The importance of crystallite size control and direct synthesis of materials with desirable properties is broadly applicable for the rational design and development of new active materials for energy storage.Recently,...The importance of crystallite size control and direct synthesis of materials with desirable properties is broadly applicable for the rational design and development of new active materials for energy storage.Recently,the use of nanoparticles and crystallite size control has redefined electrode design strategies,due in part to the large surface area/volume ratios providing more pathways for ion movement within the bulk electrode.This review is structured primarily as a case study,where reports involving a specific densely structured iron oxide,magnetite,Fe_(3)O_(4),and its use as an electrode in LIBs are used as examples.Due to the high theoretical capacity(924 mA h g^(−1)),and opportunity for implementation of a low cost electrode material,magnetite was selected as the model material for this review.Notably,crystallite size,morphology,and electrode heterostructure can all play a critical role in battery relevant electrochemistry,particularly for crystallographically dense materials such as Fe_(3)O_(4).Several examples of Fe_(3)O_(4)based composites are described,incorporating different types of conductive materials such as carbons as part of the structure.Additionally,this review also provides a brief introduction to a newer iron oxide based material with a 2D layered structure,silver ferrite,where crystallite size control was synthetically achieved.By focusing on two specific iron oxide based nanoscale inorganic materials,this review highlights and distinguishes the contributions of electroactive material crystallite size,morphology and electrode heterostructure to electrochemical behavior,facilitating the future development of next generation of battery electrodes.展开更多
CONSPECTUS:The demand for lithium ion batteries continues to expand for powering applications such as portable electronics,grid-scale energy storage,and electric vehicles.As the application requirements advance,the in...CONSPECTUS:The demand for lithium ion batteries continues to expand for powering applications such as portable electronics,grid-scale energy storage,and electric vehicles.As the application requirements advance,the innovation of lithium ion batteries toward higher energy density and power output is required.Along with the investigation of new materials,an important strategy for increasing battery energy content is to design electrodes with high areal loading to minimize the fraction of nonactive materials such as current collectors,separators,and packaging components,resulting in significant gains in energy content and the reduction of the system-level cost.However,the adoption of thick high areal loading electrodes has been impeded by sluggish charge transport and mechanical instability.With conventional slurry cast electrodes,battery function significantly deteriorates with increases in electrode thickness due to high cell polarization and the incomplete utilization of active materials.Thus,a consideration of approaches that facilitate an understanding and eventual adoption of high-loading electrodes is warranted to enable the deliberate advancement of next-generation batteries.展开更多
For the past two decades,conversion and alloying-type materials have been heralded as the natural heir to commercially available graphite anodes due to their ability to deliver high gravimetric/volumetric power.Commer...For the past two decades,conversion and alloying-type materials have been heralded as the natural heir to commercially available graphite anodes due to their ability to deliver high gravimetric/volumetric power.Commercialization of batteries with these high-energy-density active materials could impact a variety of sectors including electric vehicles,grid storage,and consumer electronics and contribute toward an ever-increasing electrified world.However,the various failure mechanisms from inherent interfacial chemical instabilities associated with these materials make them unable to be merely substituted into currently available electrode fabrication and formulation processing techniques.As a result,realizing the high theoretical capacity and achieving commercial viability of these materials will rely on the careful manipulation of interfacial chemical interactions that dictate and control various kinetic and transport processes across multiple scales of the composite electrode.This has led to a plethora of research that has focused on systematically understanding properties of the different electrode components and designing carefully constructed electrode formulations to achieve composite electrodes with increased chemical stability,enhanced local mixed conductivities,or improved mechanical resilience.This Account relates recent progress in the understanding of synergetic opportunities for energy-dense,resilient composite anodes.By understanding the interplay between components of the composite electrode,we can construct enhanced well-integrated electrodes with performance metrics that surpass empirically derived architectures.Due to the increased complexity of high-volume-expanding electrodes,performance is more than the cumulative contributions of the individual components,and therefore energy and compatibility matching are important for robust electrochemical performance across cycling,rate capability,facile lithium-ion transport,and stability.In this Account,synergistic opportunities are framed from a chemistry perspective as we focus on examining interfacial interactions that span all electrode components:the active material surface,conductive agent linkage,and polymeric binder mesoscale.Control of key interfacial chemistry can be achieved through chemical functionalization,physical interactions,and other types of linkages and thereby lead to utilization of high-energy-density active materials in robust composite electrodes.Leveraging several techniques such as the Hanson solubility parameter(HSP)analysis,X-ray photoelectron spectroscopy(XPS),and Fourier transform infrared(FT-IR)spectroscopy among others can be important in gaining mechanistic insights for key kinetic and transport phenomena that occur across multiple interface length scales.Importantly,understanding the underlying effect of interfacial manipulation on the mechanisms of transport and kinetic processes leads to the development of experimental toolsets and design frameworks applicable to not just current material classes but to forward-looking chemistries that can be applied to next-generation battery materials.Herein,we discuss interfacial control of the composite electrodes via chemical modification techniques toward the creation of reliable,long-lasting,energy-dense lithium-ion batteries.展开更多
基金supported as part of the Center for Mesoscale Transport Properties,an Energy Frontier Research Center supported by the U.S.Department of Energy,Office of Science,Basic Energy Sciences,under award#DE-SC0012673support from the National Science Foundation funded Research Experience for Undergraduates Site:Nanotechnology for Health,Energy and the Environment at Stony Brook University.
