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Coupling Sb_(2)WO_(6)microflowers and conductive polypyrrole for efficient potassium storage by enhanced conductivity and K^(+) diffusivity

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Journal of Energy Chemistry 2024年第2期89卷 250-258,I0007页

作者： Ruiqi Tian Hehe Zhang Zeyu Yuan Yuehua Man Jianlu Sun Jianchun Bao Ming-Sheng Wang xiaosi zhou School of Chemistry and Materials Science Nanjing Normal UniversityNanjing 210023JiangsuChina State Key Lab of Physical Chemistry of Solid Surfaces College of MaterialsXiamen UniversityXiamen 361005FujianChina

Although metal oxide compounds are considered as desirable anode materials for potassium-ion batteries(PIBs)due to their high theoretical capacity,the large volume variation remains a key issue in realizing metal oxide anodes with long cycle life and excellent rate property.In this study,polypyrroleencapsulated Sb_(2)WO_(6)(denoted Sb_(2)WO_(6)@PPy)microflowers are synthesized by a one-step hydrothermal method followed by in-situ polymerization and coating by pyrrole.Leveraging the nanosheet-stacked Sb_(2)WO_(6)microflower structure,the improved electronic conductivity,and the architectural protection offered by the PPy coating,Sb_(2)WO_(6)@PPy exhibits boosted potassium storage properties,thereby demonstrating an outstanding rate property of 110.3 m A h g^(-1)at 5 A g^(-1)and delivering a long-period cycling stability with a reversible capacity of 197.2 m A h g^(-1)after 500 cycles at 1 A g^(-1).In addition,the conversion and alloying processes of Sb_(2)WO_(6)@PPy in PIBs with the generation of intermediates,K_(2)WO_(4)and K_(3)Sb,is determined by X-ray photoelectron spectroscopy,transmission electron microscopy,and exsitu X-ray diffraction during potassiation/depotassiation.Density functional theory calculations demonstrate that the robust coupling between PPy and Sb_(2)WO_(6)endues it with a much stronger total density of states and a built-in electric field,thereby increasing the electronic conductivity,and thus effectively reduces the K^(+)diffusion barrier.

关键词： Sb_(2)WO_(6) Polypyrrole coating Anode Potassium-ion battery In-situ TEM observation

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Templated synthesis of imine-based covalent organic framework hollow nanospheres for stable potassium-ion batteries

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Chinese Chemical Letters 2023年第7期34卷 274-278页

作者： Jianlu Sun Ruiqi Tian Yuehua Man Yating Fei xiaosi zhou School of Chemistry and Materials Science Nanjing Normal UniversityNanjing 210023China

Covalent organic frameworks(COFs), as highly tunable porous crystalline materials, have promising applications in potassium-ion batteries(PIBs) due to their abundant charge carrier transport channels and excellent structural stability. However, the excessive stacking of interlayer electron clouds makes it difficult to expose internal active sites. Strategies to design functional COFs with controllable morphology and copious active sites are promising but still challenging. Herein, by utilizing the condensation between1,3,5-triformylbenzene(TFB) and p-phenylenediamine(PPD) and using amino-modified SiO_(2) nanospheres as templates, we synthesize core-shell NH_(2)-SiO_(2)@TP-COF. Through NaOH etching of NH_(2)-SiO_(2)@TP-COF, we obtain imine-based TP-COF hollow nanospheres, which shows excellent potassium storage performance when applied to the anode for PIBs. Ex-situ analysis and density functional theory calculations reveal that C=N groups and benzenes are active sites for K^(+) storage.

关键词： Potassium ion batteries Anode Covalent organic framework Templated synthesis Hollow nanospheres

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KVPO_(4)F/carbon nanocomposite with highly accessible active sites and robust chemical bonds for advanced potassium-ion batteries

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Green Energy & Environment 2023年第5期8卷 1469-1478页

作者： Jianzhi Xu Liping Duan Jiaying Liao Haowei Tang Jun Lin xiaosi zhou School of Chemistry and Materials Science Nanjing Normal UniversityNanjing210023China

