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Yanhua, Lei, Ning Tan, Xinglong Tao, Jingxian Xia, Da Huo, MengChao Ding, Yuliang Zhang, Zengmei Wang, Baomin Fan i Guanhui Gao. "Innovative Fabrication of Pd/Pd4S Based Highly Active Electrocatalysts for ORR in a Primary Zn-Air Battery". Journal of The Electrochemical Society 169, nr 2 (1.02.2022): 024514. http://dx.doi.org/10.1149/1945-7111/ac4dac.
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On account of their high theoretical energy density and minimal cost, Zn-air batteries have gotten a lot of interest as a viable energy storage technology. However, the problem of a high overpotential at the cathode because of the slow oxygen reduction reaction (ORR) kinetics persists. Developing an efficient cathode ORR catalyst and exceeding in performance in comparison to the existing and widely utilized Pt-based catalysts is still a formidable challenge. Herein, this study focuses on the design of a Pt-free catalyst, precisely, Pd/Pd4S based electrocatalysts to enhance ORR performance of cathode. The simple encapsulated structure containing nitrogen-doped carbon (N-doped C) coated Pd/Pd4S and CeO2 nanoparticles (Pd-Pd4S/CeO2/N-C) fabricated by a practical and trouble-free approach has a powerful electrochemical ability. Pd-Pd4S/CeO2/N-C displays a virtually identical limited current density to the commercial 20% Pt/C catalysts and better durability under alkaline conditions. Moreover, this work involves the subsequent utilization of Pd-Pd4S/CeO2/N-C in a primary Zn-air battery as the air electrode, where it manifested comparable current density and power density at 0.6 V as furnished by the Pt/C catalyst. Along with this, the primary Zn-air battery system comprising Pd-Pd4S/CeO2/N-C exhibited constant discharge comprising several hours, a specific capacity of 748 mAh gZn −1, and stability at 10 mA cm−2.
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Zhang, Xiangkun, Yun Li, Jingru Ren i Yongmin Huang. "Synthesis of a Zn/Fe–N–C electrocatalyst towards efficient oxygen reduction reaction via a facile one-pot method". Materials Research Express 9, nr 2 (1.02.2022): 025604. http://dx.doi.org/10.1088/2053-1591/ac569e.
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Abstract The high price and unsatisfactory stability of Pt-based catalysts for the sluggish oxygen reduction reaction (ORR) severely limit the development of fuel cells and metal-air batteries. Therefore, developing Pt-free electrocatalysts with excellent activities and stabilities is significant. Herein, an efficient Zn/Fe–N–C electrocatalyst is synthesized via a facile one-pot method. Owing to its curved nanosheet structure, appropriate microporous and mesoporous specific surface areas, abundant defects and high Fe–Nx content, Zn/Fe–N–C exhibits remarkable ORR activity and stability in alkaline electrolyte. Its half-wave potential is 0.843 V, which is 10 mV higher than that of Pt/C. Moreover, Zn/Fe–N–C also manifests satisfactory performance in a practical Zn-air battery. Its maximum output power density is 108.5 mW cm−2, which is equivalent to that of Pt/C. In this work, a simple synthesis method for highly active ORR electrocatalyst is provided, which can be implemented for the future design and synthesis of electrocatalysts used in fuel cells and metal-air batteries.
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Song, Dongmei, Changgang Hu, Zijian Gao, Bo Yang, Qingxia Li, Xinxing Zhan, Xin Tong i Juan Tian. "Metal–Organic Frameworks (MOFs) Derived Materials Used in Zn–Air Battery". Materials 15, nr 17 (24.08.2022): 5837. http://dx.doi.org/10.3390/ma15175837.
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It is necessary to develop new energy technologies because of serious environmental problems. As one of the most promising electrochemical energy conversion and storage devices, the Zn–air battery has attracted extensive research in recent years due to the advantages of abundant resources, low price, high energy density, and high reduction potential. However, the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) of Zn–air battery during discharge and charge have complicated multi-electron transfer processes with slow reaction kinetics. It is important to develop efficient and stable oxygen electrocatalysts. At present, single-function catalysts such as Pt/C, RuO2, and IrO2 are regarded as the benchmark catalysts for ORR and OER, respectively. However, the large-scale application of Zn–air battery is limited by the few sources of the precious metal catalysts, as well as their high costs, and poor long-term stability. Therefore, designing bifunctional electrocatalysts with excellent activity and stability using resource-rich non-noble metals is the key to improving ORR/OER reaction kinetics and promoting the commercial application of the Zn–air battery. Metal–organic framework (MOF) is a kind of porous crystal material composed of metal ions/clusters connected by organic ligands, which has the characteristics of adjustable porosity, highly ordered pore structure, low crystal density, and large specific surface area. MOFs and their derivatives show remarkable performance in promoting oxygen reaction, and are a promising candidate material for oxygen electrocatalysts. Herein, this review summarizes the latest progress in advanced MOF-derived materials such as oxygen electrocatalysts in a Zn–air battery. Firstly, the composition and working principle of the Zn–air battery are introduced. Then, the related reaction mechanism of ORR/OER is briefly described. After that, the latest developments in ORR/OER electrocatalysts for Zn–air batteries are introduced in detail from two aspects: (i) non-precious metal catalysts (NPMC) derived from MOF materials, including single transition metals and bimetallic catalysts with Co, Fe, Mn, Cu, etc.; (ii) metal-free catalysts derived from MOF materials, including heteroatom-doped MOF materials and MOF/graphene oxide (GO) composite materials. At the end of the paper, we also put forward the challenges and prospects of designing bifunctional oxygen electrocatalysts with high activity and stability derived from MOF materials for Zn–air battery.
