Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and...Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.展开更多
A detailed computational investigation,based on density functional theory,of the interaction of polyani-line(PANI)and graphene nanoribbons(GNRs)with SrTiO_(3) is presented.The adsorption of PANI in var-ious oxidation ...A detailed computational investigation,based on density functional theory,of the interaction of polyani-line(PANI)and graphene nanoribbons(GNRs)with SrTiO_(3) is presented.The adsorption of PANI in var-ious oxidation states and co-adsorption with GNRs is found to be thermodynamically favourable.Ad-sorbed PANI introduces N and C 2p states into the SrTiO_(3) bandgap,while co-adsorption of PANI and GNRs leads to a bridging of the gap and semi-metallic behaviour,thus rendering the electrical properties highly sensitive to the loading of the GNRs/PANI in the composites.Modelling the lattice dynamics of the composites predicts a 68-88%reduction in the lattice thermal conductivity due to reduced phonon group velocities.Taken together,these findings provide insight into the growing number of experimental studies highlighting the enhanced thermoelectric performance of oxide-polymer composites and indicate co-adsorption with graphene as a facile direction for future research.展开更多
Lithium metal is one of the most promising anodes for next-generation batteries due to its high capacity and low reduction potential.However,the notorious Li dendrites can cause the short life span and safety issues,h...Lithium metal is one of the most promising anodes for next-generation batteries due to its high capacity and low reduction potential.However,the notorious Li dendrites can cause the short life span and safety issues,hindering the extensive application of lithium batteries.Herein,Li_(7)La_(3)Zr_(2)O_(12)(LLZO)ceramics are integrated into polyethylene oxide(PEO)to construct a facile polymer/inorganic composite solid-state electrolyte(CSSE)to inhibit the growth of Li dendrites and widen the electrochemical stability window.Given the feasibility of our strategy,the designed PEO-LLZO-LiTFSI composite solid-state electrolyte(PLLCSSE)exhibits an outstanding cycling property of 134.2 mAh g^(-1) after 500 cycles and the Coulombic efficiency of 99.1%after 1000 cycles at 1 C in LiFePO_(4)-Li cell.When cooperated with LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)cathode,the PLL-CSSE renders a capacity retention of 82.4%after 200 cycles at 0.2 C.More importantly,the uniform dispersion of LLZO in PEO matrix is tentative tested via Raman and FT-IR spectra and should be responsible for the improved electrochemical performance.The same conclusion can be drawn from the interface investigation after cycling.This work presents an intriguing solid-state electrolyte with high electrochemical performance,which will boost the development of all-solid-state lithium batteries with high energy density.展开更多
There are some critical issues hindering the practical applications of aqueous zinc-ion batteries(zIBs),although they possess high safety and low cost as one of promising energy storge devices,such as the Zn dendrite ...There are some critical issues hindering the practical applications of aqueous zinc-ion batteries(zIBs),although they possess high safety and low cost as one of promising energy storge devices,such as the Zn dendrite growth and the by-product of Zn_(4)SO_(4)(OH)_(6)-xH_(2)O(ZHS)resulted from some side reactions in a mild electrolyte.Herein,a compact and self-repairing solid electrolyte interface(SEl)film,as labeled the PVDF-Zn(TFSI)_(2)-ZHS coating[The PVDF and Zn(TFSI)_(2)are polyvinylidene fluoride and zinc bis(trifluoromethanesulfonyl)imide,respectively],which turns the in-situ generated ZHS into a beneficial ingredient onto the pre-coated PVDF-based composite coating layer containing Zn(TFSI)_(2),was designed and fabricated by a simple doctor blade method.It is shown that the SEl layer can effectively isolate Zn from the electrolyte and homogenize the Zn^(2+)flux,and thus effectively suppress side reactions and dendrites growth.Benefiting from the hybrid SEl layer,a symmetric cell exhibits a high cycling stability over 750h at 2.0 mA/cm^(2)and 2.0 mAh/cm^(2),and meanwhile,a full-cell,coupled with K^(+) pre-intercalationα-MnO_(2)(KMO)cathode,displays excellent rate performance,stable coulombic efficiency and an acceptable cycle life.This work provides a feasible approach for simple and scalable modification of Zn anodes to achieve high performance.展开更多
