air battery 15 -- 2.4 Literature survey on bifunctional (OER & ORR) catalyst 18 -- III. Experimental 21 -- 3.1 Preparation of electrocatalysts 21 -- 3.1.1 Chemicals 21 -- 3.1.2 Synthetic approach 21 -- 3.2 Characterization 24 -- 3.2.1 Material characterization 24 -- 3.2.2 Electrochemical characterization 24 -- 3.2.3 Metal-air battery test 25 -- 3.2.4 Air cathode preparation and Zn-air cell assembly 25 -- 3.2.5 Air cathode preparation and Li-oxygen cell assembly 26 -- IV. Results and discussion 28 -- 4.1 Development of cost-effective and efficient Co3V2O8 catalyst for Zn-air battery 28 -- 4.1.1 Structural analysis 28 -- 4.1.2 Morphology analysis 31 -- 4.1.3 Studies on the electrochemical activities of catalyst 35 -- 4.1.4 Zn-air battery test 45 -- 4.1.5 Summary 47 -- 4.2 Rational design of air cathode for Li-oxygen battery 48 -- 4.2.1 Structural analysis 48 -- 4.2.2 Morphology analysis 56 -- 4.2.3 Electrochemical characterization 60 -- 4.2.4 Li-oxygen battery test 64 -- 4.2.5 Air cathode post-mortem analysis 72 -- 4.2.6 Summary 79 -- V. Conclusions 80 -- References 81 -- 국문 요약문 92
Energy Systems Engineering
Related Researcher
  • Author Shanmugam, Sangaraju Advanced Energy Materials Laboratory
  • Research Interests Electrocatalysts for fuel cells; water splitting; metal-air batteries; Polymer electrolyte membranes for fuel cells; flow batteries; Hydrogen generation and utilization
Department of Energy Science and EngineeringThesesMaster

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