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Mn_(3)O_(4) based materials for electrochemical supercapacitors: Basic principles, charge storage mechanism, progress, and perspectives

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Journal of Materials Science & Technology 2022年第35期130卷 227-248页

作者： S.A.Beknalkar A.M.Teli T.S.Bhat K.K.Pawar S.S.Patil N.S.Harale J.C.Shin P.S.Patil Thin Film Materials Laboratory Department of PhysicsShivaji UniversityKolhapur 416-009India Division of Electronics and Electrical Engineering Dongguk University-SeoulSeoul 04620South Korea School of Nano-Science and Technology Shivaji UniversityKolhapur 416-009India Department of Physics Sadguru Gadage MaharajCollege KaradSataraMississippi 415110India

The captivating properties of supercapacitors(SCs) such as high power and reasonably high energy densities made them stand up as a versatile solution to emerging energy storage applications.Thus,everyone is in pursuit of improvisation of the energy storage characteristics of SCs.Hausmannite or manganese oxide(Mn_(3)O_(4)) is a widely studied electrode material considering its fascinating features such as high theoretical capacitance(1370 F/g),variable oxidization states,prominent Jahn-Teller effect,broad potential window,environmentally benign and cost-effectiveness.A lot of research has been carried out on this material to unfold and improve its electrochemical aspects.In this review,comprehensive knowledge and innovative attempts taken to improve its energy storage of Mn_(3)O_(4)material are discussed.Firstly,the basic properties concerned with electrochemical charge storage such as valance states,crystal structure,band diagram and energy storage mechanism are discussed,followed by putting forth the limitations of Mn_(3)O_(4).Later on,various strategies adopted to improve the electrochemical attributes of Mn_(3)O_(4)such as making composite with carbon-based materials,metal-based materials,polymers or doping metal atoms are thorough.Finally,remarks on key scientific points and perspectives for further development of energy storage in Mn_(3)O_(4)conclude this review.

关键词： supercapacitors Nanostructures Mn_(3)O_(4)based composites

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Nanocellulose/nitrogen and fluorine co-doped graphene composite hydrogels for high-performance supercapacitors

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Nano Research 2023年第7期16卷 9519-9529页

作者： Yong Zhang Qingyun Zhou Wenhui Ma Chaohui Wang Xuefeng Wang Jiajun Chen Tiantian Yu Shan Fan College of Materials Science and Engineering Graphene Functional Materials Research LaboratoryQiqihar UniversityQiqihar 161006China College of Materials Science and Engineering Heilongjiang Province Key Laboratory of Polymeric Composition MaterialQiqihar UniversityQiqihar 161006China School of Chemistry and Chemical Engineering Qiqihar UniversityQiqihar 161006China Department of Practice Teaching and Equipment Management Qiqihar UniversityQiqihar 161006China

Three-dimensional graphene materials have been studied as typical supercapacitors electrode materials by virtue of their ultrahigh specific surface area and good ion transport capacity.However,improvement of the poor volumetric electrochemical performance of these graphene materials has been required although they have high gravimetric energy density.In this work,nanocellulose/nitrogen and fluorine co-doped graphene composite hydrogels(NC-NFGHs)were prepared through a convenient hydrothermal approach utilizing ammonium fluoride as the heteroatom source.Nanocellulose(NC)and high concentration of graphene oxide(GO)were utilized to adjust the structure of NC-NFGHs and increase their packing density.Subsequently,the aqueous symmetric supercapacitor based on NC-NFGH-80 exhibits remarkable gravimetric(286.6 F·g^(-1))and volumetric(421.3 F·cm^(-3))specific capacitance at 0.3 A·g^(-1),good rate performance,and remarkable cycle stability up to 10,000 cycles.Besides,the all-solid-state flexible symmetric supercapacitors(ASSC)fabricated by NC-NFGH-80 also delivered a large specific capacitance of 117.1 F·g^(-1)at 0.3 A·g^(-1)and long service life over 10,000 cycles at 10 A·g^(-1).This compact porous structure and heteroatom co-doped graphene material supply a favorable strategy for high-performance supercapacitors.

