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Recent progress in MXene layers materials for supercapacitors:High-performance electrodes

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SmartMat 2023年第1期4卷 19-53页

作者： Yitong Wang Yuhua Wang Hubei Province Key Laboratory of Science in Metallurgical Process Wuhan University of Science and TechnologyWuhanChina

In 2011,Gogotsi et al.discovered a new type of two-dimensional transition metal carbides and nitrides,called MXenes,which have become a dazzling new star in the energy storage industry.MXenes are endowed with a series of fascinating properties due to their unique structures and tunable surface chemical functional groups.The application of MXenes in electrochemical energy storage has attracted special attention,especially showing great potential in supercapacitor applications.Compared with other materials,MXenes have high mechanical flexibility,high energy density,and good electrochemical performance,so they are especially suitable as electrode materials for supercapacitors.However,similar to other 2D materials,due to the strong van der Waals forces,MXene layers inevitably undergo stacking agglomeration,resulting in severe loss of electrochemically active sites.If the self-stacking of MXenes layers can be effectively suppressed,their electrochemical performance will be enhanced.Structural optimization of MXenes and composite doping of MXenes with other materials are two strategies with significant effects.This review summarizes recent advances in MXene synthesis,fundamental properties,and composite materials,focusing on the latest electrochemical performance of MXene-based electrodes/devices,and puts forward the challenges and new opportunities that MXenes face in this emerging energy storage field.

关键词： composite materials MXene MXene-based supercapacitors

An Ultra-microporous Carbon Material Boosting Integrated Capacitance for Cellulose-Based supercapacitors

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Nano-Micro Letters 2020年第5期12卷 78-94页

作者： Chenfeng Ding Tianyi Liu Xiaodong Yan Lingbo Huang Seungkon Ryu Jinle Lan Yunhua Yu Wei?Hong Zhong Xiaoping Yang State Key Laboratory of Organic-Inorganic Composites Beijing University of Chemical TechnologyBeijing 100029People’s Republic of China Key Laboratory of Synthetic and Biological Colloids Ministry of EducationSchool of Chemical and Material EngineeringJiangnan UniversityWuxi 214122JiangsuPeople’s Republic of China Institute of Carbon Tech. Jeonju UniversityJeonju 55069South Korea School of Mechanical and Material Engineering Washington State UniversityPullman 99163USA

A breakthrough in advancing power density and stability of carbon-based supercapacitors is trapped by inefficient pore structures of electrode materials.Herein,an ultramicroporous carbon with ultrahigh integrated capacitance fabricated via one-step carbonization/activation of dense bacterial cellulose(BC)precursor followed by nitrogen/sulfur dual doping is reported.The microporous carbon possesses highly concentrated micropores(~2 nm)and a considerable amount of sub-micropores(<1 nm).The unique porous structure provides high specific surface area(1554 m^2 g^-1)and packing density(1.18 g cm^-3).The synergistic effects from the particular porous structure and optimal doping effectively enhance ion storage and ion/electron transport.As a result,the remarkable specific capacitances,including ultrahigh gravimetric and volumetric capacitances(430 F g^-1 and 507 F cm^-3 at 0.5 A g^-1),and excellent cycling and rate stability even at a high current density of 10 A g^-1(327 F g^-1 and 385 F cm^-3)are realized.Via compositing the porous carbon and BC skeleton,a robust all-solid-state cellulose-based supercapacitor presents super high areal energy density(~0.77 mWh cm^-2),volumetric energy density(~17.8 W L^-1),and excellent cyclic stability.

