Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform a...Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform an extensive structure search of ternary carbon-nitrogen-oxygen(CNO)compound under high pressure with the CALYPSO method and first principles calculations,and successfully identify three polymeric CNO compounds with Pbam,C2/m and I4m2symmetries under 100 GPa.More interestingly,these structures are also dynamically stable at ambient pressure,and are potential high energy density materials(HEDMs).The energy densities of Pbam,C2/m and I4m2 phases of CNO are about2.30 kJ/g,1.37 kJ/g and 2.70 kJ/g,respectively,with the decompositions of graphitic carbon and molecular carbon dioxide andα-N(molecular N_(2))at ambient pressure.The present results provide in-depth insights into the structural evolution and physical properties of CNO compounds under high pressures,which offer crucial insights for designs and syntheses of novel HEDMs.展开更多
Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century.While lithium-ion batteries have so far ...Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century.While lithium-ion batteries have so far been the dominant choice,numerous emerging applications call for higher capacity,better safety and lower costs while maintaining sufficient cyclability.The design space for potentially better alternatives is extremely large,with numerous new chemistries and architectures being simultaneously explored.These include other insertion ions(e.g.sodium and numerous multivalent ions),conversion electrode materials(e.g.silicon,metallic anodes,halides and chalcogens)and aqueous and solid electrolytes.However,each of these potential“beyond lithium-ion”alternatives faces numerous challenges that often lead to very poor cyclability,especially at the commercial cell level,while lithium-ion batteries continue to improve in performance and decrease in cost.This review examines fundamental principles to rationalise these numerous developments,and in each case,a brief overview is given on the advantages,advances,remaining challenges preventing cell-level implementation and the state-of-the-art of the solutions to these challenges.Finally,research and development results obtained in academia are compared to emerging commercial examples,as a commentary on the current and near-future viability of these“beyond lithium-ion”alternatives.展开更多
The microstructures on electrode level are crucial for battery performance, but the ambiguous understanding of both electrode microstructures and their structuring process causes critical challenges in controlling and...The microstructures on electrode level are crucial for battery performance, but the ambiguous understanding of both electrode microstructures and their structuring process causes critical challenges in controlling and evaluating the electrode quality during fabrication. In this review, analogous to the cell microenvironment well-known in biology, we introduce the concept of ‘‘active material microenvironment”(ME@AM)that is built by the ion/electron transport structures surrounding the AMs, for better understanding the significance of the electrode microstructures. Further, the scientific significance of electrode processing for electrode quality control is highlighted by its strong links to the structuring and quality control of ME@AM. Meanwhile, the roles of electrode rheology in both electrode structuring and structural characterizations involved in the entire electrode manufacturing process(i.e., slurry preparation, coating/printing/extrusion, drying and calendering) are specifically detailed. The advantages of electrode rheology testing on in-situ characterizations of the electrode qualities/structures are emphasized. This review provides a glimpse of the electrode rheology engaged in electrode manufacturing process and new insights into the understanding and effective regulation of electrode microstructures for future high-performance batteries.展开更多
The performance of an energetic compound is mainly decided by parameters such as density, oxygen balance, heat of formation,and stability. Among these properties, density is the most important factor because it determ...The performance of an energetic compound is mainly decided by parameters such as density, oxygen balance, heat of formation,and stability. Among these properties, density is the most important factor because it determines the detonation pressure and velocity. One of the trends in the development of high-energy-density materials(HEDMs) involves the study of energetic materials with high nitrogen levels. A compound with high nitrogen content can obtain substantial energy from the heat of formation rather than from the intramolecular oxidation of carbon skeleton to release energy in the form of a nitro group or nitrate ester. In addition to excellent performance, the newly developed energetic materials should also possess high working power and insensitivity toward external influences for ensuring the safety of charge and service, high energy release rate, long service life,good compatibility, excellent biological performance, low toxicity, safe battlefield environment, and low moisture absorption,which meet the requirements of military and civilian use. This review summarizes the research progress on global HEDMs.TNAZ, FOX-7, octanitrocubanane, TAM, TKX-50, and N5 were believed to show promise in achieving application goals. The prospective vision of HEDMs containing ions, total nitrogen, metal hydrogen, and nuclear energetic isomers, overcoming technical barriers, synthesis of all-nitrogen materials, theoretical studies on desorption/adsorption system, and challenging technical problems that need to be solved for the safety of synthetic nitrogen compounds were discussed to further elucidate the effect of this subject.展开更多