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Hong, Wei, Xia Wang, Hongying Zheng, Rong Li, Rui Wu i Jun Song Chen. "Molten-Salt-Assisted Synthesis of Nitrogen-Doped Carbon Nanosheets Derived from Biomass Waste of Gingko Shells as Efficient Catalyst for Oxygen Reduction Reaction". Processes 9, nr 12 (25.11.2021): 2124. http://dx.doi.org/10.3390/pr9122124.
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Developing superior efficient and durable oxygen reduction reaction (ORR) catalysts is critical for high-performance fuel cells and metal–air batteries. Herein, we successfully prepared a 3D, high-level nitrogen-doped, metal-free (N–pC) electrocatalyst employing urea as a single nitrogen source, NaCl as a fully sealed nanoreactor and gingko shells, a biomass waste, as carbon precursor. Due to the high content of active nitrogen groups, large surface area (1133.8 m2 g−1), and 3D hierarchical porous network structure, the as-prepared N–pC has better ORR electrocatalytic performance than the commercial Pt/C and most metal-free carbon materials in alkaline media. Additionally, when N–pC was used as a catalyst for an air electrode, the Zn–air battery (ZAB) had higher peak power density (223 mW cm−2), larger specific-capacity (755 mAh g−1) and better rate-capability than the commercial Pt/C-based one, displaying a good application prospect in metal-air batteries.
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Kim, Seonghee, Hyun Park i Oi Lun Li. "Cobalt Nanoparticles on Plasma-Controlled Nitrogen-Doped Carbon as High-Performance ORR Electrocatalyst for Primary Zn-Air Battery". Nanomaterials 10, nr 2 (28.01.2020): 223. http://dx.doi.org/10.3390/nano10020223.
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Metal–air batteries and fuel cells have attracted much attention as powerful candidates for a renewable energy conversion system for the last few decades. However, the high cost and low durability of platinum-based catalysts used to enhance sluggish oxygen reduction reaction (ORR) at air electrodes prevents its wide application to industry. In this work, we applied a plasma process to synthesize cobalt nanoparticles catalysts on nitrogen-doped carbon support with controllable quaternary-N and amino-N structure. In the electrochemical test, the quaternary-N and amino-N-doped carbon (Q-A)/Co catalyst with dominant quaternary-N and amino-N showed the best onset potential (0.87 V vs. RHE) and highest limiting current density (−6.39 mA/cm2). Moreover, Q-A/Co was employed as the air catalyst of a primary zinc–air battery with comparable peak power density to a commercial 20 wt.% Pt/C catalyst with the same loading, as well as a stable galvanostatic discharge at −20 mA/cm2 for over 30,000 s. With this result, we proposed the synergetic effect of transitional metal nanoparticles with controllable nitrogen-bonding can improve the catalytic activity of the catalyst, which provides a new strategy to develop a Pt-free ORR electrocatalyst.
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Li, Yuan, Xinyao Wang, Hong Wang, Xiaoyao Tan, Dan Liu, Jianzhou Gui, Jian Gao, Zhen Yin, Na Ma i Yun Wang. "“Pharaoh’s Snakes” Reaction-Derived Carbon with Favorable Structure and Composition as Metal-Free Oxygen Reduction Reaction Electrocatalyst". Catalysts 13, nr 7 (30.06.2023): 1059. http://dx.doi.org/10.3390/catal13071059.
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Metal-air batteries rely on the oxygen reduction reaction (ORR) for their operation. However, the ORR is kinetically slow, necessitating the use of Pt-based catalysts, which is hindered by their high cost and limited availability. Consequently, considerable efforts have been dedicated to developing metal-free catalysts for the ORR. Among these, heteroatom-doped carbons have emerged as promising candidates by manipulating their composition and microstructure. Inspired by the ancient “Pharaoh’s snakes” reaction, this study utilized sugar, melamine, and a polymerizable ionic liquid as precursors to prepare heteroatom-doped carbons with the desired composition and structure. The resulting carbon catalyst exhibited an onset potential and half-wave potential in a 0.1 M KOH electrolyte that was comparable to those of a commercial Pt/C 20 wt.% catalyst, with values of 0.97 and 0.83 VRHE, respectively. Furthermore, the catalyst demonstrated excellent stability, retaining 93% of its initial current after a 10,800-s test. To evaluate its practical application, the synthesized carbon was employed as the cathode catalyst in a Zn-air battery, which achieved a maximum power density of 90 mW cm−2. This study, therefore, presents a simple yet effective method for producing metal-free heteroatom-doped carbon ORR catalysts used in various energy conversion and storage devices.
