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High-performance Ir Based Double Anode Catalyst Layer for Anion Exchange Membrane Water Electrolysis
YIN Yan, YIN Shuoyao, CHEN Bin, FENG Yingjie, ZHANG Junfeng
Materials Reports
2024,38(6 ):23040182 -7. DOI:10.11896/cldb.23040182
Abstract
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334
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Design of high-performance low-Ir anode catalyst layer is crucial for the commercial development of anion-exchange membrane water electrolysis (AEMWE). In this study, a double catalyst layer structure based on iridium oxide (IrO
2
) and carbon loaded iridium (IrC) was constructed by catalyst coated substrate (CCS) method to improve AEMWE performance. It was found that the IrC-IrO
2
catalyst layer is beneficial to improve the Ir utilization and optimize the transport of electron and hydroxide ions within the catalyst layer due to the highly dispersed morphology of IrC. High AEMWE current density of 2.31 A/cm
2
was achieved at 2.0 V under 1 mol/L KOH by combining commercial Pt/C catalyst as cathode and IrC-IrO
2
double catalyst layer as the anode. High performance was maintained at low electrolyte concentrations as well as in pure water. This study provides an example of the efficient catalyst layer design for AEMWE technology.
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Current Status and Challenges in the Application of Cobalt-based Cathode Materials in Zinc Batteries
SHANG Wenxu, YU Wentao, HE Yi, MA Yanyi, TAN Peng
Materials Reports
2024,38(6 ):23040024 -10. DOI:10.11896/cldb.23040024
Abstract
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332
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Benefiting from abundant mineral resources, ultra-high theoretical capacity and excellent safety, aqueous zinc batteries have become a strong contender for next-generation energy storage devices. As an ideal cathode material candidate for zinc batteries, cobalt-based electrode materials have received increasing attention in recent years due to their high output voltage, high theoretical capacity and excellent redox ability (Co
2+
↔Co
3+
↔Co
4+
). Although cobalt-based catalysts applied to zinc-air batteries have been reviewed by researchers, they mainly focus on a single catalytic direction, and a systematic summary of the multifunctional properties of cobalt-based electrode materials is lacking. This review introduces the application of multifunctional properties of cobalt-based cathode materials in zinc batteries, combining both their redox and oxygen catalysis capabilities, expanding from zinc-cobalt batteries to zinc-cobalt hybrid systems. Then, the charging and discharging mechanisms in the two battery systems are introduced, following by the current optimization strategies of cobalt-based materials in zinc-cobalt batteries and the design of electrode/electrolyte three-phase interface in zinc-cobalt hybrid batteries. Finally, this paper introduces the shortcomings of the current research and provides an outlook on future research.
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Tailoring of the Surface Charge of Glucose-derived Porous Carbons and Their Performance for Electrosorption of Cd
2+
QIN Lingshuang, LIU Xing, DENG Libo
Materials Reports
2024,38(6 ):23040284 -8. DOI:10.11896/cldb.23040284
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268
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Capacitive deionization (CDI) is a promising technology for Cd
2+
removal owing to the advantages such as simple and convenient operation, low energy consumption, and free of secondary pollution. The key challenge limiting its development is the low adsorption capacity of electrode materials for Cd
2+
. In this work, we used glucose as carbon source, thiourea and sulfur as the dopant to prepare porous carbon materials co-doped with S and N through high-temperature carbonization, and explored its electrochemical adsorption performance for Cd
2+
, by using the prepared carbon material as the electrode. The symmetrical CDI system assembled with identical material for both electrodes achieved a removal capacity of 53 mg·g
-1
for Cd
2+
at 1.2 V. Furthermore, it was found that with the increase of S and N doping, the surface of carbon materials carries negative charges. Therefore, the asymmetric CDI system assembled by using it as the anode and commercial activated carbon YP-50F as the cathode, and Cd
2+
removal capacity reached 88.37 mg·g
-1
, which was 66.73% higher than symmetrical CDI system. After seven cycles of adsorption-desorption, the capacity retention rate also increased from 62.2% to 81.5%. The removal mechanism of Cd
2+
was explored by XPS, and the results showed that it was the synergism of double electric layer and surface functional groups. The matching strategy of high-perfor-mance porous carbon electrodes and asymmetric electrodes developed in this work would pave the way for practical application of CDI technology in the treatment of Cd
2+
and other heavy metal wastewater.
