Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts

Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).     

Metal–organic framework based bifunctional oxygen electrocatalysts for rechargeable zinc–air batteries: current progress and prospects

Zinc–air batteries (ZABs) are regarded as ideal candidates for next-generation energy storage equipment due to their high energy density, non-toxicity, high safety, and environmental friendliness. However, the slow oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics on the air cathode limit their efficiency and the development of highly efficient, low cost and stable bifunctional electrocatalysts is still challenging. Metal–Organic Framework (MOF) based bifunctional oxygen electrocatalysts have been demonstrated as promising alternative catalysts due to the regular structure, tunable chemistry, high specific surface area, and simple and easy preparation of MOFs, and great progress has been made in this area. Herein, we summarize the latest research progress of MOF-based bifunctional oxygen electrocatalysts for ZABs, including pristine MOFs, derivatives of MOFs and MOF composites. The effects of the catalysts'' composites, morphologies, specific surface areas and active sites on catalytic performances are specifically addressed to reveal the underlying mechanisms for different catalytic activity of MOF based catalysts. Finally, the main challenges and prospects for developing advanced MOF-based bifunctional electrocatalysts are proposed.

The research progress of MOF-based bifunctional oxygen electrocatalysts for zinc–air batteries is reviewed and the main challenges and prospects for developing advanced MOF-based bifunctional electrocatalysts are proposed.     

Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries

The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO₂ catalysts in primary and rechargeable zinc–air batteries.     

Bifunctional versus Defect-Mediated Effects in Electrocatalytic Methanol Oxidation

The most prominent and intensively studied anode catalyst material for direct methanol oxidation fuel cells consists of a combination of platinum (Pt) and ruthenium (Ru). Classically, their high performance is attributed to a bifunctional reaction mechanism where Ru sites provide oxygen species at lower overpotential than Pt. In turn, they oxidize the adsorbed carbonaceous reaction intermediates at lower overpotential; among these, the Pt site-blocking carbon monoxide. We demonstrate that well-defined Pt modified Ru(0001) single crystal electrodes, with varying Pt contents and different local PtRu configurations at the surface, are unexpectedly inactive for the methanol oxidation reaction. This observation stands in contradiction with theoretical predictions and the concept of bifunctional catalysis for this reaction. Instead, we suggest that pure Pt defect sites play a more critical role than bifunctional defect sites on the electrodes investigated in this work.     

Phosphorus‐Doped Graphitic Carbon Nitrides Grown In Situ on Carbon‐Fiber Paper: Flexible and Reversible Oxygen Electrodes

Flexible non‐metal oxygen electrodes fabricated from phosphorus‐doped graphitic carbon nitride nano‐flowers directly grown on carbon‐fiber paper exhibit high activity and stability in reversibly catalyzing oxygen reduction and evolution reactions, which is a result of N, P dual action, enhanced mass/charge transfer, and high active surface area. The performance is comparable to that of the state‐of‐the‐art transition‐metal, noble‐metal, and non‐metal catalysts. Remarkably, the flexible nature of these oxygen electrodes allows their use in folded and rolled‐up forms, and directly as cathodes in Zn–air batteries, featuring low charge/discharge overpotential and long lifetime.     

石墨烯基催化剂的设计合成与电催化应用

为了解决能源匮乏和环境污染的问题,研究人员正致力于寻找清洁可持续的新能源。 其中,氧气还原、氧气析出、析氢反应等是紧密联系新型清洁能源获取和存贮的重要电化学反应。 为了提高其能量转化效率,电催化剂(如碳载铂Pt/C)被广泛地用于降低其反应活化能、提高能量转化效率。 近年来,石墨烯作为一种具有高比表面积和优异导电性的二维碳材料受到了广泛关注。 通过表面杂原子掺杂、缺陷调控和引入催化活性组分等方式,获得了催化性能与贵金属催化剂相媲美,且低价格和高稳定性的非贵金属石墨烯基催化材料。 针对氧气还原、氧气析出和析氢反应在燃料电池、金属-空气电池和电催化水分解中的应用,本文概括综述了通过表/界面结构性质调控提高石墨烯电催化性能和稳定性,获得具有双功能或复合催化性能的石墨烯基催化剂的最新研究进展。 最后总结和展望了亟待解决的问题及未来的发展趋势。     

A bifunctional perovskite oxide catalyst:The triggered oxygen reduction/evolution electrocatalysis by moderated Mn-Ni co-doping