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Zhao, Siqi, Deliang Chen, Yawu Gao, Tao Li, Shasha Yi, Haipeng Ji, Xiaochao Zuo i in. "One-Pot Synthesis of Fe–N–C Species-Modified Carbon Nanotubes for ORR Electrocatalyst with Overall Enhanced Performance Superior to Pt/C". Nano 16, nr 03 (16.02.2021): 2150028. http://dx.doi.org/10.1142/s1793292021500284.
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Novel synthesis of efficient noble-metal-free electrocatalysts for both oxygen reduction/evolution reaction (ORR/OER) in energy conversion devices (e.g., fuel cells, metal–air batteries) is of essential significance for further sustainable development. This paper reports a facile synthesis of Fe–N–C species-modified carbon nanotubes (F/N-CNTs) for ORR application by directly pyrolyzing a fluffy hybrid precursor at a moderate temperature ([Formula: see text]C) in Ar. The fluffy hybrid precursors consisting of nitro-hydrochloric-acid-treated CNTs, melamine and Fe[Formula: see text] species are prepared via a freeze-drying method. On account of the synergistic effect of various active sites, including pyridine–N, Fe–Nx and Fe3C, and the high conductivity of the CNTs matrix, the as-obtained F/N-CNT electrocatalysts exhibit excellent ORR activities, comparable to commercial Pt/C. The addition of N heteroatoms, the dosage of Fe and the pyrolysis temperature highly influence the ORR properties of the F/N-CNT samples. The typical F/N-CNT sample obtained at the optimized parameters shows an onset potential of 1.06[Formula: see text]V and a half-wave potential of 0.91[Formula: see text]V versus reversible hydrogen electrode (RHE) in an alkaline condition, more positive than those (1.01[Formula: see text]V and 0.88[Formula: see text]V versus RHE) of Pt/C. The F/N-CNT exhibits outstanding bifunctional ORR/OER activity and excellent methanol tolerance, and the F/N-CNT-based Zn–air battery (ZAB) with an open-circuit voltage (OCV) of 1.405[Formula: see text]V presents a current density of 125[Formula: see text]mA[Formula: see text]cm[Formula: see text] and a power density of 76.5[Formula: see text]mW[Formula: see text]cm[Formula: see text]; these electrocatalytic properties are highly superior to Pt/C. The direct pyrolysis of fluffy hybrid precursors provides a concise but robust technical platform to achieve high-performance noble-metal-free electrocatalysts with ORR/OER activities superior to Pt/C.
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Luong, Samantha, Anand Chandra Singh, Xia Tong, Dayna Wiebe i Viola Ingrid Birss. "N-Doped Colloid Imprinted Carbons As Promising ORR Catalysts for Alkaline Applications". ECS Meeting Abstracts MA2022-01, nr 7 (7.07.2022): 632. http://dx.doi.org/10.1149/ma2022-017632mtgabs.