Lithium-ion capacitors(LICs)are regarded as a good choice for next-generation energy storage devices,which are expected to exhibit high energy densities,high power densities,and ultra-long cycling stability.Neverthele...Lithium-ion capacitors(LICs)are regarded as a good choice for next-generation energy storage devices,which are expected to exhibit high energy densities,high power densities,and ultra-long cycling stability.Nevertheless,only a few battery-type cathode materials with limited kinetic properties can be employed in LICs,and their electrochemical properties need to be optimized urgently.Here,we exploit a new dendrite-structured FeF_(2) consisting of closely linked primary nanoparticles using a facile solvothermal method combined with the subsequent annealing treatment.This particular architecture has favorable transport pathways for both lithium ions and electrons and exhibits an ultrafast chargedischarge capability with high reversible capacities.Furthermore,a well-designed LIC employing the prepared dendrite-structured FeF_(2) as the battery-type cathode and commercialized activated carbon(AC)as supercapacitor-type anode was constructed in an organic electrolyte containing Li ions.The LIC operates at an optimal voltage range of 1.1-3.8 V and shows a maximum high energy density of 152 W h kg^(-1) and a high power density of 4900 W kg^(-1) based on the total mass of cathode and anode.Long-term cycling stability(85%capacity retention after 2000 cycles)was achieved at 1 A g^(-1).This work suggests that the dendrite-structured FeF_(2) is a prime candidate for high-performance LICs and accelerates the development of hybrid ion capacitor devices.展开更多
Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of appl...Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of applicable K+storage materials which are able to accommodate the relatively large size and high activity of potassium.Here,we report a cocoon silk chemistry strategy to synthesize a hierarchically porous nitrogen-doped carbon(SHPNC).The as-prepared SHPNC with high surface area and rich N-doping not only offers highly efficient channels for the fast transport of electrons and K ions during cycling,but also provides sufficient void space to relieve volume expansion of electrode and improves its stability.Therefore,KIHCs with SHPNC anode and activated carbon cathode afford high energy of 135 Wh kg-1(calculated based on the total mass of anode and cathode),long lifespan,and ultrafast charge/slow discharge performance.This study defines that the KIHCs show great application prospect in the field of high-performance energy storage devices.展开更多
There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucia...There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucial for the development of high-energy-density cathodes.Here we present highperformance aqueous zinc-manganese batteries with reversible Mn2+/Mn4+ double redox.The active Mn4+is generated in situ from the Mn2+-containing MnOx nanoparticles and electrolyte.Benefitting from the low crystallinity of the birnessite-type MnO2 as well as the electrolyte with Mn2+additive,the MnOX cathode achieves an ultrahigh energy density with a peak of845.1 Wh kg-1 and an ultralong lifespan of 1500 cycles.The combination of electrochemical measurements and material characterization reveals the reversible Mn2+/Mn4+double redox(birnessite-type MnO2? monoclinic MnOOH and spinel ZnMn2O4 H?Mn2+ions).The reversible Mn2+/Mn4+double redox electrode reaction mechanism offers new opportunities for the design of low-cost,high-energy-density cathodes for advanced rechargeable aqueous batteries.展开更多
As one of new electrical energy storage systems, supercapacitors possess higher energy density than conventional capacitors and larger power density than batteries, integrating substantial merits with high energy, lar...As one of new electrical energy storage systems, supercapacitors possess higher energy density than conventional capacitors and larger power density than batteries, integrating substantial merits with high energy, large power delivery, long cycle life, obvious safety, and low cost. However, the unsatisfying energy density is the inhabiting issue for the wide commercial applications. As the energy density(E, W h kg?1) is directly proportional to specific capacitance(C, F g?1) and the square of operating voltage(V, V), in this review, we summarize the recent progress in two sections: the exploration of high-performance electrode materials to achieve high specific capacitance and the construction of high-voltage supercapacitor systems for high working voltage. The progressive explorations and developments in supercapacitors could guide the future research towards high-performance, low-cost, and safe energy storage devices.展开更多