ABO₃-type perovskite oxides(e.g.,LaCoO₃)with flexible and adjustable A-and B-sites are ideal model catalysts to unravel the relationship between the electronic structure and electrocatalytic activity(e.g.,oxygen reduction/evolution reactions,ORR/OER).It has been well understood in our recent work that the secondary metal dopant at B-site(e.g.,Mn in LaMn_xCo_1-xO₃)can regulate the electronic structure and improve the ORR/OER activity.In this work,the Mn-Ni pairs are employed as the dual dopant in LaMn_xNi_yCo_zO₃(x+y+z=1)catalysts toward bifunctional ORR and OER.The structure-property relationships between the triple metal B-site(Mn,Ni and Co)and the electrochemical performance are particularly investigated.Compared to the individual Mn doping(e.g.,LaMnCoO3(Mn:Co=1:3)catalyst),the dual Mn-Ni doping significantly improves the ORR mass activity@0.8 V by 1.54 times;meanwhile,the OER overpotential@10 mA cm^-2 is reduced from 420 to 370 mV,and the OER current density at 1.55 V is increased by 2.43 times.Reasonably,the potential gap between EDRR@-1 mA cm^-2 and EDER@10 mA cm^-2 is achieved as only 0.76 V by using the optimal LaMn_xNi_yCo_zO₃(x:y:z=1:2:3)catalyst.It is revealed that the dual Mn-Ni dopant efficiently optimizes electron structures of the LaMnNiCoO₃(1:2:3)catalyst,which not only decreases the e_g orbital electron number,but also modulates the O 2 p-band closer to the Femi level,accounting for the enhanced bifunctional activity.     

Co@Co3O4 Encapsulated in Carbon Nanotube‐Grafted Nitrogen‐Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode

Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal–air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core–shell Co@Co₃O₄ nanoparticles embedded in CNT‐grafted N‐doped carbon‐polyhedra obtained by the pyrolysis of cobalt metal–organic framework (ZIF‐67) in a reductive H₂ atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO₂, and RuO₂ and thus ranking them among one of the best non‐precious‐metal electrocatalysts for reversible oxygen electrodes.     

Bifunctional Catalysts for Reversible Oxygen Evolution Reaction and Oxygen Reduction Reaction

Metal-air batteries (MABs) and reversible fuel cells (RFCs) rely on the bifunctional oxygen catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Finding efficient bifunctional oxygen catalysts is the ultimate goal and it has attracted a great deal of attention. The dilemma is that a good ORR catalyst is not necessarily efficient for OER, and vice versa. Thus, the development of a new type of bifunctional oxygen catalysts should ensure that the catalysts exhibit high activity for both OER and ORR. Composites with multicomponents for active centers supported on highly conductive matrices could be able to meet the challenges and offering new opportunities. In this Review, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctional catalysts with low overpotentials.     

La1－xSrxNi1－yCoyO3双功能氧电极的电化学性能

采用溶胶-凝胶法制备了一系列La1－xSrxNi1－yCoyO3（x=0、0.1、0.2、0.5； y=0～1.0）型的钙钛矿催化剂，并以活性碳为载体制备双功能氧电极.对催化剂进行了XRD结构分析以及XPS表面分析.采用三电极体系测试了氧电极的稳态极化曲线和电化学交流阻抗谱并对其阴极极化和阳极极化谱图进行了分析.实验表明，对于LaNiO3化合物，B位掺杂可显著提高催化剂表面的B离子浓度, 从而提高电催化性能；而A位掺杂由于导致有序化氧空位的增多和电导的降低而造成活性下降.电极氧还原反应的极化主要由电荷转移反应和能斯特扩散过程造成.     

Application of Graphdiyne and Its Analogues in Photocatalysis and Photoelectrochemistry

Graphdiyne(GDY),a new carbon allotrope composed of sp-sp2 carbon atoms,has attracted increased attention in recent years.It has a direct band gap of 0.46-1.22 eV,high charge carrier mobility and lower work function compared to most of the typical semiconductors,which ensure successful hybridization with other semiconductors(e.g.,TiO2,g-C3N4).This review aims at discussing recent achievements of GDY and its analogues applied in photocatalytic and photoelectrochemical(PEC)reactions.Meanwhile,some challenges and new perspectives of opportunities in developing catalysts and electrodes based on GDY and its analogues are also discussed.     