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The oxygen reduction reaction (ORR) has long been of interest in relation to its many energy applications and interesting multi-pathway mechanisms. The ORR is a key reaction in a range of electrochemical energy conversion and storage devices, such as hydrogen fuel cells and metal-air batteries, respectively. These devices are expected to play an ever-increasing role in the global transition to net zero emissions. Metal-air batteries, such as Zn/air batteries, can operate at room temperature, use recyclable materials, are environmentally friendly, and are preferred in relation to consumer safety than batteries relying on organic solvents and reactive electrode species.1 High rates of the ORR are crucial for the development of high performance Zn/air batteries and catalysts play a significant role, with lowering of the catalyst cost also of increasing importance. The costs of conventional Pt-based ORR catalysts are high. Therefore, metal-free carbon-based ORR electrocatalysts are viewed as increasingly promising alternatives, especially as they are lower in cost due to the availability of the precursor materials. Carbon is also a good electrical conductor and support material, is chemically stable, and can have large surface areas. However, the ORR kinetics are sluggish on carbon and chemical and physical modifications are required to enhance its activity. In typical Zn/air batteries, the ORR occurs at the three-phase boundary (TPB) formed between the solid electrode, liquid electrolyte, and gaseous oxygen. The porosity of the catalyst layer, the wettability of the catalyst/electrolyte interface, and the gas permeability and hydrophobicity of the gas diffusion layer (GDL) are thus also important, significantly influencing the cathode performance and durability. The catalyst layer (CL) must therefore be constructed with both a high-performance catalyst and an optimized TPB length to provide high performance without compromising durability. In the current work, we have doped nitrogen into the lattice of a family of nanoporous colloid imprinted carbon (CIC) powders to increase its ORR activity. The CICs are unique for their versatility in terms of pore size control and ease of surface functionalization.2 Pore sizes in the range of 12 to 100 nm were examined and their effect on the ORR activity and mass transport limitations were investigated. To carry out N-doping, the CICs were exposed to ammonia at 800 ˚C for 7 hr. Catalyst inks were then prepared by mixing the CICs with a binder in an isopropyl alcohol/water solution. Aliquots of the ink were drop-casted on the disc of an RRDE system, or were spray coated or drop-casted on a GDL to determine the ORR performance in an in-house Zn/air battery testing cell, with the N-doped CIC catalyst layer sandwiched between an electrolyte chamber and a graphite current collector. In this setup, O2 gas was flowed through the pores in the GDL to the catalyst/electrolyte interface, a Zn wire installed in the electrolyte chamber was used as the reference electrode, and a Ni sponge was used as the counter electrode. The RRDE experiments showed that, after N doping of the CIC powders, the production of peroxide decreased significantly and the ORR onset potential increased to a very respectable value of ca. 0.9 V vs RHE, indicating the successful activation of the ORR. Electron transfer numbers were found to be greater than 3.5, indicating that either a direct or pseudo- 4 electron transfer ORR pathway is dominant. In agreement with the literature, the ORR currents in the kinetic regions increased linearly with mass loading, expected to be proportional to the total active N-doped CIC surface area.3 The N-doped CIC samples retained excellent performance up to a loading of 0.350 μg/cm2 without losing mechanical stability. Similar N-doped CICs and binders of different hydrophobicity were tested in the Zn/air battery testing system. Electrodes made with a hydrophobic NCS microporous layer (MPL) showed much better ORR performance and durability than hydrophilic NCS MPLs. Although electrodes made using hydrophobic polytetrafluoroethylene (PTFE) as the binder in the catalyst layer showed a similar initial performance to those made using hydrophilic Nafion binders, the PTFE based electrodes exhibited better durability. Furthermore, the temperature and pressure used during electrode fabrication were also found to have a significant impact on the binder distribution and ORR performance. Once optimized, a very good correlation was obtained between the N-doped CIC catalyst performance in the RRDE setup and in the Zn/air battery testing system. References J. Pan et al., Adv. Sci., 5, 1700691 (2018). X. Li et al., ACS Appl. Mater. Interfaces, 10, 2130–2142 (2018). N. Gavrilov et al., J. Power Sources, 220, 306–316 (2012).
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Dong, Xiaoyang, Jinxing Wang, Xiao Wang, Jingdong Yang, Ling Zhu, Wen Zeng, Guangsheng Huang, Jingfeng Wang i Fusheng Pan. "Prussian Blue Analogue Derived Co3O4/CuO Nanoparticles as Effective Oxygen Reduction Reaction Catalyst for Magnesium-Air Battery". Journal of The Electrochemical Society 169, nr 1 (1.01.2022): 010532. http://dx.doi.org/10.1149/1945-7111/ac4b25.
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Developing efficient, durable, and cost-effective non-noble metal catalysts for oxygen reduction reaction (ORR) is necessary to promote the efficiency and performance of Mg-air batteries. Herein, the Co3O4/CuO nanoparticles were synthesized by a low-cost and simple approach using CuCo-based prussian blue analogue (PBA) as precursor of pyrolysis at different calcination temperatures. It was found that the Co3O4/CuO nanoparticles calcined at 600 °C (CCO-600) have relatively small size and superior ORR performance. The onset potential is 0.889 V and the diffusion limiting current density achieves 6.746 mA·cm−2, as well as prominent stability in 0.1 M KOH electrolyte. The electron transfer number of the CCO-600 is 3.89 under alkaline medium, which indicates that the reaction mechanism of ORR is dominated by 4 e process similar to commercial Pt. The primary Mg-air battery with the CCO-600 as the cathode catalyst has been assembled and possesses better discharge performance than the CuCo-based PBA. The open circuit voltage of CCO-600 arrives at 1.76 V and the energy density reaches 1895.95 mWh/g. This work provides an effective strategy to develop non-noble metal ORR catalyst for the application of metal-air batteries.
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Blackstone, Chance, i Anna Ignaszak. "Van der Waals Heterostructures—Recent Progress in Electrode Materials for Clean Energy Applications". Materials 14, nr 13 (5.07.2021): 3754. http://dx.doi.org/10.3390/ma14133754.