关键词： Integrated capacitance Bacterial cellulose Microporous carbon Heteroatom doping supercapacitors

A Molecular Foaming and Activation Strategy to Porous N-Doped Carbon Foams for supercapacitors and CO2 Capture

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Nano-Micro Letters 2020年第5期12卷 1-19页

作者： Mengyuan Zhou Yaqian Lin Huayao Xia Xiangru Wei Yan Yao Xiaoning Wang Zhangxiong Wu Particle Engineering Laboratory(CPCIA)and Suzhou Key Laboratory of Green Chemical Engineering School of Chemical and Environmental EngineeringCollege of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhou 2151213JiangsuPeople’s Republic of China

Hierarchically porous carbon materials are promising for energy storage,separation and catalysis.It is desirable but fairly challenging to simultaneously create ultrahigh surface areas,large pore volumes and high N contents in these materials.Herein,we demonstrate a facile acid-base enabled in situ molecular foaming and activation strategy for the synthesis of hierarchically macro-/meso-/microporous N-doped carbon foams(HPNCFs).The key design for the synthesis is the selection of histidine(His)and potassium bicarbonate(PBC)to allow the formation of 3D foam structures by in situ foaming,the PBC/His acid-base reaction to enable a molecular mixing and subsequent a uniform chemical activation,and the stable imidazole moiety in His to sustain high N contents after carbonization.The formation mechanism of the HPNCFs is studied in detail.The prepared HPNCFs possess 3D macroporous frameworks with thin well-graphitized carbon walls,ultrahigh surface areas(up to 3200 m^2 g^-1),large pore volumes(up to 2.0 cm^3 g^-1),high micropore volumes(up to 0.67 cm^3 g^-1),narrowly distributed micropores and mesopores and high N contents(up to 14.6 wt%)with pyrrolic N as the predominant N site.The HPNCFs are promising for supercapacitors with high specific capacitances(185-240 F g^-1),good rate capability and excellent stability.They are also excellent for CO2 capture with a high adsorption capacity(~4.13 mmol g^-1),a large isosteric heat of adsorption(26.5 kJ mol^-1)and an excellent CO2/N2 selectivity(~24).

关键词： Porous carbon foams Hierarchical pore structure Nitrogen doping supercapacitors CO2 capture

Recent Developments of Transition Metal Compounds-Carbon Hybrid Electrodes for High Energy/Power supercapacitors

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Nano-Micro Letters 2021年第8期13卷 231-262页

作者： Kang Ren Zheng Liu Tong Wei Zhuangjun Fan State Key Laboratory of Heavy Oil Processing School of Materials Science and EngineeringChina University of Petroleum(East China)Qingdao 266580People’s Republic of China

Due to their rapid power delivery,fast charging,and long cycle life,supercapacitors have become an important energy storage technology recently.However,to meet the continuously increasing demands in the fields of portable electronics,transportation,and future robotic technologies,supercapacitors with higher energy densities without sacrificing high power densities and cycle stabilities are still challenged.Transition metal compounds(TMCs)possessing high theoretical capacitance are always used as electrode materials to improve the energy densities of supercapacitors.However,the power densities and cycle lives of such TMCs-based electrodes are still inferior due to their low intrinsic conductivity and large volume expansion during the charge/discharge process,which greatly impede their large-scale applications.Most recently,the ideal integrating of TMCs and conductive carbon skeletons is considered as an effective solution to solve the above challenges.Herein,we summarize the recent developments of TMCs/carbon hybrid electrodes which exhibit both high energy/power densities from the aspects of structural design strategies,including conductive carbon skeleton,interface engineering,and electronic structure.Furthermore,the remaining challenges and future perspectives are also highlighted so as to provide strategies for the high energy/power TMCs/carbon-based supercapacitors.

关键词： TMCs/carbon hybrid supercapacitors High power density Carbon skeleton Interfacial engineering Transition metal electronic structure

K2Ti6O13 Nanoparticle-Loaded Porous rGO Crumples for supercapacitors

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Nano-Micro Letters 2020年第1期12卷 115-123页

作者： Chongmin Lee Sun Kyung Kim Hankwon Chang Hee Dong Jang Department of Nanomaterials Science and Engineering University of Science and TechnologyYuseong‑guDaejeon 34113Republic of Korea Resources Utilization Research Center Korea Institute of Geoscience and Mineral ResourcesYuseong‑guDaejeon 34132Republic of Korea