纳米碳管作为氧扩散电极催化层第二相碳载体的电极特性

A novel gas diffusion electrode using binary carbon supports (carbon nanotubes and active carbon) as the catalyst layer was prepared. The electrochemical properties for oxygen reduction reaction (ORR) in alkaline electrolyte were investigated by polarization curves and electrochemical impedance spectroscopy. The results show that the binary-support electrode exhibits higher electrocatalytic activity than the single-support electrode, and the best performance is obtained when the mass ratio of carbon nanotubes and activated carbon is 50 ∶50. The results from their electrode kinetic parameters indicate that the introduction of carbon nanotubes as a secondary support provides high accessible surface area, good electronic conductivity and fast ORR kinetics. The electrocatalytic activity of binary-support electrodes is obviously improved by the deposition of Pt nanoparticles on carbon nanotubes, even at very low Pt loading (45.7 μg/cm2). In addition, the EIS analysis results show that the process of ORR may be controlled by diffusion of oxygen in the thin film for binary-support electrodes with or without Pt catalyst.     

The influence of the type of N dopping on the performance of bifunctional N-doped ordered mesoporous carbon electrocatalysts in oxygen reduction and evolution reaction

To develop more ideal bifunctional heteroatom-doped carbon electrocatalysts toward the oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) for regenerative fuel cells and rechargeable metal–air batteries, herein, tobacco-derived N-containing ordered mesoporous carbon(N-OMC) electrocatalysts with different N species distributions are designed. Results indicate that the as-prepared N-OMC with more pyrrolic and pyridinic Ns exhibits much higher activities for the ORR and OER than N-OMC with more graphitic N in both acidic and alkaline media, suggesting that the increase of pyrrolic and pyridinic Ns favors the improvement of ORR and OER activities of the N-containing carbon catalysts, and showing a great potential for the designing of more effective, lower-cost ORR and OER bifunctional electrocatalysts for future regenerative fuel cells and rechargeable metal–air batteries.     

Filling the Charge–Discharge Voltage Gap in Flexible Hybrid Zinc-Based Batteries by Utilizing a Pseudocapacitive Material

The high charge–discharge voltage gap is one of the main bottlenecks of zinc–air batteries (ZABs) because of the kinetically sluggish oxygen reduction/evolution reactions (ORR/OER) on the oxygen electrode side. Thus, an efficient bifunctional catalyst for ORR and OER is highly desired. Herein, honeycomb-like MnCo₂O_4.5 spheres were used as an efficient bifunctional electrocatalyst. It was demonstrated that both ORR and OER catalytic activity are promoted by Mn^IV-induced oxygen vacancy defects and multiple active sites. Importantly, the multivalent ions present in the material and its defect structure endow stable pseudocapacitance within the inactive region of ORR and OER; as a result, a low charge–discharge voltage gap (0.43 V at 10 mA cm⁻²) was achieved when it was employed in a flexible hybrid Zn-based battery. This mechanism provides unprecedented and valuable insights for the development of next-generation metal–air batteries.     

多壁纳米碳管空气电极的交流阻抗研究

研究了多壁纳米碳管、活性炭和石墨等空气电极的交流阻抗特性.结果表明,纳米碳管空气电极的阻抗谱由两个半圆组成,高频区半圆对应欧姆极化阻抗,低频区半圆对应电化学极化阻抗.催化剂Pt以纳米颗粒的形式沉积在碳管的外表面,明显减小了电极的欧姆阻抗和电化学极化阻抗,提高了氧还原反应的电催化活性.活性炭电极除存在电化学阻抗外,还存在薄液膜扩散阻抗(Nernst扩散),石墨电极形成的薄液膜反应区域较小,电极反应呈Warburg扩散阻抗特征,相应的电催化活性较低.采用交流阻抗等效电路分析方法,对拟合的动力学数据进行了解释.     

Transition metal-based electrocatalysts for overall water splitting

Electrochemical overall water splitting is attracting a broad focus as a promising strategy for converting the electrical output of renewable resources into chemical fuels, specifically oxygen and hydrogen. However, the urgent challenge in water electrolysis is to search for low-cost, high-efficiency catalysts based on earth-abundant elements as an alternative to the high-cost but effective noble metal-based catalysts. The transition metal-based catalysts are more appealing than the noble metal catalysts because of its low cost, high performance and long stability. Some recent advances for the development in overall water splitting are reviewed in terms of transition metal-based oxides, carbides, phosphides, sulfides, and hybrids of their mixtures as hybrid bifunctional electrocatalysts. Concentrating on different catalytic mechanisms, recent advances in their structural design, controllable synthesis, mechanistic insight, and performance-enhancing strategies are proposed. The challenges and prospects for the future development of transition metal-based bifunctional electrocatalysts are also addressed.     