We describe the sol-gel synthesis of a new family of organic-inorganic hybrid materials, in which various vinyl polymers are covalently bonded to and uniformly distributed in inorganic oxide matrices. The materials ca...We describe the sol-gel synthesis of a new family of organic-inorganic hybrid materials, in which various vinyl polymers are covalently bonded to and uniformly distributed in inorganic oxide matrices. The materials can be tailored to have both good toughness and hardness while maintaining excellent optical transparency. Doping the sol-gel metal oxides with optically active compounds such as D-glucose results in new optical rotatory composite materials. Removal of the dopant compounds from the composites affords mesoporous oxide materials; which represents a new, nonsurfactant-templated route to mesoporous molecular sieves. We have successfully immobilized a series of enzymes and other bioactive agents in mesoporous materials. Catalytical activities of the enzyme encapsulated in mesoporous materials were found to be much higher than those encapsulated in microporous materials.展开更多
Polymer-inorganic(P-Ⅰ) soft-hard heterostructures & heterojunction photocatalysts,featured by large interfacial contact, efficient charge separation, broad light absorption and maximized redox capacity, have rece...Polymer-inorganic(P-Ⅰ) soft-hard heterostructures & heterojunction photocatalysts,featured by large interfacial contact, efficient charge separation, broad light absorption and maximized redox capacity, have received great attention for their applications in energy conversion and environmental remediation. In this minireview, the classification and mechanism of P-Ⅰ heterojunctions, i.e., type-Ⅰ/Ⅱ, p-n, Z-scheme and S-scheme heterojunctions, and their preparation methods are firstly introduced. Next, the photocatalytic applications of P-Ⅰ heterojunctions, including water splitting, environmental remediation and carbon dioxide reduction, are extensively reviewed. Lastly,a brief summary and perspectives on ongoing challenges and opportunities to construct high performance P-Ⅰ soft-hard photocatalysts are intensively highlighted. We envision this review will provide a picture of the state-of-the-art achievements and promote the photocatalytic applications of P-Ⅰ heterostructures in energy conversion and environmental remediation.展开更多
Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybri...Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybrid nanoparticles, 2-(4Chloromethylphenyl) ethyltriethoxysilane (CTES) was immobilized on the surface of silica nanoparticles through condensation reaction of the silanol groups on silica with triethoxysilane group of CTES. Then ATRP of St was initiated by this surface-modified silica nanoparticles bearing benzyl chloride groups, and formed PSt graft chains on the surface of silica nanoparticles. The thickness of the graft chains increased with reaction time. End group analysis confirmed the occurrence of ATRP. Thermal analysis indicated that thermal stabilization of these resulting hybrid nanoparticles also increases with polymerization conversion. The results above show that this 'grafting from' reaction could be used for the preparation of polymer-inorganic hybrid nanoparticles with controlled structure of the polymer's end groups.展开更多
A poly(methyl acrylate)(PMA)/ZnAl layered double hydroxide(ZnAl-LDH) intercalation nanocomposite is synthesized by in situ polymerization of methyl acrylate with ogano-modified ZnAl-LDH(O-ZnAl-LDH). Its structure and ...A poly(methyl acrylate)(PMA)/ZnAl layered double hydroxide(ZnAl-LDH) intercalation nanocomposite is synthesized by in situ polymerization of methyl acrylate with ogano-modified ZnAl-LDH(O-ZnAl-LDH). Its structure and morphology are confirmed by X-ray diffraction(XRD) and transmission electron microscopy(TEM) image. The d 001 of O-ZnAl-LDH is expanded to 2.85 nm after polymerization from 2.63 nm, which indicates the intercalation of PMA chains into the galleries of O-ZnAl-LDH. The (001) diffraction of PMA/ZnAl-LDH nanocomposite is broad due to the exfoliation of some O-ZnAl-LDH layers. The TEM image shows that the most of the layers of O-ZnAl-LDH are stacked with a distance of about 3 nm while some of them are exfoliated and dispersed disorderly in the PMA matrix.展开更多
基金supported by the Jilin Province Science and Technology Department Program(YDZJ202201ZYTS304)the Science and Technology Project of Jilin Provincial Education Department(JJKH20220428KJ)+3 种基金the Jilin Province Science and Technology Department Program(YDZJ202101ZYTS047)the National Natural Science Foundation of China(21905110,21905041,22279045,22102020)the Special foundation of Jilin Province Industrial Technology Research and Development(2019C042)the Fundamental Research Funds for the Central Universities(2412020FZ008)。
文摘Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.