Micrometre-sized electroactive particles with high tapping density show significant potential for commercial application since they effectively alleviate low Coulombic efficiency and excessive solid electrolyte interp...Micrometre-sized electroactive particles with high tapping density show significant potential for commercial application since they effectively alleviate low Coulombic efficiency and excessive solid electrolyte interphase(SEI)issues brought by nanostructures.Furthermore,optimizing the electrode architecture using novel design concepts can improve the energy density.Beyond the electrode material structure design strategy,binder plays a vital role in providing the mechanical stability and regulating the charge transport.This highlight presents the latest development to design high-capacity batteries by optimizing the binder structures in electrodes and emphasizes the significance of binder design for further commercial application.展开更多
The search for high energy density materials(HEDMs)in polymeric nitrogen compounds has gained considerable attention.Previous theoretical predictions and experiments have revealed that metal ions can be used to stabil...The search for high energy density materials(HEDMs)in polymeric nitrogen compounds has gained considerable attention.Previous theoretical predictions and experiments have revealed that metal ions can be used to stabilize the pentazolate(N-5)anion.In this work,by employing a machine learning-accelerated crystal structure searching method and first-principles calculations,we found that the new pentazolate salts,CaN(10)and BaN(10),are energetically favorable at high pressures.Phonon dispersion calculations reveal that they are quenchable at ambient pressure.Ab initio molecular dynamics simulations verify their dynamic stability at finite temperature.Bader charge and electron localization function illustrates that alkaline earth atoms serve as electron donors,contributing to the stability of N5 rings.Bonding calculations reveal covalent bonds between nitrogen atoms and weak interactions between N5 rings.Similar to other pentazolate salts,these polymeric nitrides have high energy densities of approximately 2.35 kJ/g for CaN(10)and 1.32 kJ/g for BaN(10).The predictions of CaN(10)and BaN(10)structures indicate that these salts are potential candidates for green nitrogen-rich HEDMs.展开更多
基金the National Natural Science Foundation of China(Grant Nos.12174352 and 12111530103)the Fundamental Research Funds for the Central UniversitiesChina University of Geosciences(Wuhan)(Grant No.G1323523065)。
文摘Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform an extensive structure search of ternary carbon-nitrogen-oxygen(CNO)compound under high pressure with the CALYPSO method and first principles calculations,and successfully identify three polymeric CNO compounds with Pbam,C2/m and I4m2symmetries under 100 GPa.More interestingly,these structures are also dynamically stable at ambient pressure,and are potential high energy density materials(HEDMs).The energy densities of Pbam,C2/m and I4m2 phases of CNO are about2.30 kJ/g,1.37 kJ/g and 2.70 kJ/g,respectively,with the decompositions of graphitic carbon and molecular carbon dioxide andα-N(molecular N_(2))at ambient pressure.The present results provide in-depth insights into the structural evolution and physical properties of CNO compounds under high pressures,which offer crucial insights for designs and syntheses of novel HEDMs.
基金J.Wang acknowledges the support by MOE,Singapore Ministry of Education(MOE2018-T2-2-095)for research work conducted at the National University of Singapore.Z.L.Liu acknowledges the A*STAR’s Central Research Funds(CRF)Award(Project:SC25/21-111312)+1 种基金Y.Gao acknowledges financial support by ST Engineering Advanced Material Engineering Pte.Ltd.and Singapore Economic Development BoardOpen access funding provided by Shanghai Jiao Tong University
文摘Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century.While lithium-ion batteries have so far been the dominant choice,numerous emerging applications call for higher capacity,better safety and lower costs while maintaining sufficient cyclability.The design space for potentially better alternatives is extremely large,with numerous new chemistries and architectures being simultaneously explored.These include other insertion ions(e.g.sodium and numerous multivalent ions),conversion electrode materials(e.g.silicon,metallic anodes,halides and chalcogens)and aqueous and solid electrolytes.However,each of these potential“beyond lithium-ion”alternatives faces numerous challenges that often lead to very poor cyclability,especially at the commercial cell level,while lithium-ion batteries continue to improve in performance and decrease in cost.This review examines fundamental principles to rationalise these numerous developments,and in each case,a brief overview is given on the advantages,advances,remaining challenges preventing cell-level implementation and the state-of-the-art of the solutions to these challenges.Finally,research and development results obtained in academia are compared to emerging commercial examples,as a commentary on the current and near-future viability of these“beyond lithium-ion”alternatives.