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Research Progress and Challenges of Anode for Reversible Zinc-Air Batteries
WANG Yue, ZHOU Benji, XU Nengneng, QIAO Jinli
Materials Reports
2024,38(6 ):23040162 -10. DOI:10.11896/cldb.23040162
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Zinc-air battery has attracted wide attention because of its high safety, large capacity, low cost and environmental friendliness. Among them, the design and development of cathode bifunctional catalyst for zinc-air battery has made breakthrough progress. Therefore, the reversibility of zinc anode has become the key to determine the charging and discharging performance of zinc-air battery. However, the zinc anode still faces serious challenges such as dendrite, deformation, passivation and hydrogen evolution corrosion, which directly hinders the practical application of reversible zinc-air batteries. Therefore, this paper systematically introduces the research status of zinc anode from four aspects, dendrite formation, electrode deformation, passivation and hydrogen evolution corrosion. The effects of additives, coatings, separators and charging methods on the growth of zinc dendrites are discussed. The mechanism of electrode deformation and common solutions are studied. The key factors and influencing mechanism of zinc anode passivation are summarized. The inhibition of alloy components on hydrogen evolution corrosion is analyzed. Finally, based on the current research status of zinc anode, this paper looks forward to various strategies and research directions for obtaining stable and reversible zinc anode.
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Progress in Preparation and Electrochemical Application of Single-wall Carbon Nanohorns
SU Xiankai, XIE Zhipeng, ZHANG Da, HOU Shengping, YANG Bin, LIANG Feng
Materials Reports
2024,38(6 ):22100192 -13. DOI:10.11896/cldb.22100192
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Single-wall carbon nanohorns (SWCNHs) are hollow conical carbon nanomaterials produced by curling a single layer of graphene. SWCNHs cannot exist alone in a normal state, but instead as spherical aggregates formed by thousands of SWCNHs. Due to their excellent electrical and thermal properties, low density, and high specific surface area, SWCNHs are regarded as promising carbon nanomaterials for electrochemical application. SWCNHs are usually prepared by laser ablation, arc discharge, and joule heating methods, and these process do not use metal catalysts, so as to avoid impurity contamination, which broadens the application of SWCNHs. Over the last two decades, SWCNHs have been widely used in supercapacitors, electrochemical sensors, and lithium-ion, solar, fuel, and metal-CO
2
batteries. Numerous studies have shown that SWCNH-based electrochemical devices offer high efficiency, stability, and safety. Promoting the industrial production and large-scale application of SWCNHs in the electrochemical field is of great significance to the development of new energy and high-end manufacturing industries in China. This study summarizes the structure, characteristics, and preparation methods of SWCNHs, reviews the research progress of SWCNHs in the field of electrochemistry, and prospects future research directions and development trends of SWCNHs.
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Design and Reversibility Study of Nitrogen-doped Porous Carbon Surface Functional Layer for Zinc Anodes
CHEN Jingjian, XU Nengneng, LU Tuo, WEI Qunshan
Materials Reports
2024,38(6 ):23040217 -6. DOI:10.11896/cldb. 23040217
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Zinc anode has become a key factor limiting the cycling performance of zinc-air batteries due to challenges such as dendrite growth, hydrogen evolution, deformation, and passivation. In this study, carbon materials with abundant mesoporous structures were prepared using quaternary ammonium salts as carbon and nitrogen sources through a hard template method, and they were used as a surface functional layer for the zinc anode (N-MC@Zn). The N-MC@Zn material had a high specific surface area of 590.06 m
2
·g
-1
and an average pore size of 22 nm. The research showed that constructing a nitrogen-doped porous carbon functional layer on the surface of the zinc anode effectively mitigated the negative effects caused by the aforementioned challenges. In particular, the abundant pores in the porous carbon coating provided a buffer zone for zinc deposition/stripping, greatly accelerating the deposition kinetics and stabilizing the deposition/stripping process of zinc ions, thus alleviating hydrogen evolution corrosion of the zinc anode. Furthermore, the anisotropy within the porous carbon coating prevented the growth of dendrites by avoiding the tip effect. Based on these advantages, N-MC@Zn exhibited excellent discharge and charge stability (140 h, 700 cycles), rate capability (from 0.5C to 10C), and discharge capacity. These results demonstrate that porous carbon materials can serve as high-performance functional layer materials for zinc anodes and provide a new perspective for the design of zinc anode coatings.
