Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)...Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)O dis-solved in N,N-dimethylformamide,and were converted into Fe-Co embedded in N-doped porous carbon polyhedra by pyrolysis in a nitrogen atmosphere.During pyrolysis,the or-ganic ligands transformed into N-doped porous carbon which improved their structural stability and also their electrical contact with other materials.The Fe and Co are tightly bound together because of their encapsulation by the carbon nitride and are well dispersed in the carbon matrix,and improve the material’s conductivity and stability and provide additional capacity.When used as the anode for lithium-ion batteries,the material gives an initial capacity of up to 2230.7 mAh g^(-1)and a reversible capa-city of 1146.3 mAh g^(-1)is retained after 500 cycles at a current density of 0.5 A g^(-1),making it an excellent candidate for this purpose.展开更多
Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic framew...Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.展开更多
Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and act...Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and activated MIL-101(Fe))were synthesized and added to PEO-based solid composite electrolytes(SCEs).Furthermore,the role of the—NH_(2)groups and open metal sites(OMSs)were both examined.Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations.At last,we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO,Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries.This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.展开更多
All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance ...All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4)full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.展开更多
Lithium-sulfur(Li-S)batteries are regarded as one of the promising candidates for the next-generation energy storage system owing to their high capacity and energy density.However,the durable operation for the batteri...Lithium-sulfur(Li-S)batteries are regarded as one of the promising candidates for the next-generation energy storage system owing to their high capacity and energy density.However,the durable operation for the batteries is blocked by the shuttle behavior of soluble lithium polysulfides and the sluggish kinetics in the redox process.Here,VN nanoparticles on nitrogen-doped graphene(VN/NG)composite is synthesized by simple calcining method to modify the separators,which can not only chemically trap polysulfides,but also catalyze the conversion reaction between the polysulfides and the insoluble Li2S during the charge/discharge process.The catalytic effects of VN/NG are verified by the calculated activation energy(E_(a)),which is smaller than the counterpart with NG toward both directions of redox.Because of the synergistic adsorption-catalysis of VN/NG,the cells with VN/NG-modified separators deliver a superior rate performance(791 mAh g^(-1) at 5C)and cycling stability(863 mAh g^(-1) after 300 cycles with a low decaying rate of 0.068%per loop at 1C).This work provides a simple preparation strategy and fundamental understanding of the bifunctional catalyst for high-performance Li-S batteries.展开更多
Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)co...Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.展开更多
For all-solid-state lithium batteries(ASSLBs),polymer-blended solid composite electrolytes(SCEs)have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the...For all-solid-state lithium batteries(ASSLBs),polymer-blended solid composite electrolytes(SCEs)have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the growth of lithium dendrites.In this work,SCEs based on PVDF-HFP/PMMA matrix containing MOFs(NH2-MIL-53(Al))and LiTFSI were designed and synthesized employing an easy solution casting method.The synthesized samples were examined by XRD,SEM,EDS,and electrochemical tests.It was found that MPP-2 SCE not only has excellent ionic conductivity at 60℃of 5.54×10^(−4)S cm^(−1),but also exhibits superior interfacial compatibility in Li||Li symmetric batteries,which can constantly cycle for about 800 h at 0.1 mA cm^(−2)with no short-circuiting.The assembled Li|MPP-2|LiFePO4 cell exhibited a first discharge specific capacity of up to 157.1 mAh g^(−1)at 60℃and 0.2 C.This work may help to further advance the progress of ASSLBs in the future.展开更多
文摘Metal-organic frameworks(MOFs)are import-ant as possible energy storage materials.Nitrogen-doped iron-cobalt MOFs were synthesized by a one-pot solvo-thermal method using CoCl_(3)·6H_(2)O and FeCl_(3)·6H_(2)O dis-solved in N,N-dimethylformamide,and were converted into Fe-Co embedded in N-doped porous carbon polyhedra by pyrolysis in a nitrogen atmosphere.During pyrolysis,the or-ganic ligands transformed into N-doped porous carbon which improved their structural stability and also their electrical contact with other materials.The Fe and Co are tightly bound together because of their encapsulation by the carbon nitride and are well dispersed in the carbon matrix,and improve the material’s conductivity and stability and provide additional capacity.When used as the anode for lithium-ion batteries,the material gives an initial capacity of up to 2230.7 mAh g^(-1)and a reversible capa-city of 1146.3 mAh g^(-1)is retained after 500 cycles at a current density of 0.5 A g^(-1),making it an excellent candidate for this purpose.