KVPO_(4)F(KVPF)has been extensively investigated as the potential cathode material for potassium-ion batteries(PIBs)owing to its high theoretical capacity,superior operating voltage,and three-dimensional Kt conduction pathway.Nevertheless,the electrochemical behavior of KVPF is limited by the inherent poor electronic conductivity of the phosphate framework and unstable electrode/electrolyte interface.To address the above issues,this work proposes an infiltration-calcination method to confine the in-situ grown KVPF into the mesoporous carbon CMK-3(denoted KVPF@CMK-3).The assembled KVPF@CMK-3 nanocomposite features three-dimensional interconnected carbon channels,which not only offer abundant active sites and significantly accelerate K t/electron transport,but also prevent the growth of KVPF nanoparticle agglomerates,hence stabilizing the structure of the material.Additionally,V–F–C bonds are created at the interface of KVPF and CMK-3,which reduce the loss of F and stabilize the electrode interface.Thus,when tested as a cathode material for PIBs,the KVPF@CMK-3 nanocomposite delivers superior reversible capacitiy(103.2 mAh g^(-1) at 0.2 C),outstanding rate performance(90.1 mAh g^(-1) at 20 C),and steady cycling performance(92.2 mAh g^(-1) at 10 C and with the retention of 88.2%after 500 cycles).Moreover,its potassium storage mechanism is further examined by ex-situ XRD and ex-situ XPS techniques.The above synthetic strategy demonstrates the potential of KVPF@CMK-3 to be applied as the cathode for PIBs.

关键词： Potassium-ion batteries Cathode KVPO_(4)F CMK-3 V–F–C bond

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Sn_(4)P_(3)nanoparticles confined in multilayer graphene sheets as a high-performance anode material for potassium-ion batteries

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Journal of Energy Chemistry 2022年第3期31卷 413-421,I0011页

作者： Yichen Du Zuyue Yi Bingbing Chen Jingyi Xu Zhuangzhuang Zhang Jianchun Bao xiaosi zhou Jiangsu Key Laboratory of New Power Batteries Jiangsu Collaborative Innovation Center of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing 210023JiangsuChina

Phosphorus-based anodes are highly promising for potassium-ion batteries(PIBs)because of their large theoretical capacities.Nevertheless,the inferior potassium storage properties caused by the poor electronic conductivity,easy self-aggregation,and huge volumetric changes upon cycling process restrain their practical applications.Now we impregnate Sn_(4)P_(3)nanoparticles within multilayer graphene sheets(Sn_(4)P_(3)/MGS)as the anode material for PIBs,greatly improving its potassium storage performance.Specifically,the graphene sheets can efficiently suppress the aggregation of Sn_(4)P_(3)nanoparticles,enhance the electronic conductivity,and sustain the structural integrity.In addition,plenty of Sn_(4)P_(3)nanoparticles impregnated in MGS offer a large accessible area for the electrolyte,which decreases the diffusion distance for K^(+)and electrons upon K^(+)insertion/extraction,resulting in an improved rate capability.Consequently,the optimized Sn_(4)P_(3)/MGS containing 80 wt%Sn_(4)P_(3)(Sn_(4)P_(3)/MGS-80)exhibits a high reversible capacity of 378.2 and 260.2 m Ah g;at 0.1 and 1 A g^(-1),respectively,and still delivers a large capacity retention of 76.6%after the 1000th cycle at 0.5 A g^(-1).

关键词： Sn4P3 Multilayer graphene sheets Ball milling Potassium-ion batteries Anode

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Facile synthesis of KVPO_(4)F/reduced graphene oxide hybrid as a high-performance cathode material for potassium-ion batteries

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Journal of Energy Chemistry 2022年第5期31卷 284-292页

作者： Jianzhi Xu Jiaying Liao Yifan Xu Jianbo Li Chuannan Zhu Jun Lin xiaosi zhou Jiangsu Key Laboratory of New Power Batteries Jiangsu Collaborative Innovation Center of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing 210023JiangsuChina

Potassium-ion batteries(PIBs) as a substitute for lithium-ion batteries have aroused widespread attention and have been rapidly developed. In the positive electrode materials, polyanionic compound has a high working voltage and large reversible capacity on account of its distinct framework and the strong inducing effect of the anionic group. Herein, a KVPO_(4)F/reduced graphene oxide(KVPF/r GO) hybrid was fabricated via a simple multi-step approach as the polyanionic cathode material for PIBs. Profiting from the small size of KVPF nanoparticles and their uniform distribution in the r GO framework, the assynthesized KVPF/r GO hybrid manifests a large discharge capacity of 103.2 mAh g^(-1) with an outstanding energy density of 436.5 Wh kg^(-1). Through r GO decoration, the hybrid also demonstrates remarkable rate and cycling properties. By employing ex-situ X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) techniques, the potassium storage mechanism of KVPF was clearly revealed. The facile preparation procedure and superior properties endow it great application prospects in large-scale energy storage.