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Recent Research Progress of MOFs Derivatives for Urea Oxidation
ZHANG Xia, WU Ying, YUEN Mufung, WANG Chundong
Materials Reports
2024,38(6 ):23020193 -10. DOI:10.11896/cldb.23020193
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Urea oxidation reaction (UOR) plays an essential role in reducing the strain of contemporary hydrogen energy production and wastewater treatment, and the development of electrocatalysts with superior performance can aid in lowering the amount of energy required. Derivatives of metal-organic frameworks (MOFs) materials have garnered a lot of attention for their potential as electrocatalysts, by addressing the inherent flaws of poor conductivity and stability. With reference to the design and construction of MOF-derivatives, we review and summarize some studies based on: (i) the reaction mechanism of nickel-based/non-nickel-based UOR; (ii) strategies to improve the electronic conductivity by means of structural modulation, morphology control, interfacial engineering, and defect engineering, outlining the change in physical properties of the materials with respect to the catalytic activity correlation;(iii) analyses of the applications of UOR-based MOFs derivatives. Finally, we give some perspectives on the most recent research challenges and developments in UOR.
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Research Progress of Graphitic Carbon Nitride in Polymer Electrolyte Membrane
LIU Shouyi, WANG Yuhao, LIU Lili, OUYANG Yunxiang, LI Na, HU Zhaoxia, CHEN Shouwen
Materials Reports
2024,38(6 ):23030250 -7. DOI:10.11896/cldb.23030250
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Fuel cells have attracted wide attention due to the high energy conversion efficiency, near-zero pollution and low noise. Polymer electrolyte membrane (PEM) is an important component of fuel cells, its performance determines the practical output of fuel cells. To address the shortcomings of PEMs in terms of stability and ionic conductivity, inorganic nanomaterial doping is applied to PEMs as a conventional modification method. In recent years, graphitic carbon nitride (g-C
3
N
4
) has been widely used in the preparation and modification of PEMs due to its unique structural characteristics and excellent physic-chemical properties. This review mainly describes the structural properties of g-C
3
N
4
, summarizes the typical preparation methods of g-C
3
N
4
-based composite PEMs, focuses on the current research and application of g-C
3
N
4
, demonstrates its important achievements in the modification aspect, and gives an outlook on its future development in PEMs.
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Research Advances of Metal-based Phosphide Nanomaterials Toward Electrocatalytic Applications
LIU Hui, YANG Niuwa, MA Mengyuan, TIAN Shaonan, ZHANG Yu, YANG Jun
Materials Reports
2024,38(8 ):23080249 -17. DOI:10.11896/cldb.23080249
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Nanometer sized metal phosphides and their nanocomposites with noble metals have unique physical/chemical properties that have been found wide applications in electrocatalysis. For instance, in methanol oxidation reaction, the shift of electron clouds from noble metals, e.g. Pt and Pd, to the phosphor (P) due to larger electronegativity of the latter would enhance thetolerance of noble metals for the CO-like interme-diates produced during methanol oxidation. Also, in hydrogen evolution reaction (HER) of electrocatalytic water splitting, the P element in the phosphide-based nanocomposites could strengthen the H
+
adsorption by serving as proton acceptor, thus promoting the HER. In addition, in oxygen evolution reaction (OER), the metal phosphides could be easily transformed into metal oxides/hydroxides for forming metal phosphide-metal oxide/hydroxide interfaces that is capable to boost the OER. It is well known that the catalytic performance of a catalyst strongly depends on its structure, components and their interactions as well as the electronic configuration of the active sites. In this context, rational regulation of the above-mentioned properties of metal phosphide-based nanocomposites is of necessity to improve their electrocatalytic performance. It is noteworthy that the materials in this review include metal phosphides and their nanocomposites with different nobles. We would firstly introduce the synthesis and characterization of metal phosphide-based nanocomposites, and subsequently, we focus on reviewing recent advances and challenges in making use of the lattice strain effect and electronic coupling effect to boost the performance of metal phosphide-based nanocomposites in typical electrochemical reactions. Eventually, regarding further improvement in elecrtocatalytic performance, we make some perspectives on the future synthetic strategies and development of the metal phosphide-based nanocomposites.