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The unique layered morphology of van der Waals (vdW) heterostructures give rise to a blended set of electrochemical properties from the 2D sheet components. Herein an overview of their potential in energy storage systems in place of precious metals is conducted. The most recent progress on vdW electrocatalysis covering the last three years of research is evaluated, with an emphasis on their catalytic activity towards the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). This analysis is conducted in pair with the most active Pt-based commercial catalyst currently utilized in energy systems that rely on the above-listed electrochemistry (metal–air battery, fuel cells, and water electrolyzers). Based on current progress in HER catalysis that employs vdW materials, several recommendations can be stated. First, stacking of the two types vdW materials, with one being graphene or its doped derivatives, results in significantly improved HER activity. The second important recommendation is to take advantage of an electronic coupling when stacking 2D materials with the metallic surface. This significantly reduces the face-to-face contact resistance and thus improves the electron transfer from the metallic surface to the vdW catalytic plane. A dual advantage can be achieved from combining the vdW heterostructure with metals containing an excess of d electrons (e.g., gold). Despite these recent and promising discoveries, more studies are needed to solve the complexity of the mechanism of HER reaction, in particular with respect to the electron coupling effects (metal/vdW combinations). In addition, more affordable synthetic pathways allowing for a well-controlled confined HER catalysis are emerging areas.
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Wang, Keliang, Xiaotian Liu, Yayu Zuo, Manhui Wei, Yu Xiao, Pengfei Zhang, Jianyin Xiong i Pucheng Pei. "A Highly Active Bifunctional Catalyst of Mn–Co–Fe–N/S@CNT for Rechargeable Zinc-Air Batteries". Journal of The Electrochemical Society 168, nr 11 (1.11.2021): 110529. http://dx.doi.org/10.1149/1945-7111/ac3718.
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Rechargeable zinc-air batteries are promising candidates for energy storage due to their high energy density, environmentally friendliness, and low cost. However, such batteries are limited by the high cost and sluggish kinetics of noble metal catalysts. Here, we present a highly active bifunctional catalyst of Mn–Co–Fe–N/S@CNT, where the catalyst is synthesized by Mn, Co, and Fe oxides doped with N and S on porous carbon nanotubes. Mn–Co–Fe–N/S@CNT has higher electrocatalytic activity than the commercial catalysts of Pt/C and RuO2, demonstrating that the half-wave potential of the oxygen reduction reaction (ORR) of Mn–Co–Fe–N/S@CNT is 0.807 V (0.9 V with Pt/C), the initial potential is 0.85 V (0.789 V with Pt/C), the limiting current is 5.66 mA cm−2 at 0.2 V (5.69 mA cm−2 with Pt/C), and oxygen evolution reaction overpotential of Mn–Co–Fe–N/S@CNT is 0.386 V at 10 mA cm−2 (0.371 V with RuO2). Moreover, a rechargeable zinc-air battery using Mn–Co–Fe–N/S@CNT outputs a discharging voltage of 1.2 V and a stable cycle life of over 150 h at 10 mA cm−2.
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Fang, Can, Qingfeng Yi, Alin Chen, Yuebing Wang, Yaping Wang i Xiaofang LI. "Fabrication of FeCo/Multidimensional Carbon-Based Nanocomposites as Excellent Cathodic Catalysts of Zn-Air Battery". Journal of The Electrochemical Society, 15.11.2022. http://dx.doi.org/10.1149/1945-7111/aca2e3.
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Abstract Herein, N-doped carbon nanosheets/nanotubes composite loaded Fe-Co nanoparticles were prepared via a facile pyrolysis of the solid mixture composed of dicyandiamide, sucrose, cobalt nitrate, iron nitrate, iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc). The samples were characterized by SEM, TEM, XRD, XPS and BET techniques. The electroactivity of the prepared catalysts towards oxygen reduction reaction (ORR) was tested in a full pH range including acidic, neutral and alkaline media. In 0.1mol L-1 KOH solution, the ORR onset potential and half-wave potential of the FeCo-FePc/NTu-CNsh are 1.03 and 0.91 V, which are very close to the performance of commercial Pt/C catalyst (40%). In neutral solution (1 M KCl+4 M NH4Cl), FeCo-FePc/NTu-CNsh presents an ORR onset potential of 0.93 V and half-wave potential of 0.82 V, which are superior to Pt/C with onset potential of 0.92 V and half-wave potential of 0.81 V. The home-made Zn-air battery with the prepared samples as the cathodic catalysts reveal excellent performance, and the FeCo-FePc/NTu-CNsh Zn-air battery presents a maximum power density of 281.8 mW·cm-2 as well as the high stability at different discharging current densities
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Zheng, Yue, Li Huang, Rui Gao, Lirong Zheng, Zhongbo Hu i Xiangfeng Liu. "Boosting Oxygen Reduction Activity of Co3O4 through a Synergy of Ni Doping and Carbon Species Dotting for Zn-air battery". Journal of The Electrochemical Society, 12.06.2023. http://dx.doi.org/10.1149/1945-7111/acdd9f.