基金the financial support from the National Natural Science Foundation of China and the start-up projectthe Sichuan-University-Dazhou Joint project(00309053A2037)+1 种基金the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘The microstructures on electrode level are crucial for battery performance, but the ambiguous understanding of both electrode microstructures and their structuring process causes critical challenges in controlling and evaluating the electrode quality during fabrication. In this review, analogous to the cell microenvironment well-known in biology, we introduce the concept of ‘‘active material microenvironment”(ME@AM)that is built by the ion/electron transport structures surrounding the AMs, for better understanding the significance of the electrode microstructures. Further, the scientific significance of electrode processing for electrode quality control is highlighted by its strong links to the structuring and quality control of ME@AM. Meanwhile, the roles of electrode rheology in both electrode structuring and structural characterizations involved in the entire electrode manufacturing process(i.e., slurry preparation, coating/printing/extrusion, drying and calendering) are specifically detailed. The advantages of electrode rheology testing on in-situ characterizations of the electrode qualities/structures are emphasized. This review provides a glimpse of the electrode rheology engaged in electrode manufacturing process and new insights into the understanding and effective regulation of electrode microstructures for future high-performance batteries.
文摘The performance of an energetic compound is mainly decided by parameters such as density, oxygen balance, heat of formation,and stability. Among these properties, density is the most important factor because it determines the detonation pressure and velocity. One of the trends in the development of high-energy-density materials(HEDMs) involves the study of energetic materials with high nitrogen levels. A compound with high nitrogen content can obtain substantial energy from the heat of formation rather than from the intramolecular oxidation of carbon skeleton to release energy in the form of a nitro group or nitrate ester. In addition to excellent performance, the newly developed energetic materials should also possess high working power and insensitivity toward external influences for ensuring the safety of charge and service, high energy release rate, long service life,good compatibility, excellent biological performance, low toxicity, safe battlefield environment, and low moisture absorption,which meet the requirements of military and civilian use. This review summarizes the research progress on global HEDMs.TNAZ, FOX-7, octanitrocubanane, TAM, TKX-50, and N5 were believed to show promise in achieving application goals. The prospective vision of HEDMs containing ions, total nitrogen, metal hydrogen, and nuclear energetic isomers, overcoming technical barriers, synthesis of all-nitrogen materials, theoretical studies on desorption/adsorption system, and challenging technical problems that need to be solved for the safety of synthetic nitrogen compounds were discussed to further elucidate the effect of this subject.
基金funding support from the National Natural Science Foundation of China(51804173)the Shandong Provincial Natural Science Foundation(ZR2018BB030)+1 种基金the Qingdao Science and Technology Plan Applied Basic Research(Youth Special Project,18-2-2-22-jch)the funding support from “Distinguished Taishan Scholar”project。
文摘Lithium-ion capacitors(LICs)are regarded as a good choice for next-generation energy storage devices,which are expected to exhibit high energy densities,high power densities,and ultra-long cycling stability.Nevertheless,only a few battery-type cathode materials with limited kinetic properties can be employed in LICs,and their electrochemical properties need to be optimized urgently.Here,we exploit a new dendrite-structured FeF_(2) consisting of closely linked primary nanoparticles using a facile solvothermal method combined with the subsequent annealing treatment.This particular architecture has favorable transport pathways for both lithium ions and electrons and exhibits an ultrafast chargedischarge capability with high reversible capacities.Furthermore,a well-designed LIC employing the prepared dendrite-structured FeF_(2) as the battery-type cathode and commercialized activated carbon(AC)as supercapacitor-type anode was constructed in an organic electrolyte containing Li ions.The LIC operates at an optimal voltage range of 1.1-3.8 V and shows a maximum high energy density of 152 W h kg^(-1) and a high power density of 4900 W kg^(-1) based on the total mass of cathode and anode.Long-term cycling stability(85%capacity retention after 2000 cycles)was achieved at 1 A g^(-1).This work suggests that the dendrite-structured FeF_(2) is a prime candidate for high-performance LICs and accelerates the development of hybrid ion capacitor devices.
基金financially supported by the Fundamental Research Funds of the Central Universities(No.531118010112)the Double FirstClass University Initiative of Hunan University(No.531109100004)+1 种基金the Fundamental Research Funds of the Central Universities(No.531107051048)support from the Hunan Key Laboratory of TwoDimensional Materials(No.801200005)。
文摘Potassium-ion hybrid capacitors(KIHCs) have attracted increasing research interest because of the virtues of potassium-ion batteries and supercapacitors.The development of KIHCs is subject to the investigation of applicable K+storage materials which are able to accommodate the relatively large size and high activity of potassium.Here,we report a cocoon silk chemistry strategy to synthesize a hierarchically porous nitrogen-doped carbon(SHPNC).The as-prepared SHPNC with high surface area and rich N-doping not only offers highly efficient channels for the fast transport of electrons and K ions during cycling,but also provides sufficient void space to relieve volume expansion of electrode and improves its stability.Therefore,KIHCs with SHPNC anode and activated carbon cathode afford high energy of 135 Wh kg-1(calculated based on the total mass of anode and cathode),long lifespan,and ultrafast charge/slow discharge performance.This study defines that the KIHCs show great application prospect in the field of high-performance energy storage devices.