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Performance Research of CO
2
Electrolysis of Mn Doped Pr
0.5
Ba
0.5
Fe
0.9
Mn
0.1
O
3-δ
Perovskite as SOEC Cathode
TANG Jiangcheng, ZHAO Xianxing, CAI Runtian, YANG Chenghao, CHI Bo
Materials Reports
2024,38(8 ):23040185 -6. DOI:10.11896/cldb.23040185
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Cathode is the site where the CO
2
reduction reaction occurs in solid oxide electrolysis cell (SOEC) for CO
2
electrolysis, and it is also the key component for SOEC to achieve high performance. The electrochemical performance of Pr
0.5
Ba
0.5
Fe
0.9
Mn
0.1
O
3-δ
(PBFM) perovskite as SOEC cathode catalyst to convert CO
2
to CO was studied. The result shows that the cell based on PBFM cathode shows a higher current density of 1.7 A·cm
-2
at applied 1.8 V voltage and 850 ℃. There is an approximately 30% performance improvement compared to the SOEC based on PBF cathode. Meanwhile, the polarization impedance has also decreased by about 60%. The increased current density originates from the improved oxygen vacancy. Furthermore, the cell with this active catalyst exhibits a stable CO
2
electrolysis performance for 70 h operation at a stable voltage of 1.3 V at 800 ℃, and no carbon deposition is detected after the long-term test. The research suggests that PBFM can be a talented candidate as SOEC cathode for CO
2
electrolysis.
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Research Progress of Ionomers for Anion Exchange Membrane Water Electrolysis
ZHAO Cenkai, ZOU Jiexin, WANG Min, LI Siming, ZHAO Wei, ZHANG Shilin, TENG Juejin, WANG Yanjiao, WU Mingbo, HU Han, LI Yawei
Materials Reports
2024,38(8 ):23080132 -11. DOI:10.11896/cldb.23080132
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Nowadays, as the energy scarce increasing, hydrogen energy has emerged as a renewable and environmental-friendly new energy source. It serves as an important energy carrier for global energy conservation and carbon reduction. Traditional alkaline water electrolysis (AWE) is the most common method for hydrogen production, but it requires alkaline solution with high pH as the electrolyte and can only operate at low current density; proton exchange membrane water electrolysis (PEMWE) technology, on the other hand, can be operated at high current density with high efficiency, making it the most promising water electrolysis technology for hydrogen production. However, the expensive catalyst and need for acid-resistant components are important challenges that hinder its development. Anion exchange membrane water electrolysis (AEMWE) is a promising new technology for green and cost-effective hydrogen production. Comparing with AWE, it avoids the circulation of concentrated alkaline solution. Comparing with PEMWE, it offers advantages such as lower cost and lower corrosiveness. Ionomers, as a key component of the triple phase boundary (TPB) in the membrane electrode assembly (MEA), play a crucial role in the catalytic capabilities and water management of AEMWE. This review firstly aims to provide an overview of AEMWE technology and the importance of ionomer in MEA. It also summarizes the structures and characteristics of representative ionomers adopted in AEMWE. Finally, this review explores strategies to improve the electrolytic performance of AEMWE through ionomer regulations from three aspects: structural regulation, content regulation and additive re-gulation.