One-dimensional alkali metal titanates containing potassium,sodium,and lithium are of great concern owing to their high ion mobility and high specific surface area.When those titanates are combined with conductive materials such as graphene,carbon nanotube,and carbon nanofiber,they are able to be employed as efficient electrode materials for supercapacitors.Potassium hexa-titanate(K2Ti6O13,KTO),in particular,has shown superior electrochemical properties compared to other alkali metal titanates because of their large lattice parameters induced by the large radius of potassium ions.Here,we present porous rGO crumples(PGC)decorated with KTO nanoparticles(NPs)for application to supercapacitors.The KTO NP/PGC composites were synthesized by aerosol spray pyrolysis and post-heat treatment.KTO NPs less than 10 nm in diameter were loaded onto PGCs ranging from 3 to 5μm.Enhanced porous structure of the composites was obtained by the activation of rGO by adding an excessive amount of KOH to the composites.The KTO NP/PGC composite electrodes fabricated at the GO/KOH/TiO2 ratio of 1:3:0.25 showed the highest performance(275 F g−1)in capacitance with different KOH concentrations and cycling stability(83%)after 2000 cycles at a current density of 1 A g−1.

关键词： Potassium hexa-titanate Porous graphene crumples supercapacitors

3D Carbon Frameworks for Ultrafast Charge/Discharge Rate supercapacitors with High Energy‑Power Density

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Nano-Micro Letters 2021年第1期13卷 112-122页

作者： Changyu Leng Zongbin Zhao Yinzhou Song Lulu Sun Zhuangjun Fan Yongzhen Yang Xuguang Liu Xuzhen Wang Jieshan Qiu State Key Lab of Fine Chemicals School of Chemical EngineeringLiaoning Key Lab for Energy Materials and Chemical EngineeringDalian University of TechnologyDalian 116024People’s Republic of China College of Chemical Engineering Beijing University of Chemical TechnologyBeijing 100029People’s Republic of China School of Materials Science and Engineering China University of PetroleumQingdao 266580ShandongPeople’s Republic of China Key Lab of Interface Science and Engineering in Advanced Materials Ministry of EducationTaiyuan University of TechnologyTaiyuan 030024People’s Republic of China

Carbon-based electric double layer capacitors(EDLCs)hold tremendous potentials due to their high-power performance and excellent cycle stability.However,the practical use of EDLCs is limited by the low energy density in aqueous electrolyte and sluggish diffusion kinetics in organic or/and ionic liquids electrolyte.Herein,3D carbon frameworks(3DCFs)constructed by interconnected nanocages(10-20 nm)with an ultrathin wall of ca.2 nm have been fabricated,which possess high specific surface area,hierarchical porosity and good conductive network.After deoxidization,the deoxidized 3DCF(3DCFDO)exhibits a record low IR drop of 0.064 V at 100 A g^−1 and ultrafast charge/discharge rate up to 10 V s^−1.The related device can be charged up to 77.4%of its maximum capacitance in 0.65 s at 100 A g^−1 in 6 M KOH.It has been found that the 3DCF-DO has a great affinity to EMIMBF4,resulting in a high specific capacitance of 174 F g^−1 at 1 A g^−1,and a high energy density of 34 Wh kg^−1 at an ultrahigh power density of 150 kW kg^−1 at 4 V after a fast charge in 1.11 s.This work provides a facile fabrication of novel 3D carbon frameworks for supercapacitors with ultrafast charge/discharge rate and high energy-power density.