关键词： compact graphene composite hydrogel high packing density N/F co-doping gravimetric/volumetric performances supercapacitors

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High mass loading NiCo_(2)O_(4) with shell-nanosheet/core-nanocage hierarchical structure for high-rate solid-state hybrid supercapacitors

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Green Energy & Environment 2022年第4期7卷 723-733页

作者： Wang Yang Liqiang Hou Peng Wang Yun Li Rui Li Bo Jiang Fan Yang Yongfeng Li State Key Laboratory of Heavy Oil Processing China University of Petroleum(Beijing)Changping102249China

Rational design of advanced structure for transition metal oxides(TMOs) is attractive for achieving high-performance supercapacitors.However, it is hampered by sluggish reaction kinetics, low mass loading, and volume change upon cycling. Herein, hierarchical Ni Co_(2)O_(4) architectures with 2D-nanosheets-shell and 3D-nanocages-core(2D/3D h-NCO) are directly assembled on nickel foam via a facile one-step way.The 2D nanosheets are in-situ generated from the self-evolution of initial NCO nanospheres. This 2D/3D hierarchical structures ensure fast ion/electron transport and maintain the structural integrity to buffer the volume expansion. The 2D/3D h-NCO electrode with an ultrahigh mass loading(30 mg cm^(-2)) achieves a high areal capacity of 4.65 C cm^(-2)(equivalent to 1.29 mAh cm^(-2)) at a current density of 4 mA cm^(-2), and retains 3.7 C cm^(-2) even at 50 mA cm^(-2). Furthermore, the assembled solid-state hybrid supercapacitor yields a high volumetric energy density of 4.25 mWh cm^(-3) at a power density of 39.3 mW cm^(-3), with a high capacity retention of 92.4% after 5000 cycles. Therefore, this work provides a new insight to constuct hierarchical electrodes for energy storage application.

关键词： Transition-metal oxides Hierarchical structure High mass loading Free-standing supercapacitors

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Structure-guided Capacitance Relationships in Oxidized Graphene Porous Materials Based supercapacitors

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Energy & Environmental Materials 2023年第4期6卷 58-69页

作者： Srinivas Gadipelli Hanieh Akbari Juntao Li Christopher A.Howard Hong Zhang Paul R.Shearing Dan J.L.Brett College of Physics Sichuan UniversityChengdu 610064China Electrochemical Innovation Lab Department of Chemical EngineeringUniversity College LondonLondonWC1E 7JEUK Department of Physics and Astronomy University College LondonLondonWC1E 6BTUK

supercapacitors formed from porous carbon and graphene-oxide(GO)materials are usually dominated by either electric double-layer capacitance,pseudo-capacitance,or both.Due to these combined features,reduced GO materials have been shown to offer superior capacitance over typical nanoporous carbon materials;however,there is a significant variation in reported values,ranging between 25 and 350 F g^(−1).This undermines the structure(e.g.,oxygen functionality and/or surface area)-performance relationships for optimization of cost and scalable factors.This work demonstrates important structure-controlled charge storage relationships.For this,a series of exfoliated graphene(EG)derivatives are produced via thermal-shock exfoliation of GO precursors and following controlled graphitization of EG(GEG)generates materials with varied amounts of porosity,redox-active oxygen groups and graphitic components.Experimental results show significantly varied capacitance values between 30 and 250 F g^(−1)at 1.0 A g^(−1)in GEG structures;this suggests that for a given specific surface area the redox-active and hydrophilic oxygen content can boost the capacitance to 250–300%higher compared to typical mesoporous carbon materials.GEGs with identical oxygen functionality show a surface area governed capacitance.This allows to establish direct structure-performance relationships between 1)redox-active oxygen functional concentration and capacitance and 2)surface area and capacitance.

关键词： electric double-layer capacitance graphene-oxide pseudocapacitance structure-performance relationships supercapacitors

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Ultrafastly activated needle coke as electrode material for supercapacitors

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Progress in Natural Science:Materials International 2022年第6期32卷 786-792页

作者： Cuihua Zeng Cunpeng Duan Zhaoxin Guo Zhedong Liu Shuming Dou Qunyao Yuan Peng Liu Jingchao Zhang Jiawei Luo Weidi Liu Jinfeng Zhang Yanan Chen Wenbin Hu School of Materials Science and Engineering Tianjin University Institute of Frontier and Interdisciplinary Science and Key Laboratory of Particle Physics and Particle Irradiation (MOE) Shandong University Australian Instiute for Bioengineering and Nanotechnology The University of Queensland

The uniform porous structure makes activated porous carbons(APCs) superior electrode material.Traditionally,APCs are produced by a combination of time-consuming high-temperature heat treatment and activation,with a production time of up to several hours.The produced APCs have relatively low specific surface area(SSA) and porosity.Therefore,the electrochemical performance is poor,which limits its application in high-power energy storage devices.Here,APCs materials are directly synthesized by a high temperature shock(HTS) strategy using needle coke as a precursor.The structure of as-prepared APC is characterized by XRD,SEM and Raman,and electrochemical tests confirmed its good electrochemical performance.In the two-electrode system,the super-capacitor with HTS-APC as the electrode material provides a high energy density of 35 Wh kg-1and a high power density of 875 W kg-1in EMIMBF4ionic liquid.This work is instructive for the rapid synthesis of electrode materials,and also provides guidance for the large-scale application of porous carbon materials.