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Mechanism of Interfacial Effects in Sodium-ion Storage Devices
WEI Yifan, XIA Huicong, ZHANG Jianan
Materials Reports
2024,38(8 ):23120085 -9. DOI:10.11896/cldb.23120085
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Rechargeable sodium-ion batteries (SIBs) are the next generation of secondary batteries. During charging and discharging, the behavior of sodium ion (Na
+
) storage at the electrode interface and electrode-electrolyte interface determines the performance of SIBs, which plays an important role in the high energy density and long cycle stability required by the large-scale energy storage battery system. Although electrode materials have been extensively studied, there is very little work on the construction of stable and efficient SIBs interfaces compared to the large number of electrode materials studied. Although there are a few researches and explorations on the mechanism of interfacial effect, the researches on the regulation strategies of interfacial effect are still in the initial stage, and the results obtained are not in-depth enough to draw systematic conclusions. Here in, the mechanism of interfacial effect in Na
+
storage process is reviewed. The interface is divided into heterogeneous interface of electrode material, solid electrolyte interphase and cathode electrolyte interphase. The mechanism of interfacial effect in intercalation reaction, transformation reaction and alloy reaction and its influence on the overall battery performance were summarized. This provides guidance for the optimization of electrode structure and electrode-electrolyte interface structure, which is very important for the performance optimization of SIBs. In addition, it analyzes the challenges in SIB interfacial effects research and suggests several promising methods and opportunities for advancing the understanding of interfacial effects mechanisms.
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In-situ Synthesis of Mott-Schottky Co/Co
9
S
8
Heterojunction Anchored on Carbon Nanosheets for Efficient Electrochemical Performance
FANG Yu, LI Jing, KONG Weichao, ZHOU Xue, XU Lin, SUN Dongmei, TANG Yawen
Materials Reports
2024,38(8 ):23040234 -7. DOI:10.11896/cldb.23040234
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321
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Using K
3
[Co(CN)
6
] as Co source, thiurea as S source and natural hydrophilic polymer chitosan rich in -OH and -NH
2
as carbon source, the Co precursor and S source were uniformly distributed in the C precursor by forming CS-K
3
[Co(CN)
6
] hydrogel. The main driving force of hydrogel formation is the coordination crosslinking of metal Co ions with -NH
2
in chitosan and the bridging between Co ions via -CN. Thanks to the uniformly dispersed precursor and the catalysis of the Co formed at the initial stage of subsequent pyrolysis, N, S co-doped carbon nanosheets with encaged Co/Co
9
S
8
heterojunction (Co/Co
9
S
8
@N, S-CNSs) were constructed in situ by simply regulating the atomic ratio of Co to S. The morphology, composition and structure of the prepared electrocatalysts and the oxygen evolution reaction performance were analyzed with SEM, TEM, BET, XRD, Raman, XPS and electrochemical workstations. The results show that the Mott-Schottky type Co/Co
9
S
8
interface effectively regulates the electronic structure and charge-transport characteristics of the active center. The loading of two-dimensional doped porous carbon nanosheets makes the active sites more evenly dispersed, while providing high-speed electron and mass transfer channels, as well as avoiding the migration and aggregation of active sites during the catalytic process. The synergistic action of these two allows the proposed Co/Co
9
S
8
@N, S-CNSs catalyst have better electrocatalytic performances. At a current density of 10 mA·cm
-2
, the overpotential of the proposed catalyst for basic oxygen evolution reaction/OER is only 304 mV, which is better than that of the commercial RuO
2
. This study is helpful for the development of cheap transition metal catalysts with excellent electrocatalytic properties.
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Recent Developments in the Electrocatalytic Reduction of CO
2
in Acidic Environments
SUN Yazhou, XU Sha, ZOU Jinhan, WU Zhihua, XIE Shunji
Materials Reports
2024,38(8 ):23040216 -6. DOI:10.11896/cldb.23040216
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Electrocatalytic conversion of CO
2
into high-value chemicals and fuels by renewable energy provides a viable approach to the global climate change and energy crisis, and its development has great potential for practical production. At present, most of the basic and neutral reaction systems studied, CO
2
is liable to interact with hydroxide (OH
-
) to form carbonate or bicarbonate, resulting in CO
2
loss, lowering the energy conversion efficiency and stability of the reaction system. The above problems will be solved by the research and development of electrocatalytic CO
2
reduction reaction (CO
2
RR) in acid. This review has shed light on the effects of reaction device, catalyst, reaction microenvironment on the performance of CO
2
RR and the microscopic reaction mechanism systematically in acidic CO
2
RR. Finally, foresight tactics are put forward for catalyst design, reaction mechanism research, reaction microenvironment regulation, and reactor design and optimization in acidic CO
2
RR.