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Abstract Oxygen reduction reaction (ORR) undertakes an indispensable driving role for metal-air batteries with sluggish kinetics. In this work, we proposed a synergic strategy of Ni doping and carbon species dotting to compose Co3O4 with intrinsic large specific area and oxygen vacancies. The Ni-doped Co3O4/C (NCC-1) with four electron transfer mode conducts extraordinary electrocatalytic performance than commercial 20 wt% Pt/C and excellent tolerance to methanol poisoning. This series of improvements are attributed to the rapid dynamics drove by variable transition metal valence with elevated electronic conductivity derived from dotted carbon species. X-ray photoelectron spectroscopy results at different reduction stages show that the doped Co3O4/C affects ORR performance by adjusting the species of *O at the active sites and the formation of intermediates including *OH and *O. More Co3+ active sites exposed on the NCC-1 surface, higher catalytic activity is provided by the conversion of Co(Ⅱ)/Co(Ⅲ) and Ni(Ⅱ)/Ni(Ⅲ). What is purposeful in practicability. the NCC-1/IrO2 based Zn-air batteries show an excellent charge-discharge response and cyclability than that of 20% Pt/IrO2 based Zn-air batteries, highlighting the implemented potentiality of NCC-1 based metal-air-battery. This study offers new insights into designing non-noble-metal based oxygen reduction electrocatalysts for more energy storage devices.
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Ilnicka, Anna, Malgorzata Skorupska, Magdalena Tyc, Kinga Kowalska, Piotr Kamedulski, Wojciech Zielinski i Jerzy P. Lukaszewicz. "Green algae and gelatine derived nitrogen rich carbon as an outstanding competitor to Pt loaded carbon catalysts". Scientific Reports 11, nr 1 (29.03.2021). http://dx.doi.org/10.1038/s41598-021-86507-5.
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AbstractThe development of effective catalysts for the oxygen reduction reaction (ORR) is a significant challenge in energy conversion systems, e.g., Zn–air batteries. Herein, green-algae- and gelatine-derived porous, nitrogen-rich carbons were extensively investigated as electrode materials for electrochemical catalytic reactions. These carbon-based catalysts were designed and optimized to create a metal-free catalyst via templating, carbonization, and subsequent removal of the template. The additional incorporation of graphene improved electronic conductivity and enhanced the electrochemical catalytic reaction. Porous carbons with heteroatoms were used as effective platinum-free ORR electrocatalysts for energy conversion; the presence of nitrogen in the carbon provided more active sites for ORR. Our catalyst also displayed notable durability in a rechargeable Zn–air battery energy system. More importantly, the nitrogen-containing porous carbons were found to have comparable ORR performance in alkaline media to commercially available electrocatalysts. The manuscript demonstrates that nitrogen atom insertion is an appropriate approach when aiming to eliminate noble metals from the synthesis route. N-doped carbons are competitive materials compared to reference platinum-based catalysts.
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Sun, Qiming, Yiwei Zhao, Xiaodan Yu, Chao Zhang i Shuangxi Xing. "Interface Engineering of CoO/N-Doped Carbon Nanomaterials as a Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries". Journal of The Electrochemical Society, 16.06.2022. http://dx.doi.org/10.1149/1945-7111/ac797b.
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Abstract Robust bifunctional and highly efficient electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) exhibits great prospect in a zinc-air battery (ZAB). Here, we demonstrated a facile route to synthesize a bifunctional electrocatalyst with CoO nanoparticles embedded in N-doped carbon by interface engineering. The precursor which consists of ball-milled polyaniline (BM-PANI), carbon nanotubes (CNTs) and cobalt acetate tetrahydrate (Co(Ac)2·4H2O) was obtained via homogeneous mixture in the presence of ethanol, and thus, satisfactory interface was formed. After calcination, the synthesized CoO/N-doped carbon composite material presents a half-wave potential of 0.818 V for ORR and an overpotential of 0.417 V at 10 mA cm-2 for OER, which endows it a power density of 92.04 mW cm-2 in a homemade rechargeable ZAB and a high stability outperforming commercial Pt/C. This work highlights the mixture of precursors by interface engineering, thus improving the synergistic effect between metal oxide and carbon and elevating the electrocatalytic activity.
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Liu, Hui, Juemin Song, Jiaxi Zhang, Zheng Li, Hongjie Fang, Qian Zhang, Xuehua He, Wanli Xu, Changbo Lu i Kun Yu. "Facile One-Pot Synthesis of α–MnO2/CeO2 Nanowires for Mg-Air Batteries". Journal of The Electrochemical Society, 2.09.2022. http://dx.doi.org/10.1149/1945-7111/ac8edb.