关键词： supercapacitors Activated porous carbons (APCs) High temperature shock (HTS) method Cost-effective

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Strengths,weaknesses,opportunities,and threats(SWOT)analysis of supercapacitors:A review

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Journal of Energy Chemistry 2023年第4期79卷 611-638页

作者： Pragati A.Shinde Qaisar Abbas Nilesh R.Chodankar Katsuhiko Ariga Mohammad Ali Abdelkareem Abdul Ghani Olabi Sustainable Energy&Power Systems Research Centre RISEUniversity of SharjahP.O.Box 27272SharjahUnited Arab Emirates International Center for Materials Nanoarchitectonics(WPI-MANA) National Institute for Materials Science(NIMS)1-1 NamikiTsukuba 305-0044Japan Department of Energy and Material Engineering Dongguk University-SeoulSeoul 04620Republic of Korea Graduate School of Frontier Sciences The University of Tokyo5-1-5 KashiwanohaKashiwaChiba 277-8561Japan Mechanical Engineering and Design School of Engineering and Applied ScienceAston UniversityAston TriangleBirmingham B47ETUK School of Computing Engineering and Physical SciencesUniversity of The West of ScotlandGlasgowPA12BEUK

The development of clean and sustainable energy sources has received widespread interest in the past few decades due to the rolling energy demands while extenuating the rising tiers of greenhouse gases and environmental pollution.Due to their intermittent nature,these green and sustainable sources require appropriate energy storage systems.Amongst different energy storage technologies,electrochemical energy storage devices,particularly supercapacitors(SCs),have fascinated global attention for their utilization in electric vehicles,power supports,portable electronics,and many others application requiring electric energy devices for their operation.Thus,the growth of SCs in the commercial market has squeezed requirements,and further developments are obligatory for their effective industrialization.In the meantime,SCs also face technical complications and contests for their introduction in industrial settings because of their low energy density and high Levelized cost.The present study combines core strengths,weaknesses,opportunities,and threats(SWOT)analysis of SCs with new perspectives and recent ideas.The challenges and the future progressive prospects of SCs are also presented in detail.This review will afford consistent direction and new superhighways for the further development of SCs as standalone and complementary energy storage systems.

关键词： supercapacitors Energy storage Strengths Opportunities

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Extrusion-Based 3D-Printed supercapacitors:Recent Progress and Challenges

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Energy & Environmental Materials 2022年第3期5卷 800-822页

作者： Xiao Yan Yueyu Tong Xinzhong Wang Feng Hou Ji Liang Research Centre for Information Technology Shenzhen Institute of Information TechnologyShenzhen 518172China Institute for Superconducting&Electronic Materials Australian Institute of Innovative MaterialsUniversity of WollongongNorth Wollongong NSW 2500Australia Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education School of Materials Science and EngineeringTianjin UniversityTianjin 300072China

supercapacitors have been regarded as promising power supplies for future electronics due to their high power density,superior stability,easy integration,and safety.Extrusion-based three-dimensional printing technologies hold promise to satisfy the demands for integrated and flexible supercapacitors because of their highly versatile manufacturing process.In this review article,a comprehensive and timely review of these state-of-theart technologies is presented.We start with a brief introduction of fundamental concepts of supercapacitors,including energy storage mechanisms and device structures.Then,the latest progress of extrusionbased three-dimensional printing technologies(e.g.,fused deposition modeling,inkjet printing,and direct ink writing)along with their applications for manufacturing supercapacitors is summarized.The choice of printable materials(e.g.,graphene,carbon nanotubes,metal oxides,and MXenes),printing process,and the resulted electrochemical performances of supercapacitors are especially emphasized.Finally,the development of extrusion-based three-dimensional printing supercapacitors is summarized,with existing challenges diagnosed,possible solutions proposed,and future outlooks forecasted.We hope this review can offer insights to further improve the performance of three-dimensional-printed supercapacitors for practical applications.

关键词： 3D printing direct ink writing fused deposition modeling inkjet printing supercapacitors

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Pore-structure regulation and heteroatom doping of activated carbon for supercapacitors with excellent rate performance and power density

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Waste Disposal and Sustainable Energy 2023年第3期5卷 417-426页

作者： Jian Zhang Huachao Yang Zhesong Huang HuiHui Zhang Xinchao Lu Jianhua Yan Kefa Cen Zheng Bo State Key Laboratory of Clean Energy Utilization Institute for Thermal Power EngineeringCollege of Energy EngineeringZhejiang UniversityHangzhou310027ZhejiangChina