基金NDW thanks the EPSRC DTP competition 2018-19 at the University of Huddersfield for funding(EP/R513234/1)JMS is currently supported by a UKRI Future Leaders Fellowship(MR/T043121/1)+2 种基金previously held a University of Manchester Presidential Fellowship.Calculations were performed on the Orion computing fa-cility and the Violeta HPC at the University of Huddersfield,and the THOMAS and YOUNG facilities at the UK Materials and Molecular Modelling Hub(MMM Hub)which is partially funded by the EPSRC(EP/P020194/1 and EP/T022213/1)via our membership of the UK’s HEC Materials Chemistry Consortium(MCC),which is also funded by the EPSRC(EP/R029431/1 and EP/X035859/1).
文摘A detailed computational investigation,based on density functional theory,of the interaction of polyani-line(PANI)and graphene nanoribbons(GNRs)with SrTiO_(3) is presented.The adsorption of PANI in var-ious oxidation states and co-adsorption with GNRs is found to be thermodynamically favourable.Ad-sorbed PANI introduces N and C 2p states into the SrTiO_(3) bandgap,while co-adsorption of PANI and GNRs leads to a bridging of the gap and semi-metallic behaviour,thus rendering the electrical properties highly sensitive to the loading of the GNRs/PANI in the composites.Modelling the lattice dynamics of the composites predicts a 68-88%reduction in the lattice thermal conductivity due to reduced phonon group velocities.Taken together,these findings provide insight into the growing number of experimental studies highlighting the enhanced thermoelectric performance of oxide-polymer composites and indicate co-adsorption with graphene as a facile direction for future research.
基金financially supported partly by the National Key Research and Development Program of China(2018YFE0111600)the Tianjin Sci.&Tech.Program(17YFZCGX00560)the Young Elite Scientists Sponsorship Program by Tianjin(TJSQNTJ-2017-05)。
文摘Lithium metal is one of the most promising anodes for next-generation batteries due to its high capacity and low reduction potential.However,the notorious Li dendrites can cause the short life span and safety issues,hindering the extensive application of lithium batteries.Herein,Li_(7)La_(3)Zr_(2)O_(12)(LLZO)ceramics are integrated into polyethylene oxide(PEO)to construct a facile polymer/inorganic composite solid-state electrolyte(CSSE)to inhibit the growth of Li dendrites and widen the electrochemical stability window.Given the feasibility of our strategy,the designed PEO-LLZO-LiTFSI composite solid-state electrolyte(PLLCSSE)exhibits an outstanding cycling property of 134.2 mAh g^(-1) after 500 cycles and the Coulombic efficiency of 99.1%after 1000 cycles at 1 C in LiFePO_(4)-Li cell.When cooperated with LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)cathode,the PLL-CSSE renders a capacity retention of 82.4%after 200 cycles at 0.2 C.More importantly,the uniform dispersion of LLZO in PEO matrix is tentative tested via Raman and FT-IR spectra and should be responsible for the improved electrochemical performance.The same conclusion can be drawn from the interface investigation after cycling.This work presents an intriguing solid-state electrolyte with high electrochemical performance,which will boost the development of all-solid-state lithium batteries with high energy density.
基金supported by the National Natural Science Foundation of Guangdong Province(No.2022A1515010173)the National Natural Science Foundation of China(No.22178125)and the 111 Project(No.B20003).
文摘There are some critical issues hindering the practical applications of aqueous zinc-ion batteries(zIBs),although they possess high safety and low cost as one of promising energy storge devices,such as the Zn dendrite growth and the by-product of Zn_(4)SO_(4)(OH)_(6)-xH_(2)O(ZHS)resulted from some side reactions in a mild electrolyte.Herein,a compact and self-repairing solid electrolyte interface(SEl)film,as labeled the PVDF-Zn(TFSI)_(2)-ZHS coating[The PVDF and Zn(TFSI)_(2)are polyvinylidene fluoride and zinc bis(trifluoromethanesulfonyl)imide,respectively],which turns the in-situ generated ZHS into a beneficial ingredient onto the pre-coated PVDF-based composite coating layer containing Zn(TFSI)_(2),was designed and fabricated by a simple doctor blade method.It is shown that the SEl layer can effectively isolate Zn from the electrolyte and homogenize the Zn^(2+)flux,and thus effectively suppress side reactions and dendrites growth.Benefiting from the hybrid SEl layer,a symmetric cell exhibits a high cycling stability over 750h at 2.0 mA/cm^(2)and 2.0 mAh/cm^(2),and meanwhile,a full-cell,coupled with K^(+) pre-intercalationα-MnO_(2)(KMO)cathode,displays excellent rate performance,stable coulombic efficiency and an acceptable cycle life.This work provides a feasible approach for simple and scalable modification of Zn anodes to achieve high performance.