文摘The importance of crystallite size control and direct synthesis of materials with desirable properties is broadly applicable for the rational design and development of new active materials for energy storage.Recently,the use of nanoparticles and crystallite size control has redefined electrode design strategies,due in part to the large surface area/volume ratios providing more pathways for ion movement within the bulk electrode.This review is structured primarily as a case study,where reports involving a specific densely structured iron oxide,magnetite,Fe_(3)O_(4),and its use as an electrode in LIBs are used as examples.Due to the high theoretical capacity(924 mA h g^(−1)),and opportunity for implementation of a low cost electrode material,magnetite was selected as the model material for this review.Notably,crystallite size,morphology,and electrode heterostructure can all play a critical role in battery relevant electrochemistry,particularly for crystallographically dense materials such as Fe_(3)O_(4).Several examples of Fe_(3)O_(4)based composites are described,incorporating different types of conductive materials such as carbons as part of the structure.Additionally,this review also provides a brief introduction to a newer iron oxide based material with a 2D layered structure,silver ferrite,where crystallite size control was synthetically achieved.By focusing on two specific iron oxide based nanoscale inorganic materials,this review highlights and distinguishes the contributions of electroactive material crystallite size,morphology and electrode heterostructure to electrochemical behavior,facilitating the future development of next generation of battery electrodes.
基金The preparation of this manuscript was supported as part of the Center for Mesoscale Transport Properties,funded by the U.S.Department of Energy,Office of Science,Basic Energy Sciences,under award no.DE-SC0012673E.S.T.acknowledges support from the William and Jane Knapp Chair in Energy and the Environment。
文摘CONSPECTUS:The demand for lithium ion batteries continues to expand for powering applications such as portable electronics,grid-scale energy storage,and electric vehicles.As the application requirements advance,the innovation of lithium ion batteries toward higher energy density and power output is required.Along with the investigation of new materials,an important strategy for increasing battery energy content is to design electrodes with high areal loading to minimize the fraction of nonactive materials such as current collectors,separators,and packaging components,resulting in significant gains in energy content and the reduction of the system-level cost.However,the adoption of thick high areal loading electrodes has been impeded by sluggish charge transport and mechanical instability.With conventional slurry cast electrodes,battery function significantly deteriorates with increases in electrode thickness due to high cell polarization and the incomplete utilization of active materials.Thus,a consideration of approaches that facilitate an understanding and eventual adoption of high-loading electrodes is warranted to enable the deliberate advancement of next-generation batteries.
基金This work was performed as part of the Center for Mesoscale Transport Properties,an Energy Frontier Research Center supported by the U.S.Department of Energy,Office of Science,Basic Energy Sciences,under award#DE-SC0012673.E.R.also appreciates support from Lehigh University through funds associated with the Carl Robert Anderson Chair in Chemical Engineering.E.S.T.acknowledges support as the William and Jane Knapp Chair for Energy and the Environment at Stony Brook University。
文摘For the past two decades,conversion and alloying-type materials have been heralded as the natural heir to commercially available graphite anodes due to their ability to deliver high gravimetric/volumetric power.Commercialization of batteries with these high-energy-density active materials could impact a variety of sectors including electric vehicles,grid storage,and consumer electronics and contribute toward an ever-increasing electrified world.However,the various failure mechanisms from inherent interfacial chemical instabilities associated with these materials make them unable to be merely substituted into currently available electrode fabrication and formulation processing techniques.As a result,realizing the high theoretical capacity and achieving commercial viability of these materials will rely on the careful manipulation of interfacial chemical interactions that dictate and control various kinetic and transport processes across multiple scales of the composite electrode.This has led to a plethora of research that has focused on systematically understanding properties of the different electrode components and designing carefully constructed electrode formulations to achieve composite electrodes with increased chemical stability,enhanced local mixed conductivities,or improved mechanical resilience.This Account relates recent progress in the understanding of synergetic opportunities for energy-dense,resilient composite anodes.By understanding the interplay between components of the composite electrode,we can construct enhanced well-integrated electrodes with performance metrics that surpass empirically derived architectures.Due to the increased complexity of high-volume-expanding electrodes,performance is more than the cumulative contributions of the individual components,and therefore energy and compatibility matching are important for robust electrochemical performance across cycling,rate capability,facile lithium-ion transport,and stability.In this Account,synergistic opportunities are framed from a chemistry perspective as we focus on examining interfacial interactions that span all electrode components:the active material surface,conductive agent linkage,and polymeric binder mesoscale.Control of key interfacial chemistry can be achieved through chemical functionalization,physical interactions,and other types of linkages and thereby lead to utilization of high-energy-density active materials in robust composite electrodes.Leveraging several techniques such as the Hanson solubility parameter(HSP)analysis,X-ray photoelectron spectroscopy(XPS),and Fourier transform infrared(FT-IR)spectroscopy among others can be important in gaining mechanistic insights for key kinetic and transport phenomena that occur across multiple interface length scales.Importantly,understanding the underlying effect of interfacial manipulation on the mechanisms of transport and kinetic processes leads to the development of experimental toolsets and design frameworks applicable to not just current material classes but to forward-looking chemistries that can be applied to next-generation battery materials.Herein,we discuss interfacial control of the composite electrodes via chemical modification techniques toward the creation of reliable,long-lasting,energy-dense lithium-ion batteries.