Activated carbon(AC)has attracted tremendous research interest as an electrode material for supercapacitors owing to its high specific surface area,high porosity,and low cost.However,AC-based supercapacitors suffer from limited rate performance and low power density,which mainly arise from their inherently low electrical conductivity and sluggish ion dynamics in the micropores.Here,we propose a simple yet effective strategy to address the aforementioned issue by nitrogen/fluorine doping and enlarging the micropore size.During the treatment,the decomposition products of NH4F react with the carbon atoms to dope the AC with nitrogen/fluorine and simultaneously enlarge the pores by etching.The treated AC shows a higher specific surface area of 1826 m2 g^(−1)(by~15%),more micropores with a diameter around 0.93 nm(by~33%),better wettability(contact angle decreased from 120°to 45°),and excellent electrical conductivity(96 S m^(−1))compared with untreated AC(39 S m^(−1)).The as-fabricated supercapacitors demonstrate excellent specific capacitance(26 F g^(−1)at 1 A g^(−1)),significantly reduced electrical resistance(by~50%),and improved rate performance(from 46.21 to 64.39%at current densities of 1 to 20 A g^(−1)).Moreover,the treated AC-based supercapacitor achieves a maximum energy density of 25 Wh kg^(−1)at 1000 W kg^(−1)and a maximum power density of 10,875 W kg^(−1)at 15 Wh kg^(−1),which clearly outperforms pristine AC-based supercapacitors.This synergistic treatment strategy provides an effective way to improve the rate performance and power density of AC-based supercapacitors.

关键词： Activated carbon Heteroatom doping Pore-size modification Rate performance supercapacitors

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Effect of structural variation in biomass-derived nonfluorinated ionic liquids electrolytes on the performance of supercapacitors

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Journal of Energy Chemistry 2022年第6期31卷 174-184,I0005页

作者： Inayat Ali Khan Yong-Lei Wang Faiz Ullah Shah Chemistry of Interfaces.Lulea University of Technology.SE-97187 Luled Sweden Department of Materials and Environmental Chemistry.Arrhenius Laboratory.Stockholm University.SE-10691Stockholm.Sweden

There is a growing interest in sustainable and high performance supercapacitors(SCs) operating at elevated temperatures as they are highly demanded in heat-durable electronics. Here, we present a biomass-derived nonfluorinated ionic liquid(IL) [P_(4444)][HFuA] and its structural analogue [P_(4444)][TpA]as electrolytes for supercapacitors comprising multiwall carbon nanotubes and activated charcoal(MWCNTs/AC) mixed carbon composite electrodes. A detailed investigation of the effect of scan rate, temperature, potential window and orientation of ions on the electrodes surfaces is performed. The supercapacitors exhibited relatively lower specific capacitance for both [P_(4444)][HFuA] and [P_(4444)][TpA] ILs at room temperature. However, the specific capacitance has significantly increased with an increase in temperature and potential window. The equivalent serie resistances of the SCs is deceased with increasing temperatures, which is a result of improved ionic conductivities of the IL electrolytes. In CV cycling at60 °C, the capacitor with [P_(4444)][HFuA] IL-based electrolyte retained about 90% of its initial capacitance,while the capacitor with [P_(4444)][TpA] IL-based electrolyte retained about 83% of its initial capacitance.Atomistic computations revealed that the aromatic [FuA]^(-) and [TpA]^(-) anions displayed perpendicular distribution that can effectively neutralize charges on the carbon surfaces. However, the [HFuA]-anion exhibited somewhat tilted configurations on the carbon electrode surfaces, contributing to their outstanding capacitive performance in electrochemical devices.

关键词： Biomass Ionic liquids Carbon electrodes supercapacitors Molecular dynamic simulations

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Advanced MOF-based electrode materials for supercapacitors and electrocatalytic oxygen reduction

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Nano Research 2023年第1期16卷 1338-1361页

作者： Bolong Yang Bingjie Li Zhonghua Xiang State Key Laboratory of Organic-Inorganic Composites Beijing University of Chemical TechnologyBeijing 100029China The First Affiliated Hospital of Zhengzhou University Zhengzhou 450052China

Metal-organic frameworks(MOFs)have attracted a lot of attention due to their diverse structures,favorable porous properties,and tunable chemical compositions in the multiple fields.Notably,MOF-based materials(including pristine MOFs,MOF composites,and their derivatives)play the vital role in electrochemical energy storage and conversion systems,due to their ability for regulating chemical composition at the molecular level and their highly porous frameworks for facilitating the mass and charge transfer.supercapacitors and fuel cells are used as one of energy storage and conversion systems respectively,and it is unstoppable to design and synthesize high-efficiency electrode materials for them.This review starts with the strategies for designing targeted MOF-based materials in electrochemical energy storage and conversion applications followed by the state-ofthe-art MOF-based materials discussed as to their potential applications in supercapacitors and electrocatalytic oxygen reduction reaction(ORR).Finally,the challenges and perspectives of MOF-based materials applied for supercapacitors and electrocatalytic ORR are discussed.

关键词： metal-organic frameworks(MOFs) MOF composites MOF derivatives supercapacitors electrocatalytic oxygen reduction reaction(ORR)

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