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Abstract We synthesized MnO2/CeO2 electrocatalysts by in situ decoration of α–MnO2 with CeO2 particles during a one-step hydrothermal process. The morphology, composition, and electrochemical properties were studied in the context of application to the oxygen reduction reaction (ORR) and Mg-air battery. According to the results, α–MnO2/CeO2 microfibers exhibited better ORR performance than α–MnO2 microfibers due to the synergistic result between the introduction of Ce3+ in CeO2 lattice and the enhancement of Mn3+ content in MnO2 lattice. α–MnO2/CeO2 microfibers provided a higher surface area and more catalytic active sites than α–MnO2 microfibers by controlling the molar ratio of Ce3+/Mn7+ for the precursor. When the mole ratio of Ce3+ and Mn7+ in the precursors was 10%, the four-electron transfer process of the MnO2/CeO2 microfibers (MC-140-12-10) was found to be similar to that of the 20 wt% Pt/C commercial catalysts. MC-140-12-10 microfibers also showed the excellent long-term stability after 25,000 s and superior Mg–air battery performances than α–MnO2. Hence, the work paves the way for developing Mg-air batteries through a simple synthesis and cost-effective ORR catalyst.
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Wang, Ruixiang, Yanyang Wang, Zheqin Chen, XiaoCong Zhong, Yongmin Xie, Xiaobo Ji, Jiaming Liu, Shubiao Xia i Zhifeng Xu. "PVP-Assisted Iron-Doped ZIF-8 as an Efficient Fe-N-C Oxygen Reduction Electrocatalyst for Zinc-Air Batteries". Journal of The Electrochemical Society, 16.06.2022. http://dx.doi.org/10.1149/1945-7111/ac797f.
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Abstract Transition metal/nitrogen carbon composite (M/NC) is a highly active oxygen reduction reaction (ORR) electrocatalyst, widely used in fuel cells and zinc-air batteries. Herein, a uniform and regular PVP-assisted iron-doped nano dodecahedron (ZP0.1F/NC) is prepared by a simple and efficient one-step in-solution reaction, followed by controlled in-situ pyrolysis. The synthesized electrocatalyst showed excellent electrocatalytic ORR activity in an alkaline medium. Compared with standard 20% Pt/C electrocatalyst, ZP0.1F/NC exhibited onset potential (Eonset) (0.974 V vs. 0.967 V), half-wave potential (E1/2) (0.861 V vs. 0.857 V) and the limiting current density (jd) was 6.373 mA cm-2 vs. 5.401 mA cm-2, also better than the Fe doped ZIF-8 nitrogen composite (ZF/NC), PVP auxiliary ZIF-8 (ZP0.1/NC) and pure ZIF-8 nitrogen composite (Z/NC) synthesized by the same procedure. In addition, the zinc-air battery assembled with ZP0.1F/NC also exhibits outstanding discharge capacity, with a specific capacity and energy density of 793.3 mAh g-1 and 974.9 Wh kgZn-1, respectively, much higher than that of commercial 20% Pt/C-based zinc-air battery (719.8 mAh g-1, 842.6 Wh kgZn-1), indicating its great potential in practical energy conversion and storage.
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Tan, Mingxiu, Qing Wang, Shasha Wang, Wuxin Liu, Dengyang Wang, Shaohua Luo, Pengqing Hou i in. "Ternary (N, B, F)-Doped Biocarbon Derived from Bean Residues as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions". Journal of The Electrochemical Society, 21.09.2022. http://dx.doi.org/10.1149/1945-7111/ac93ba.
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Abstract Development of efficient metal-free carbon-based electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are of great significance for Zn-air batteries. Herein, a porous biocarbon bifunctional catalyst (C-NBF-G) was directly synthesized via simple alkali activation and carbonization from bean residues. C-NBF-G exhibited hierarchical porous structures, ternary heteroatom (N, B, and F) doping, a large specific surface area, and a relatively high degree of graphitization. The synergistic action of these characteristics contributed to the outstanding catalytic properties of C-NBF-G for ORR and OER. The catalyst demonstrated an onset potential of 0.94 V, half-wave potential of 0.824 V, and a limiting current density of 5.92 mA cm-2, comparable to those of the commercial 20 wt% Pt/C catalysts. C-NBF-G also exhibited an OER overpotential of 333 mV at 10 mA cm-2 and a Tafel slope of 114 mV dec-1, lower than those of the commercial Pt/C and RuO2 catalysts. These results proved the promising performance of C-NBF-G as a bifunctional catalyst for the ORR and OER.
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Varathan, Prabakaran, AKHILA kumar SAHU, Prabu Moni i Sumanta kumar Das. "High Performance Air Breathing Zinc-Air Battery with Pt−Ni and Pt−Co Bifunctional Electrocatalyst on N Activated Mesoporous Carbon". Journal of The Electrochemical Society, 8.05.2023. http://dx.doi.org/10.1149/1945-7111/acd352.