关键词： KVPO_(4)F Potassium-ion battery Cathode Reduced graphene oxide Ex-situ XRD

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Synthesis of multicore-shell FeS_(2)@C nanocapsules for stable potassiumion batteries

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Journal of Energy Chemistry 2022年第10期31卷 126-132,I0004页

作者： Zhuangzhuang Zhang Liping Duan Yifan Xu Chuanfeng Zhao Jianchun Bao Jian Shen xiaosi zhou Jiangsu Key Laboratory of New Power Batteries Jiangsu Collaborative Innovation Center of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing 210023JiangsuChina

Transition-metal sulfides are widely used as anodes for potassium-ion batteries(PIBs) due to their low cost and high theoretical capacity.The practical application of such materials,however,is still impeded by their inherent low conductivity and obvious volume change during cycling.Herein,a flexible etchassisted sulfidation strategy is reported.According to the strategy,the multicore-shell(MCS) nanocapsule structure is constructed,and then mesoporous FeS2 nanoparticles are encapsulated in the hollow carbon shell with adjustable interior space.The product,MCS-FeS2@C-20,not only features optimized inner space,but also delivers a large reversible capacity(519 mAh g^(-1) at a current density of 50 mA g^(-1)),good rate capability(107 mAh g^(-1) at a high current density of 5 A g^(-1)) and excellent cycling stability(capacity retention rate of 84.2% over 500 cycles at 0.5 A g^(-1)),making it the promising anode material for PIBs.Notably,potassium-ion full cells(MCS-FeS_(2)@C-20//K_(0.4)CoO_(2)) also show an improved potassium storage performance.

关键词： Potassium-ion battery Anode FeS_(2) Yolk-shell structure Carbon protection

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Coupling Ternary Selenide SnSb_(2)Se_(4) with Graphene Nanosheets for High-Performance Potassium-Ion Batteries

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Energy & Environmental Materials 2023年第4期6卷 280-288页

作者： Ruiqi Tian Liping Duan Yifan Xu Yuehua Man Jianlu Sun Jianchun Bao xiaosi zhou School of Chemistry and Materials Science Nanjing Normal UniversityNanjing 210023China

Although chalcogenide anodes possess higher potassium storage capacity than intercalated-based graphite,their drastic volume change and the irreversible electrochemical reactions still hinder the effective electron/ion transfer during the potassiation/depotassiation process.To solve the above problems,this article proposes the synthesis of a lamellar nanostructure where graphene nanosheets are embedded with SnSb_(2)Se_(4)nanoparticles(SnSb_(2)Se_(4)/GNS).In the product,fine monodisperse SnSb_(2)Se_(4)nanoparticles are coupled with graphene nanosheets to form a porous network framework,which can effectively mitigate the drastic volume changes during electrode reactions and guarantee efficient potassium-ion storage through the synergistic interactions among multiple elements.Various electrochemical analyses prove that SnSb_(2)Se_(4)inherits the advantages of the binary Sb2Se3 and SnSe while avoiding their disadvantages,confirming the synergistic effect of the ternary–chalcogenide system.When tested for potassium storage,the obtained composite delivers a high specific capacity of 368.5 mAh g^(-1)at 100 mA g^(-1)and a stable cycle performance of 265.8 mAh g^(-1)at 500 mA g^(-1)over 500 cycles.Additionally,the potassium iron hexacyanoferrate cathode and the SnSb_(2)Se_(4)/GNS anode are paired to fabricate the potassium-ion full cell,which shows excellent cyclic stability.In conclusion,this strategy employs atomic doping and interface interaction,which provides new insights for the design of high-rate electrode materials.

关键词： anode ex situ XRD potassium-ion battery SnSb_(2)Se_(4) synergistic effect

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Synthesis of yolk-shell Bi_(2)O_(3)@TiO_(2) submicrospheres with enhanced potassium storage

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Science China Chemistry 2022年第9期65卷 1807-1816页

作者： Yifan Xu Hehe Zhang Tangjing Ding Ruiqi Tian Dongmei Sun Ming-Sheng Wang xiaosi zhou Jiangsu Key Laboratory of New Power Batteries Jiangsu Collaborative Innovation Center of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing 210023China State Key Lab of Physical Chemistry of Solid Surfaces College of MaterialsXiamen UniversityXiamen 361005China

Due to their enormous potential for large-scale energy storage,rechargeable potassium-ion batteries have been widely researched and developed.However,the drastic volume change of electrode materials induced by the huge size of potassium ions during cycling remains a challenge for the construction of stable anodes.Herein,we propose a novel weak acid etching strategy to design and fabricate robust yolk-shell spheres with enough internal void space,in which the Bi_(2)O_(3) nanospheres are well confined in the compartments of TiO_(2) submicrospheres(y-Bi_(2)O_(3)@TiO_(2)).In situ transmission electron microscopy(TEM)and ex situ Xray diffraction(XRD)are conducted to elucidate the structural evolution of y-Bi_(2)O_(3)@TiO_(2) and the interaction between K^(+)and Bi_(2)O_(3) during cycling.Thanks to the yolk-shell nanoarchitecture and the superior buffering property of outer TiO_(2) covering,the as-obtained composite shows a high specific capacity of 383.5 mAh g^(−1) at 100 mA g^(−1),a considerable rate capacity of 134.1 mAh g^(−1) at 2 A g^(−1) and a stable cycling performance of 216.8 mAh g^(−1) at 500 mA g^(−1) over 500 cycles when used for potassium storage.Subsequently,the potassium-ion full battery,constructed by pairing y-Bi_(2)O_(3)@TiO_(2) anode with the thermally annealed 3,4,9,10-perylenetetracarboxylic dianhydride(PTCDA)cathode,exhibits an outstanding cycling stability.Hopefully,this carefully-designed strategy can inspire the further development of superior energy storage materials in the near future.