关键词： 3D carbon frameworks Nanocages Ultrafast charge/discharge rate High energy-power density supercapacitors

A Hybrid Electrode of Co_3O_4@PPy Core/Shell Nanosheet Arrays for High-Performance supercapacitors

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Nano-Micro Letters 2016年第2期8卷 143-150页

作者： Xiaojun Yang Kaibing Xu Rujia Zou Junqing Hu State Key Laboratory for Modification of Chemical Fibers and Polymer Materials College of Materials Science and Engineering Donghua University

Herein, combining solverthermal route and electrodeposition, we grew unique hybrid nanosheet arrays consisting of Co_3O_4 nanosheet as a core, PPy as a shell. Benefiting from the PPy as conducting polymer improving an electron transport rate as well as synergistic effects from such a core/shell structure, a hybrid electrode made of the Co_3O_4@PPy core/shell nanosheet arrays exhibits a large areal capacitance of 2.11 F cm-2at the current density of 2 m A cm^(-2), a *4-fold enhancement compared with the pristine Co_3O_4electrode; furthermore, this hybrid electrode also displays good rate capability(*65 % retention of the initial capacitance from 2 to 20 m A cm^(-2)) and superior cycling performance(*85.5 % capacitance retention after 5000 cycles). In addition, the equivalent series resistance value of the Co_3O_4@PPy hybrid electrode(0.238 X) is significantly lower than that of the pristine Co_3O_4electrode(0.319 X). These results imply that the Co_3O_4@PPy hybrid composites have a potential for fabricating next-generation energy storage and conversion devices.

关键词： Co3O4@PPy Core/shell nanosheet arrays supercapacitors

3D Hierarchical Co–Al Layered Double Hydroxides with Long-Term Stabilities and High Rate Performances in supercapacitors

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Nano-Micro Letters 2017年第2期9卷 88-96页

作者： Jiantao Zai Yuanyuan Liu Xiaomin Li Zi-feng Ma Rongrong Qi Xuefeng Qian Shanghai Electrochemical Energy Devices Research Center School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix CompositesShanghai Jiao Tong UniversityShanghai 200240People’s Republic of China

Three-dimensional(3D) flower-like Co–Al layered double hydroxide(Co–Al-LDH) architectures composed of atomically thin nanosheets were successfully synthesized via a hydrothermal method in a mixed solvent of water and butyl alcohol. Owing to the unique hierarchical structure and modification by butyl alcohol, the electrochemical stability and the charge/mass transport of the Co–Al-LDHs was improved. When used in supercapacitors, the obtained Co–Al-LDHs deliver a high specific capacitance of 838 Fg^(-1) at a current density of 1 Ag^(-1)and excellent rate performance(753 Fg^(-1) at 30 Ag^(-1) and 677 Fg^(-1) at 100 Ag^(-1)), as well as excellent cycling stability with 95% retention of the initial capacitance even after 20,000 cycles at a current density of 5 Ag^(-1). This work provides a promising alternative strategy to enhance the electrochemical properties of supercapacitors.

关键词： Co–Al layered double hydroxides(Co–Al-LDHs) Nanosheets 3D hierarchical architectures Butyl alcohol supercapacitors

A Facile and Template-Free One-Pot Synthesis of Mn_3O_4 Nanostructures as Electrochemical supercapacitors

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Nano-Micro Letters 2016年第2期8卷 165-173页

作者： Zhenjun Qi Adnan Younis Dewei Chu Sean Li School of Materials Science and Engineering University of New South Wales

In this paper, we report an effective, simple, and cost-effective strategy of electrochemical deposition to prepare hausmannite Mn_3O_4 thin films for the applications of supercapacitors. Various precursor concentrations and deposition durations were manipulated to tailor the surface morphologies of Mn_3O_4 nanostructures and to optimize their electrochemical performances. The Mn_3O_4 samples prepared at 0.05 M Mn(NO3)2solution for 30 min delivered a large gravimetric specific capacitance of 210 F g-1at a current density of 0.5 A g-1, and a good rate capability over other samples. This superior electrochemical performance may be attributed to the improved electrode conductivity with increased accessible area for electrolytes ions. Furthermore, a nanocomposite film based on Mn_3O_4/carbon foam was fabricated by utilizing the developed optimized conditions. The Mn_3O_4/carbon foam films exhibit an excellent specific capacitance with negligible degradation in retaining specific capacitance values up to 4000 cycles. These findings could further broaden the applications of hausmannite Mn_3O_4 in electrochemical energy storage electrodes.

关键词： Electrochemical deposition supercapacitors Charge storage