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Abstract In a future perspective, the world demands energy conversion and storage devices with high efficiency, lower cost, reliability, and sustainability. Zinc air batteries (ZABs) have proven capable as metal anodes for producing such energy, as they are earth-abundant, economical, and environmentally resilient, suitable for efficient domestic and industrial applications. We developed a catalyst which serves as an excellent bi-functional cathode catalyst for ZAB platinum alloy with the transition metals (nickel and cobalt) supported on the nitrogen doped bio derived high mesoporous carbon using a facile method. This catalyst shows the remarkable performance on both the oxygen reduction reaction and oxygen evolution reaction. Platinum alloy (Pt-Ni and Pt-Co) supported on N-activated bio derived mesoporous carbon (N-MC) shows low over potential and high half wave potential over the commercial catalyst in the ORR. While performance analysis in in-house designed air breathing ZAB, the outstanding performances are achieved with the specific capacity of 746 mAh g-1 for Pt-Co/N-MC and 726 mAh g-1 Pt-Ni/N-MC, which surpass the commercial Pt-Ru/C catalyst which shows a specific capacity of 420 mAh g-1 and also admirable cycling stability over 110 cycles were observed. Undoubtedly, Pt-Co/N-MC and Pt-Ni/N-MC are promising candidates for bi-functional air cathode catalyst for ZAB
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Liu, Yi, Mi Chen, Mussadiq Shah i Zhiwei Liu. "Graphene Oxide Addition Induces the Improvement of ORR Catalysis Properties of Low-Cost Mn-Based Catalyst Used for Al-Air Battery". Journal of The Electrochemical Society, 12.06.2023. http://dx.doi.org/10.1149/1945-7111/acdda2.
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Abstract To further improve the oxygen reduction reaction (ORR) activity of low-cost Mn-based catalyst, graphene oxide (GO) was added in the preparation of one dimensional (1D) α-MnO2 nanorod using KMnO4-MnSO4 system via hydrothermal method. Experimental results showed that the GO addition (20wt.%) could induce the formation of MnO(OH) nanorod. The Mn-based@GO catalyst had more surface defects and oxygen vacancies compared with pure α-MnO2. The onset potential, half-wave potential (E1/2) and limiting current density were significantly enhanced from 0.86 V/0.66 V/3.56 mA cm-2 to 0.91 V/0.77 V/5.41 mA cm-2, indicating that GO addition could greatly improve the catalytic activity of Mn-based catalyst. Furthermore, the discharge voltage, power density, mass energy density of Al-air battery using Mn based@GO catalyst were greatly improved comparing with the usage of pure MnO2 catalyst, and it was also found that the application effect of Mn-based @GO catalyst in the Al-air battery was almost comparable to the commercial 20% Pt/C catalyst. Our research revealed for the first time the commercial potential of the novel and low-cost MnO2/MnO(OH)@GO nanocomposite in the Al-air battery.
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Wang, Ruixiang, Yuanliang Yuan, Xiaocong Zhong, Yirui Zhu, Jiaming Liu, Yongmin Xie, Shuiping Zhong i Zhifeng Xu. "Nitrogen and Phosphorus-codoped Carbon Nanotube/Fe2P Nanoparticle Hybrids Toward Efficient Oxygen Reduction and Zinc-air Batteries". Journal of The Electrochemical Society, 7.06.2022. http://dx.doi.org/10.1149/1945-7111/ac766a.
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Abstract Incorporating metal compound nanoparticles in carbonaceous matrix is a valid strategy to fabricate highly efficient oxygen reduction electrocatalysts. Here, N, P-codoped carbon nanotubes embedded with Fe2P nanoparticles (Fe2P/NPCt) were synthesized using a microemulsion template method. Results show carbon nanotubes have a large specific surface area (987 m2 g-1) with an inner diameter of ~60 nm. About 5.90 wt.% nitrogen (35.18% pyridinic N) and 2.56 wt.% phosphorus (mainly in the form of P-C and P-Fe) was doped in Fe2P/NPCt. HRTEM and XRD results confirmed the well dispersed Fe2P nanoparticles in 5~10 nm on carbon nanotubes. The electrochemical performance of Fe2P/NPCt was evaluated in 0.10 M KOH using cyclic voltammetry, linear scanning voltammetry, and chronoamperometry. Fe2P/NPCt exhibits high electrocatalytic activity toward oxygen reduction with an onset potential of 1.029 V (vs. RHE) and a limited current density of 6.79 mA cm-2, surpassing those of 20% Pt/C (0.950 V and 5.20 mA cm-2). Furthermore, Fe2P/NPCt presents outstanding durability and good methanol tolerance during long-term ORR. When assembled in a primary zinc-air battery (ZAB), the maximum power density and specific capacity of ZAB reach 175.48 mW cm-2 and 744.1 mAh g-1, respectively, outperforming ZAB equipped with 20% Pt/C.