skip to main content


Title: Proton‐Mediated and Ir‐Catalyzed Iron/Iron‐Oxide Redox Kinetics for Enhanced Rechargeability and Durability of Solid Oxide Iron–Air Battery
Abstract

Long duration energy storage (LDES) is an economically attractive approach to accelerating clean renewable energy deployment. The newly emerged solid oxide iron–air battery (SOIAB) is intrinsically suited for LDES applications due to its excellent low‐rate performance (high‐capacity with high efficiency) and use of low‐cost and sustainable materials. However, rechargeability and durability of SOIAB are critically limited by the slow kinetics in iron/iron‐oxide redox couples. Here the use of combined proton‐conducting BaZr0.4Ce0.4Y0.1Yb0.1O3(BZC4YYb) and reduction‐promoting catalyst Ir to address the kinetic issues, is reported. It is shown that, benefiting from the facilitated H+diffusion and boosted FeOx‐reduction kinetics, the battery operated under 550 °C, 50% Fe‐utilization and 0.2 C, exhibits a discharge specific energy density of 601.9 Wh kg–1‐Fe with a round‐trip efficiency (RTE) of 82.9% for 250 h of a cycle duration of 2.5 h. Under 500 °C, 50% Fe‐utilization and 0.2 C, the same battery exhibits 520 Wh kg–1‐Fe discharge energy density with an RTE of 61.8% for 500 h. This level of energy storage performance promises that SOIAB is a strong candidate for LDES applications.

 
more » « less
Award ID(s):
1801284
NSF-PAR ID:
10370449
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Science
Volume:
9
Issue:
30
ISSN:
2198-3844
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Long duration energy storage (LDES) is economically attractive to accelerate widespread renewable energy deployment. But none of the existing energy storage technologies can meet LDES cost requirements. The newly emerged solid oxide iron air battery (SOIAB) with energy-dense solid Fe as an energy storage material is a competitive LDES-suitable technology compared to conventional counterparts. However, the performance of SOIAB is critically limited by the kinetics of Fe3O4reduction (equivalent to charging process) and the understanding of this kinetic bottleneck is significantly lacking in the literature. Here, we report a systematic kinetic study of Fe3O4-to-Fe reduction in H2/H2O environment, particularly the effect of catalyst (iridium) and supporting oxides (ZrO2and BaZr0.4Ce0.4Y0.1Yb0.1O3). With in situ created Fe3O4, the degree of reduction is measured by the change of H2O and H2concentrations in the effluent using a mass spectrometer, from which the kinetic rate constant is extracted as a function of inlet H2concentration and temperature. We find that kinetics can be nicely described by Johson-Mehl-Avrami (JMA) model. We also discuss the stepwise reduction mechanisms and activation energy for the reduction process.

     
    more » « less
  2. Long duration electricity storage (LDES) with 10+ hour cycle duration is an economically competitive strategy to accelerate the penetration of renewable energy into the utility market. Unfortunately, none of the available energy storage technologies can meet the LDES requirements in terms of duration and cost. The newly emerged solid-oxide iron–air batteries (SOIABs) with energy-dense solid iron as an energy storage material have inherent advantages for LDES applications. Herein, we report for the first time the LDES capability of SOIABs even at a laboratory scale. We show that SOIABs with an Ir-catalyzed Fe-bed can achieve excellent energy density (625 W h kg −1 ), long cycle duration (12.5 h) and high round-trip efficiency (∼90%) under LDES-related working conditions. Given the excellent low-rate performance and the use of earth-abundant, low-cost Fe as an energy storage material, we conclude that the SOIAB is a well-suited battery technology for LDES applications. 
    more » « less
  3. Long duration electricity storage (LDES) with 10+ hour cycle duration is an economically competitive option to accelerate the penetration of renewable energy into the utility market. Unfortunately, none of the available energy storage technologies can meet the LDES’ requirements for duration and cost. We here report a focused kinetic study on Fe-oxide reduction process, which is a key step for solid oxide iron-air battery; the latter has been recently demonstrated as a LDES compatible battery. The study clearly shows that Ir is an excellent catalyst to boost the sluggish Fe-oxide reduction kinetics. 
    more » « less
  4. Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1 
    more » « less
  5. Abstract

    The growing demand for bioelectronics has generated widespread interest in implantable energy storage. These implantable bioelectronic devices, powered by a complementary battery/capacitor system, have faced difficulty in miniaturization without compromising their functionality. This paper reports on the development of a promising high‐rate cathode material for implantable power sources based on Li‐exchanged Na1.5VOPO4F0.5anchored on reduced graphene oxide (LNVOPF‐rGO). LNVOPF is unique in that it offers dual charge storage mechanisms, which enable it to exhibit mixed battery/capacitor electrochemical behavior. In this work, electrochemical Li‐ion exchange of the LNVOPF structure is characterized by operando X‐ray diffraction. Through designed nanostructuring, the charge storage kinetics of LNVOPF are improved, as reflected in the stored capacity of 107 mAh g−1at 20C. A practical full cell device composed of LNVOPF and T‐Nb2O5, which serves as a pseudocapacitive anode, is fabricated to demonstrate not only high energy/power density storage (100 Wh kg−1at 4000 W kg−1) but also reliable pulse capability and biocompatibility, a desirable combination for applications in biostimulating devices. This work underscores the potential of miniaturizing biomedical devices by replacing a conventional battery/capacitor couple with a single power source.

     
    more » « less