基金financially supported by National Natural Science Foundation of China(No.21701083)Zhenjiang Key Laboratory of Marine Power Equipment Performance(SS2018006)+1 种基金The Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX19_0612)Project of Jiangsu University(High-Tech Ship)Collaborative Innovation Center(2019,1174871801-11).
文摘Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.
基金financially supported by National Natural Science Foundation of China(21701083)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_3137)。
文摘Metal-organic frameworks(MOFs)are becoming more and more popular as the fillers in polymer electrolytes in recent years.In this study,a series of MOFs(NH_(2)-MIL-101(Fe),MIL-101(Fe),activated NH_(2)-MIL-101(Fe)and activated MIL-101(Fe))were synthesized and added to PEO-based solid composite electrolytes(SCEs).Furthermore,the role of the—NH_(2)groups and open metal sites(OMSs)were both examined.Different ratios of MOFs vs polymers were also studied by the electrochemical characterizations.At last,we successfully designed a novel solid composite electrolyte containing activated NH_(2)-MIL-101(Fe),PEO,Li TFSI and PVDF for the high-performance all-solid-state lithium-metal batteries.This work might provide new insight to understand the interactions between polymers and functional groups or OMSs of MOFs better.
基金financially supported by National Natural Science Foundation of China(No.21701083)。
文摘All solid-state electrolytes have the advantages of good mechanical and thermal properties for safer energy storage,but their energy density has been limited by low ionic conductivity and large interfacial resistance caused by the poor Li~+transport kinetics due to the solid-solid contacts between the electrodes and the solid-state electrolytes.Herein,a novel gel polymer electrolyte(UPP-5)composed of ionic liquid incorporated metal-organic frameworks nanoparticles(IL@MOFs)is designed,it exhibits satisfying electrochemical performances,consisting of an excellent electrochemical stability window(5.5 V)and an improved Li^(+)transference number of 0.52.Moreover,the Li/UPP-5/LiFePO_(4)full cells present an ultra-stable cycling performance at 0.2C for over 100 cycles almost without any decay in capacities.This study might provide new insight to create an effective Li^(+)conductive network for the development of all-solid-state lithium-ion batteries.
基金supported by the National Natural Science Foun-dation of China(21706171,21606158,21978193 and U1810204)the Natural Science Foundation of Shanxi Province(201805D131004 and 201901D211064)。
文摘Lithium-sulfur(Li-S)batteries are regarded as one of the promising candidates for the next-generation energy storage system owing to their high capacity and energy density.However,the durable operation for the batteries is blocked by the shuttle behavior of soluble lithium polysulfides and the sluggish kinetics in the redox process.Here,VN nanoparticles on nitrogen-doped graphene(VN/NG)composite is synthesized by simple calcining method to modify the separators,which can not only chemically trap polysulfides,but also catalyze the conversion reaction between the polysulfides and the insoluble Li2S during the charge/discharge process.The catalytic effects of VN/NG are verified by the calculated activation energy(E_(a)),which is smaller than the counterpart with NG toward both directions of redox.Because of the synergistic adsorption-catalysis of VN/NG,the cells with VN/NG-modified separators deliver a superior rate performance(791 mAh g^(-1) at 5C)and cycling stability(863 mAh g^(-1) after 300 cycles with a low decaying rate of 0.068%per loop at 1C).This work provides a simple preparation strategy and fundamental understanding of the bifunctional catalyst for high-performance Li-S batteries.
基金financially supported by National Natural Science Foundation of China(21701083)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_3137)。
文摘Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.
基金supported by National Natural Science Foundation of China(grant Nos.21701083,22179054)The Ministry of Science and Technology of the People's Republic of China(grant No.G2023014022L)Jiangsu Provincial Key Research and Development Program(grant No.BZ2023010).
文摘For all-solid-state lithium batteries(ASSLBs),polymer-blended solid composite electrolytes(SCEs)have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the growth of lithium dendrites.In this work,SCEs based on PVDF-HFP/PMMA matrix containing MOFs(NH2-MIL-53(Al))and LiTFSI were designed and synthesized employing an easy solution casting method.The synthesized samples were examined by XRD,SEM,EDS,and electrochemical tests.It was found that MPP-2 SCE not only has excellent ionic conductivity at 60℃of 5.54×10^(−4)S cm^(−1),but also exhibits superior interfacial compatibility in Li||Li symmetric batteries,which can constantly cycle for about 800 h at 0.1 mA cm^(−2)with no short-circuiting.The assembled Li|MPP-2|LiFePO4 cell exhibited a first discharge specific capacity of up to 157.1 mAh g^(−1)at 60℃and 0.2 C.This work may help to further advance the progress of ASSLBs in the future.
