In the quest for the development of safer lithium-metal batteries(LMBs),the integration of inorganic fillers and ionic liquids into polymer matrices has emerged as a promising strategy to enhance safety,ionic conducti...In the quest for the development of safer lithium-metal batteries(LMBs),the integration of inorganic fillers and ionic liquids into polymer matrices has emerged as a promising strategy to enhance safety,ionic conductivity and battery performance.This study introduces a novel composite ionogel(IG)synthesized through a facile one-pot method,incorporating butyl methacrylate(BMA)and poly(ethylene glycol)diacrylate(PEGDA)with the ionic liquid 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide(PYR_(14)FSI)and garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)nanoparticles.A distinctive feature of the approach is the use of an organosilane functionalization of the LLZTO nanoparticles,which ensures their full integration into the polymer matrix during free-radical polymerization.Moreover,this method effectively eliminates the Li_(2)CO_(3)passivation layer that typically forms on the surface of the LLZTO nanoparticles,thus,further contributing to an enhanced performance.As a result,a LMB with the functionalized LLZTO IG electrolyte delivered more than 160 mA h g^(−1)with a very good capacity retention of 97.7%after 400 cycles in Li|IG|LFP cells.展开更多
Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the po...Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the polymerization mechanism typically employed relies on the presence of an initiator,and is hindered by oxygen,thus impeding the industrial scale-up of the GPEs production.In this work,an UV-mediated thiol-ene polymerization,employing polyethylene glycol diacrylate(PEGDA)as oligomer,was carried out in a liquid electrolyte solution(1M LiTFSI in EC/DEC)to obtain a self-standing GPE.A comparative study between two different thiol-containing crosslinkers(trimethylolpropane tris(3-mercaptopropionate)-T3 and pentaerythritol tetrakis(3-mercaptopropionate)-T4)was carried out,studying the effects of the crosslinking environment and the GPE production methods on the cell performances.All the produced GPEs present an excellent room temperature ionic conductivity above 1 mS cm^(-1),as well as a wide electrochemical stability window up to 4.59 V.When cycled at a current density of C/10 for more than 250 cycles,all of the tested cells showed a stable cycling profile and a specific capacity>100 mAh g^(-1),indicating the suitability of such processes for up-scaling.展开更多
Food production demand is constantly growing,entailing a proportional increment in fertilisers and pharmaceuticals use,which are eventually introduced to the environment,leading,among others,to an imbalance in the nit...Food production demand is constantly growing,entailing a proportional increment in fertilisers and pharmaceuticals use,which are eventually introduced to the environment,leading,among others,to an imbalance in the nitrogen cycle.Electrochemical nitrate reduction reaction is a delocalised route for nitrates elimination and green ammonia production.In the present study,we carry out nitrates electroreduction over a commercial MoS_(2)catalyst,focusing on optimising selected input factors affecting the reaction.Concretely,Doehlert design of experiment and response surface methodology are employed to find the proper combination of supporting salt concentration in the electrolyte,applied potential,and catalyst loading at the working electrode,with the overall aim to boost Faradaic efficiency(FE)and ammonia production.As a matter of fact,varying these input factors,the obtained FE values ranged from∼2%to∼80%,highlighting the strength of the newly conceived approach.Moreover,our multivariate strategy allows the quantification of each factor effect and elucidates hidden interactions between them.Finally,successful extended durability tests are performed for 100 h at both FE and productivity(P)optimal conditions.In parallel,cell electrodes are characterised by in-depth structural,morphological,and surface techniques,before and after ageing,overall demonstrating the outstanding stability of the proposed electrochemical reactor.展开更多
基金the German Federal Ministry for Education and Research(BMBF)for financial support within the FB2-Hybrid project(03XP0428B)Moreover,D.Bresser and T.Diemant would like to acknowledge financial support from the Helmholtz Association.
文摘In the quest for the development of safer lithium-metal batteries(LMBs),the integration of inorganic fillers and ionic liquids into polymer matrices has emerged as a promising strategy to enhance safety,ionic conductivity and battery performance.This study introduces a novel composite ionogel(IG)synthesized through a facile one-pot method,incorporating butyl methacrylate(BMA)and poly(ethylene glycol)diacrylate(PEGDA)with the ionic liquid 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide(PYR_(14)FSI)and garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)nanoparticles.A distinctive feature of the approach is the use of an organosilane functionalization of the LLZTO nanoparticles,which ensures their full integration into the polymer matrix during free-radical polymerization.Moreover,this method effectively eliminates the Li_(2)CO_(3)passivation layer that typically forms on the surface of the LLZTO nanoparticles,thus,further contributing to an enhanced performance.As a result,a LMB with the functionalized LLZTO IG electrolyte delivered more than 160 mA h g^(−1)with a very good capacity retention of 97.7%after 400 cycles in Li|IG|LFP cells.
基金the project PNRR-NGEU,which has received funding from the MUR-DM 352/2022.
文摘Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the polymerization mechanism typically employed relies on the presence of an initiator,and is hindered by oxygen,thus impeding the industrial scale-up of the GPEs production.In this work,an UV-mediated thiol-ene polymerization,employing polyethylene glycol diacrylate(PEGDA)as oligomer,was carried out in a liquid electrolyte solution(1M LiTFSI in EC/DEC)to obtain a self-standing GPE.A comparative study between two different thiol-containing crosslinkers(trimethylolpropane tris(3-mercaptopropionate)-T3 and pentaerythritol tetrakis(3-mercaptopropionate)-T4)was carried out,studying the effects of the crosslinking environment and the GPE production methods on the cell performances.All the produced GPEs present an excellent room temperature ionic conductivity above 1 mS cm^(-1),as well as a wide electrochemical stability window up to 4.59 V.When cycled at a current density of C/10 for more than 250 cycles,all of the tested cells showed a stable cycling profile and a specific capacity>100 mAh g^(-1),indicating the suitability of such processes for up-scaling.
基金This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement No. 948769, project title: SuN_2rise)the 《HYDREAM》 project–funded by European Union-Next Generation EU–within the PRIN 2022 program (D.D. 104-02/02/2022 Ministero dell’Università e della Ricerca)supported by the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 101107906
文摘Food production demand is constantly growing,entailing a proportional increment in fertilisers and pharmaceuticals use,which are eventually introduced to the environment,leading,among others,to an imbalance in the nitrogen cycle.Electrochemical nitrate reduction reaction is a delocalised route for nitrates elimination and green ammonia production.In the present study,we carry out nitrates electroreduction over a commercial MoS_(2)catalyst,focusing on optimising selected input factors affecting the reaction.Concretely,Doehlert design of experiment and response surface methodology are employed to find the proper combination of supporting salt concentration in the electrolyte,applied potential,and catalyst loading at the working electrode,with the overall aim to boost Faradaic efficiency(FE)and ammonia production.As a matter of fact,varying these input factors,the obtained FE values ranged from∼2%to∼80%,highlighting the strength of the newly conceived approach.Moreover,our multivariate strategy allows the quantification of each factor effect and elucidates hidden interactions between them.Finally,successful extended durability tests are performed for 100 h at both FE and productivity(P)optimal conditions.In parallel,cell electrodes are characterised by in-depth structural,morphological,and surface techniques,before and after ageing,overall demonstrating the outstanding stability of the proposed electrochemical reactor.