基金supported by the National Natural Science Foundation of China(Grant No.51772331)the National Key Technologies R&D Program(Grant No.2018YFB1106000).
文摘There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucial for the development of high-energy-density cathodes.Here we present highperformance aqueous zinc-manganese batteries with reversible Mn2+/Mn4+ double redox.The active Mn4+is generated in situ from the Mn2+-containing MnOx nanoparticles and electrolyte.Benefitting from the low crystallinity of the birnessite-type MnO2 as well as the electrolyte with Mn2+additive,the MnOX cathode achieves an ultrahigh energy density with a peak of845.1 Wh kg-1 and an ultralong lifespan of 1500 cycles.The combination of electrochemical measurements and material characterization reveals the reversible Mn2+/Mn4+double redox(birnessite-type MnO2? monoclinic MnOOH and spinel ZnMn2O4 H?Mn2+ions).The reversible Mn2+/Mn4+double redox electrode reaction mechanism offers new opportunities for the design of low-cost,high-energy-density cathodes for advanced rechargeable aqueous batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.51572129&U1407106)Natural Science Foundation of Jiangsu Province(Grant No.BK20131349)+1 种基金A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Fundamental Research Funds for the Central Universities(Grant No.30915011204)
文摘As one of new electrical energy storage systems, supercapacitors possess higher energy density than conventional capacitors and larger power density than batteries, integrating substantial merits with high energy, large power delivery, long cycle life, obvious safety, and low cost. However, the unsatisfying energy density is the inhabiting issue for the wide commercial applications. As the energy density(E, W h kg?1) is directly proportional to specific capacitance(C, F g?1) and the square of operating voltage(V, V), in this review, we summarize the recent progress in two sections: the exploration of high-performance electrode materials to achieve high specific capacitance and the construction of high-voltage supercapacitor systems for high working voltage. The progressive explorations and developments in supercapacitors could guide the future research towards high-performance, low-cost, and safe energy storage devices.
文摘Micrometre-sized electroactive particles with high tapping density show significant potential for commercial application since they effectively alleviate low Coulombic efficiency and excessive solid electrolyte interphase(SEI)issues brought by nanostructures.Furthermore,optimizing the electrode architecture using novel design concepts can improve the energy density.Beyond the electrode material structure design strategy,binder plays a vital role in providing the mechanical stability and regulating the charge transport.This highlight presents the latest development to design high-capacity batteries by optimizing the binder structures in electrodes and emphasizes the significance of binder design for further commercial application.
基金financial support from the National Key R&D Program of China(Grant No.2016YFA0300404)the National Natural Science Foundation of China(Grant Nos.11974162,and 11834006)+1 种基金the Fundamental Research Funds for the Central Universitiesfinancial support from the Project funded by China Postdoctoral Science Foundation(Grant No.2019M651767)。
文摘The search for high energy density materials(HEDMs)in polymeric nitrogen compounds has gained considerable attention.Previous theoretical predictions and experiments have revealed that metal ions can be used to stabilize the pentazolate(N-5)anion.In this work,by employing a machine learning-accelerated crystal structure searching method and first-principles calculations,we found that the new pentazolate salts,CaN(10)and BaN(10),are energetically favorable at high pressures.Phonon dispersion calculations reveal that they are quenchable at ambient pressure.Ab initio molecular dynamics simulations verify their dynamic stability at finite temperature.Bader charge and electron localization function illustrates that alkaline earth atoms serve as electron donors,contributing to the stability of N5 rings.Bonding calculations reveal covalent bonds between nitrogen atoms and weak interactions between N5 rings.Similar to other pentazolate salts,these polymeric nitrides have high energy densities of approximately 2.35 kJ/g for CaN(10)and 1.32 kJ/g for BaN(10).The predictions of CaN(10)and BaN(10)structures indicate that these salts are potential candidates for green nitrogen-rich HEDMs.