关键词： Bi_(2)O_(3) amorphous TiO_(2) yolk-shell structure anode potassium-ion batteries

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Cocoon-shaped P3-type K0.5Mn0.7Ni0.3O2 as an advanced cathode material for potassium-ion batteries

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Journal of Energy Chemistry 2023年第1期76卷 332-338,I0008页

作者： Liping Duan Jianzhi Xu Yifan Xu Ruiqi Tian Yingying Sun Chuannan Zhu Xiangyin Mo xiaosi zhou Jiangsu Key Laboratory of New Power Batteries Jiangsu Collaborative Innovation Center of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing 210023JiangsuChina

Potassium ion batteries(PIBs)are emerging as potential next-generation energy storage systems on account of their low cost and high theoretical energy density.Nevertheless,they also face challenges of low specific capacity and suboptimal cycling stability.Herein,we synthesize a cocoon-like P3-type K_(0.5)Mn_(0.7)Ni_(0.3)O_(2)(KMNO)cathode material by a self-template method.The KMNO cocoons possess a hierarchical layered architecture composed of nanoparticle stacking,which can accelerate the transport kinetics of potassium ions,mitigate the stress caused by K^(+)intercalation and deintercalation,and improve structural stability.In addition,Ni can not only alleviate the Jahn-Teller distortion and suppress the phase transition to stabilize the structure,but also act as an electrochemically active element,providing the capacity of two electrons from Ni2+to Ni4+.Combining the advantages of structure and nickel substitution,the P3-type KMNO cocoons are used for electrochemical performance testing of PIB cathodes,delivering an excellent rate capability of 57.1 m A h g^(-1)at 500 m A g^(-1)and a remarkable cycling stability of 77.0%over 300 cycles at 100 m A g^(-1).Impressively,the KMNO cocoons//pitch-derived soft carbon assembled full battery exhibits superior electrochemical performance with a reversible capacity of 79.7 m A h g^(-1)at 50 m A g^(-1).Moreover,ex-situ XRD also further reveals a solid solution phase reaction with a volume change of only 1.46%.This work furnishes a suitable approach to fabricating highperformance layered oxide cathodes for PIBs with outstanding cycling stability and rate capability.

关键词： Layered metal oxides Cathode Potassium-ion batteries Cocoons Ex-situ XRD

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Multifunctional cellular carbon foams derived from chitosan toward self-cleaning, thermal insulation, and highly efficient microwave absorption properties

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Nano Research 2024年第3期17卷 927-938页

作者： Beibei Zhan Yanling Hao xiaosi Qi Yunpeng Qu Junfei Ding Jing-liang Yang Xiu Gong Yanli Chen Qiong Peng Wei Zhong College of Physics Guizhou Province Key Laboratory for Photoelectrics Technology and ApplicationGuizhou UniversityGuiyang 550025China Minzu Normal University of Xingyi Xingyi 562400China National Laboratory of Solid State Microstructures and Jiangsu Provincial Laboratory for NanoTechnology Nanjing UniversityNanjing 210093China

To adapt the practical demand,designing and constructing the multifunctional microwave absorbers(MAs)is the key future direction of research and development.However,effective integrating the multiple functions into a single material remains a huge challenge.Herein,cellular carbon foams(CCFs)with different porous structures were elaborately designed and fabricated in high efficiency through a facile continuous freeze-drying and carbonization processes using a sustainable biomass chitosan as the precursor.The obtained results revealed that the thermal treated temperature and g-C_(3)N_(4) amount played a great impact on the carbonization degrees,pore sizes,and morphologies of CCFs,which led to their tunable electromagnetic(EM)parameters,improved conduction loss,and polarization loss abilities.Owing to the special cellular structure,the designed CCFs samples simultaneously displayed the strong absorption capabilities,broad absorption bandwidths,and thin matching thicknesses.Meanwhile,the as-prepared CCFs exhibited the strong hydrophobicity and good thermal insulation,endowing its attractive functions of self-cleaning and thermal insulation.Therefore,our findings not only presented a facile approach to produce different porous structures of CCFs,but also provided an effective strategy to develop multifunctional high-performance MAs on basis of three-dimensional CCFs.

关键词： multifunctional microwave absorbers carbon foams cellular structure self-cleaning thermal insulation

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