Material design and surface chemistry for advanced rechargeable zinc–air batteries

Zinc–air batteries (ZABs) have been considered as a next-generation battery system with high energy density and abundant resources. However, the sluggish multi-step reaction of the oxygen is the main obstacle for the practical application of ZABs. Therefore, bifunctional electrocatalysts with high stability and activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are greatly required to promote the catalytic reaction. In this review, we first explain the reaction mechanism of the ZABs, mainly focusing on multiple oxygen intermediates. Then, the latest studies on bifunctional electrocatalysts for the air cathodes and their progress of the ZABs are discussed with following aspects: platinum group metal, metal-free, transition metal, and metal compound-derived electrocatalysts. Finally, we highlight the advanced ZAB systems with the design of the full-temperature range operation, the all-solid-state, and the newly reported non-alkaline electrolyte, summarizing the remaining challenges and requirements of the future research directions.

This work reviews latest research on the bifunctional electrocatalysts for air cathodes, introducing the advanced zinc–air batteries with the full-temperature range operation, all-solid-states, and newly reported non-alkaline electrolytes.     

金属-空气电池中双功能电催化剂微纳结构设计（英文）

金属-空气二次电池在可再生电能的存储和转换方面具有广阔的应用前景.在金属-空气二次电池的空气侧,放电时发生氧还原反应(ORR),充电时发生氧析出反应(OER).然而,ORR和OER反应的动力学过程缓慢,因此限制了金属-空气二次电池的实际应用.因此,发展高性能ORR和OER电催化剂对金属-空气二次电池的发展尤为重要.目前,大多数的研究集中在ORR或OER的单功能电催化剂上,而关于双功能电催化剂的研究和综述相对较少.两个反应均具有较高的过电位和较缓慢的动力学过程,而且充电过程的高电压会导致ORR催化剂失活,反之亦然.因此,开发针对这两个反应均具有高活性和高稳定性的双功能电催化剂极具挑战性.近年来,研究者对具有低成本和高性能双功能电催化剂进行了探索.这些双功能电催化剂包括碳基材料,过渡金属材料和复合材料.双功能电催化剂可以通过提高本征活性和表观活性两种策略来提高其整体的活性.其中,本征活性与晶体结构和电子结构密切相关,即可以通过调节晶体结构和电子结构来提高其本征活性.例如,可以改变金属-氧键的强度、氧空位浓度等来调变电催化活性.在碳基材料中掺杂杂原子可以改变碳的电荷密度分布,从而实现对电催化活性的提高.此外,其表观活性还可以通过改变形貌并利用协同作用来改善.构建特殊微纳结构是提高电催化活性的最常用策略之一.在这种情况下,电催化剂具有较高的比表面积,大量的活性位点和良好的电子传导性.同时,复合电催化剂组分之间在加速电催化过程中的协同作用不容忽视.本文将聚焦双功能电催化剂的微纳结构设计,并简要讨论了纳米结构的精细调控和对反应机理的认识.我们认为,未来的工作应继续加强ORR和OER的新型双功能电催化剂的开发,发展更多的合成方法对电催化剂的微纳结构进行调变,并对反应机理进行更深入的研究.首先,通过对结构的精细调变提高电催化剂的本征活性和表观活性.此外,通过多种原位表征方法揭示反应机理,这有助于电催化剂的设计和催化活性的进一步提升.基于此,开发出性能优异的双功能电催化剂以加快用于存储和转换可再生能源的可充电金属-空气二次电池的商业化进程.     

Pt/纳米碳管空气电极氧还原反应的电催化性能

以不同质量比的铂、纳米碳管、活性炭为催化层制备空气电极并测定其稳态极化曲线和交流阻抗.研究发现,纳米碳管经硝酸处理后其氧还原反应性能得到提高,特别是将表面氧化后再沉积Pt,对氧的电还原反应影响更显著.以质量比4∶1的活性炭/纳米碳管载Pt制备的空气电极,在过电位ηc为500～600mV下,氧还原电流可达600～700mA·cm-2.EIS测试表明,纳米碳管载Pt后的欧姆极化阻抗和电化学阻抗均非常小.