基金This work has been supported by the US National Institutes of Health (No. RO1-DE09848 to YW) and Natural Science Foundation of China (NSFC Nos. 29674001 and 19810760343 to KYQ and YW).
文摘We describe the sol-gel synthesis of a new family of organic-inorganic hybrid materials, in which various vinyl polymers are covalently bonded to and uniformly distributed in inorganic oxide matrices. The materials can be tailored to have both good toughness and hardness while maintaining excellent optical transparency. Doping the sol-gel metal oxides with optically active compounds such as D-glucose results in new optical rotatory composite materials. Removal of the dopant compounds from the composites affords mesoporous oxide materials; which represents a new, nonsurfactant-templated route to mesoporous molecular sieves. We have successfully immobilized a series of enzymes and other bioactive agents in mesoporous materials. Catalytical activities of the enzyme encapsulated in mesoporous materials were found to be much higher than those encapsulated in microporous materials.
基金The National Natural Science Foundation of China(Nos.21374075 and 22169009)Jiangxi Provincial Natural Science Foundation(No.20212ACB204007)the Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry(20212BCD42018)are acknowledged for financial support。
文摘Polymer-inorganic(P-Ⅰ) soft-hard heterostructures & heterojunction photocatalysts,featured by large interfacial contact, efficient charge separation, broad light absorption and maximized redox capacity, have received great attention for their applications in energy conversion and environmental remediation. In this minireview, the classification and mechanism of P-Ⅰ heterojunctions, i.e., type-Ⅰ/Ⅱ, p-n, Z-scheme and S-scheme heterojunctions, and their preparation methods are firstly introduced. Next, the photocatalytic applications of P-Ⅰ heterojunctions, including water splitting, environmental remediation and carbon dioxide reduction, are extensively reviewed. Lastly,a brief summary and perspectives on ongoing challenges and opportunities to construct high performance P-Ⅰ soft-hard photocatalysts are intensively highlighted. We envision this review will provide a picture of the state-of-the-art achievements and promote the photocatalytic applications of P-Ⅰ heterostructures in energy conversion and environmental remediation.
基金This project was supported by the National Natural Science Foundation of China to K.Y Qiu (Grant No. 29874002) and Outstanding Young Scientist Award to Y. Wei (Grant No. 29825504)
文摘Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybrid nanoparticles, 2-(4Chloromethylphenyl) ethyltriethoxysilane (CTES) was immobilized on the surface of silica nanoparticles through condensation reaction of the silanol groups on silica with triethoxysilane group of CTES. Then ATRP of St was initiated by this surface-modified silica nanoparticles bearing benzyl chloride groups, and formed PSt graft chains on the surface of silica nanoparticles. The thickness of the graft chains increased with reaction time. End group analysis confirmed the occurrence of ATRP. Thermal analysis indicated that thermal stabilization of these resulting hybrid nanoparticles also increases with polymerization conversion. The results above show that this 'grafting from' reaction could be used for the preparation of polymer-inorganic hybrid nanoparticles with controlled structure of the polymer's end groups.
文摘A poly(methyl acrylate)(PMA)/ZnAl layered double hydroxide(ZnAl-LDH) intercalation nanocomposite is synthesized by in situ polymerization of methyl acrylate with ogano-modified ZnAl-LDH(O-ZnAl-LDH). Its structure and morphology are confirmed by X-ray diffraction(XRD) and transmission electron microscopy(TEM) image. The d 001 of O-ZnAl-LDH is expanded to 2.85 nm after polymerization from 2.63 nm, which indicates the intercalation of PMA chains into the galleries of O-ZnAl-LDH. The (001) diffraction of PMA/ZnAl-LDH nanocomposite is broad due to the exfoliation of some O-ZnAl-LDH layers. The TEM image shows that the most of the layers of O-ZnAl-LDH are stacked with a distance of about 3 nm while some of them are exfoliated and dispersed disorderly in the PMA matrix.
