Interfacially engineered induced nickel-based heterostructures as efficient catalysts for Li-O2 batteries
Graphical abstract
Introduction
The theoretical energy density of Li-O2 battery is similar to that of gasoline system, almost 10 times that of the most advanced lithium-ion battery, has been attracted extensive attention [1], [2], [3]. However, Li-O2 batteries still have many challenges in practical application, such as extremely low round-trip efficiency, poor rate capacity and pitiful cycle life [4,5]. The main reason for these problems lies in the slow oxygen redox reaction/oxygen evolution reaction (ORR/OER) dynamics of the battery, which associates with the deposition and decomposition processes of the final product Li2O2 [6], [7], [8]. Hence, a basic understanding of the evolutionary process of Li2O2 and targeted effective engineering design, such as the exploit of high-efficiency cathode, is crucial to improve the electrochemical properties of Li-O2 batteries [9], [10], [11]. The two-electron reaction process in the Li-O2 battery has been widely revealed [12,13]. In this process, LiO2, as the bridge of the reaction, and take an significance role in the deposition and decomposition of Li2O2, which also affects the electrochemical performance of Li-O2 battery [14], [15], [16]. It is well known that in the process of discharge, the adsorption path of LiO2 with the cathode is crucial to the subsequent nucleation and growth of Li2O2 [17], [18], [19]. Too strong or too weak adsorption will lead to the accumulation of Li2O2 on the cathode into film (surface adsorption path) and large particle shape (solution mediated path), respectively [20], [21], [22], which is be harmful to the capacity improvement and the transfer of electrons and ions. On the other hand, in the battery reaction process, especially in the charging process, the electronic interaction between the discharge products/intermediate species and the catalyst, is also an important factor affecting the round-trip efficiency of battery [23,24].
It is well known that the adsorption of discharge products/intermediates and their electronic interaction with catalysts can effectively improve the electrochemical reaction kinetics by reasonably adjusting the electronic structure of catalysts [25], [26], [27], [28]. Heterostructure construction is a flexible strategy by which the electronic structure and distribution can be easily adjusted [29], [30], [31]. Firstly, differences in Fermi levels between heterostructure will lead to redistribution of electrons between interfaces, which optimize the adsorption of LiO2 on the cathode [32], [33], [34]. In addition, the built-in electric field on the heterostructure can tailor the interface electronic structure and promote the charge transfer rate between different regions of the interface [35], [36], [37]. Finally, heterostructure formation promotes the distortion of local fine atoms, which can be used as additional active sites of ORR/OER, which is beneficial to improve the catalytic efficiency and enhance the battery capacity [38]. Because of these above advantages, the construction of heterostructure has been widely studied in the field of metal-air batteries [39], [40], [41]. For example, An et al. synthesized a CuS/NiS2 atomic-level coupling interface for Zn-air batteries [42]. Due to the strong Jahn-Teller effect of Cu in CuS, abundant vacancy defects and lattice distortions are generated at the CuS/NiS2 interface, showing excellent ORR/OER catalytic activity. The strategy of improving electrochemical performance by constructing heterostructure has also been developed in the field of Lithium-oxygen batteries in recent years [43,44]. Wang et al. reported NiCo2S4@NiO core-shell arrays, the built-in interfacial potential between NiCo2S4 and NiO can significantly enhance the interfacial charge transfer kinetics [45], which promoted the formation of large-scale pea-like Li2O2, and Li-O2 batteries based on NiCo2S4@NiO cathode exhibited an improved over-potential of 0.88 V and cycling stability. Although the introduction of heterostructure can improve the catalytic performance of Li-O2 batteries cathode to some extent, however, the capacity, round-trip efficiency as well as cycle stability of Li-O2 batteries are still far from satisfactory [46], [47], [48]. In addition, how the adsorption behavior between the heterostructure and the intermediate LiO2 affects the deposition and decomposition of Li2O2, and how the electronic interaction between the heterostructure and LiO2 improves the performance of Li-O2 batteries needs to be further systematically studied.
On this basis, NiO nanosheets were firstly grown on carbon cloth substrates (NiO/CC) by simple hydrothermal and calcination methods, and then a series of Se-doped NiO/CC were synthesized at different temperatures (Se@NiO/CC). Surprisingly, the Se@NiO/CC based cathode exhibit low over-potential (1.14 V), highest discharge capacity (9883 mAh g−1) and long cycling stability (111 cycles). The built-in electric field formed by the heterostructure accelerates the transport of Li+ and electrons [49], thereby improving the ORR/OER dynamics. At the same time, the local lattice distortion derived from the heterostructure can serve as an additional active site of ORR/OER, which is beneficial to improvement of the Li-O2 battery capacity. The model is studied systematically through the combination of theoretical calculations and experiments, and the results showed that Se@NiO/CC has an appropriate adsorption of LiO2, which promoted the formation/decomposition of discharge products. In the meantime, the interaction between Se@NiO/CC and the intermediate LiO2 accelerates the transport during discharge and charge processes. This study provides a new perspective for the rational design and synthesis of heterostructure for Li-O2 batteries, which is crucial for the development of high-performance Li-O2 batteries.
Section snippets
Preparation and materials
Lithium anodes were purchased from China Energy Lithium Co, Ltd. (Tianjin, China). Lithium triflate (LiCF3SO3), Nickel nitrate (Ni(NO3)2·6H2O), ethanol, 2-methylimidazole, Selenium powder (Se) were purchased from Sinopharm Chemical Reagent Co. Ltd., Shanghai, China. These reagents are of analytical grade and require no further purification.
Synthetic materials
Preparation of NiO/CC cathode: Carbon cloth (CC) was treated with acetone and deionized water for 30 min, and then washed with deionized water. Fisrtly,
Characterization of material properties
Fig 1a shows the synthesis of Se@NiO/CC. Firstly, NiO nanosheets loaded on CC (NiO/CC) were obtained by hydrothermal and subsequent calcination strategy, and then heteroatomic Se was introduced into NiO/CC in Ar atmosphere. Fig. 1b shows a scanning electron microscope (SEM) image of the pristine carbon cloth (CC), which consists of woven carbon fibers with a diameter of circa 9 μm. Fig. 1c illustrated the SEM image of the NiO/CC, and found that CC is uniformly covered by smooth nanosheets. It
Conclusions
In conclusion, Se@NiO/CC-2 with unique heterostructure was successfully prepared by hydrothermal and treatment method. When Se@NiO/CC-2 is used as cathode of Li-O2 battery, the battery has low ove-rpotential (1.14 V), excellent discharge capacity (9883 mAh g−1) and long cycle stability (111 cycles). This significantly improved electrochemical performance results from a built-in electric field that forms along the heterostructures, which accelerates charge transfer dynamics during charge and
CRediT authorship contribution statement
Liqin Wang: Writing – original draft, Methodology, Formal analysis. Youcai Lu: Supervision, Conceptualization, Writing – review & editing. Mengran Xie: Writing – review & editing. Shaoze Zhao: Data curation. Zhongjun Li: Supervision, Writing – review & editing. Qingchao Liu: Conceptualization, Project administration, Project administration, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work is financially supported by National Science Foundation of China (No. 21170055), Key Scientific Research Project of Henan Province (NO. 22A150025), Teacher Training Fund of Zhengzhou University (No. 32211806), Young talents Enterprise Cooperative Innovation Team of Zhengzhou University (No. 32320418). There are no conflicts to declare.
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