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Preparation of PVA Based Gel Polymer Electrolytes and Its Application in Energy Storage Devices
NIU Zheng, LUO Xi, XU Nengneng, CHEN Gang, QIAO Jinli
Materials Reports
2024,38(8 ):23040146 -11. DOI:10.11896/cldb.23040146
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Development of high-performance solid polymer electrolyte membranes (SPEMs) is a subject of intense research owing to its promising applications in electrochemical energy storage and conversion devices. Gel polymer electrolytes (GPEs) based on polyvinyl alcohol (PVA) are ideal electrolyte materials owing to their strong hydrophilicity, non-toxic, good compatibility and excellent chemical stability. In this paper, the preparation and synthesis of PVA based hydrogel electrolytes are summarized, and their basic physical properties and electrochemical properties are discussed. Specifically, the research progress of PVA based gel electrolytes in supercapacitors, flexible zinc air batteries, lithium-ion batteries and solar hydrothermal batteries is systematically reviewed, and their excellent electrochemical application potential is analyzed. At last, the future development of PVA based GPEs in this field is prospected.
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Application of Electrically-conductive (Cu, Mn)
3
O
4
Contact Layer on Anode-Side of SOEC
HUANG Xurui, YU Yutian, LEI Jinyong, HAO Jingxuan, YU Chuanxin, PAN Jun, YANG Yiping, LIAO Zihao, GUAN Chengzhi, WANG Jianqiang
Materials Reports
2024,38(8 ):23040278 -4. DOI:10.11896/cldb.23040278
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In SOEC stack, several issues including high contact resistance, oxidation of interconnect surface as well as anode‘ Cr poisoning’ exist between the interconnect and anode, which can significantly result in performance degradation for the stack. In this study, the (Cu, Mn)
3
O
4
-based spinel was evaluated as the SOEC anode-side contact material. A mixture of Mn and CuO was thermally converted into the spinel layer to lower the sintering temperature and enhance the performance. A simulated interconnect/contact/anode cell was fabricated to investigate the effectiveness of the reactively-sintered contact layer on the electrical performance and chemical compatibility. The tested cell exhibited extremely stable behavior with an ASR of only 20.13—20.32 mΩ·cm
2
. While the Cr-rich oxide scale was effectively reduced, no obvious interdiffusion was observed between the contact layer and adjacent cell component at each interface. The (Cu, Mn)
3
O
4
contact layer improved the electrochemical performance of the test cell, significantly reduced the contact resistance.
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Advances in the Application of Waste Tire Pyrolysis Carbon Black for Energy Storage and Conversion
CHEN Meiling, SUN Yanzhi, WU Yufeng, YUAN Haoran, PAN Junqing
Materials Reports
2024,38(8 ):23100011 -11. DOI:10.11896/cldb.23100011
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With the rapid development of vehicles, plenty of waste tires are produced globally, resulting in serious resource waste and environmental pollution, etc. The pyrolysis process is considered a high-efficiency method for the final treatment of waste tires and has obtained wide application. As a main by-product of the waste tire pyrolysis process, the high-value recycling and utilization of pyrolytic carbon black(CBp) is conducive to the healthy development of the pyrolysis industry and upgrading in full value chains. The CBp contains 75%—81% amorphous carbon, which can be demineralized and modified to obtain porous carbon materials with enhanced electrical conductivity and other properties comparable to commercial carbon black, demonstrating an important role in energy storage and energy conversion applications. This paper combines the purification method of CBp from waste tires and the modification method, mainly focusing on the research progress of CBp in supercapacitors, se-condary batteries and electrocatalysis, etc., and reviews and analyzes the current situation of CBp resourcefulness research and application.
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