Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which ot...Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.展开更多
Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescen...Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.展开更多
Recently,graphene has drawn considerable attention in the field of electronics,owing to its favorable conductivity and high carrier mobility.Crucial to the industrialization of graphene is its high-quality microfabric...Recently,graphene has drawn considerable attention in the field of electronics,owing to its favorable conductivity and high carrier mobility.Crucial to the industrialization of graphene is its high-quality microfabrication via chemical vapor deposition.However,many problems remain in its preparation,such as the not fully understood cracking mechanism of the carbon source,the mechanism of its substrate oxidation,and insufficient defect repair theory.To help close this capability gap,this study leverages density functional theory to explore the role of O in graphene growth.The effects of Cu substrate oxidation on carbon source cracking,nucleation barriers,crystal nucleus growth,and defect repairs are discussed.OCu was found to reduce energy change during dehydrogenation,rendering the process easier.Moreover,the adsorbed O in graphene or its Cu substrate can promote defect repair and edge growth.展开更多
Gaseous promotors have readily been adopted during the direct synthesis of graphene over insulators to enhance the growth quality and/or boost the growth rate.The understanding of the real functions of carbon-containi...Gaseous promotors have readily been adopted during the direct synthesis of graphene over insulators to enhance the growth quality and/or boost the growth rate.The understanding of the real functions of carbon-containing promotors has still remained elusive.In this study,we identify the critical roles of a representative CO_(2)promotor played in the direct growth of graphene.The comparative experimental trials validate CO_(2)as an effective modulator to decrease graphene nucleation density,improve growth kinetics,mitigate adlayer formation.The first-principles calculations illustrate that the generation of gas-phase OH species in CO_(2)-assisted system helps decrease the energy barriers of CH4 decomposition and carbon attachment to the growth front,which might be the key factor to allow high-quality direct growth.Such a CO_(2)-promoted strategy enables the conformal coating of graphene film over curved insulators,where the sheet resistance of grown graphene on quartz reaches as low as 1.26 kΩ·sq^(−1)at an optical transmittance of~95.8%.The fabricated endoscope lens based on our conformal graphene harvests an apoptosis of 82.8%for noninvasive thermal therapy.The work presented here is expected to motivate further investigations in the controllable growth of high-quality graphene on insulating substrates.展开更多
Carbon source precursor is a critical factor governing chemical vapor deposition growth of graphene films.Methane(CH4),has been the most commonly used precursor in the last decade,but it presents challenges in terms o...Carbon source precursor is a critical factor governing chemical vapor deposition growth of graphene films.Methane(CH4),has been the most commonly used precursor in the last decade,but it presents challenges in terms of decomposition efficiency and growth rate.Here we thoroughly evaluated acetylene(C2H_(2)),a precursor that is probably for providing carbon dimer(C2)species,for fast growth of large-scale graphene films.We find that the graphene growth behaviors fueled by C2H_(2) exhibit unconventional localized growth behavior with significant advantages in terms of high growth rate,which mainly ascribe to the as-decomposed C2 species.Therefore,a C2-fueled scanning growth strategy is proposed,and the fast scanning growth rate of 40 cm/min was experimentally demonstrated.This growth strategy is compatible with the approach of unidirectional growth of single-crystal graphene films,and the as-grown graphene films are of high-quality.This work demonstrates a reliable and promising strategy for the rapid synthesis of high-quality graphene film and may pave the avenue to cost-effective mass production of graphene materials in the roll-to-roll system.展开更多
Tin-based compounds are deemed as suitable anode candidates affording promising sodium-ion storages for rechargeable batteries andhybrid capacitors.However,synergistically tailoring the electrical conductivity and str...Tin-based compounds are deemed as suitable anode candidates affording promising sodium-ion storages for rechargeable batteries andhybrid capacitors.However,synergistically tailoring the electrical conductivity and structural stability of tin-based anodes to attain durablesodium-ion storages remains challenging to date for its practical applications.Herein,metal-organic framework(MOF)derived SnSe/C wrappedwithin nitrogen-doped graphene(NG@SnSe/C)is designed targeting durable sodium-ion storage.NG@SnSe/C possesses favorable electricalconductivity and structure stability due to the"inner"carbon framework from the MOF thermal treatment and"outer"graphitic cage from thedirect chemical vapor deposition synthesis.Consequently,NG@SnSe/C electrode can obtain a high reversible capacity of 650 mAh·g^-1 at 0.05 A·g^1,a favorable rate performance of 287.8 mAh·g^1 at 5 A·g^1 and a superior cycle stability with a negligible capacity decay of 0.016%percycle over 3,200 cycles at 0.4 A·g^1.Theoretical calculations reveal that the nitrogen-doping in graphene can stabilize the NG@SnSe/Cstructure and improve the electrical conductivity.The reversible Na-ion storage mechanism of SnSe is further investigated by in-situ X-raydiffraction/ex-s/tu transmission electron microscopy.Furthermore,assembled sodium-ion hybrid capacitor full-cells comprising our NG@SnSe/Canode and an active carbon cathode harvest a high energy/power density of 115.5 Wh·kg^-1/5,742 W·kg^-1,holding promise for next-generationen ergy storages.展开更多
Sodium-ion batteries (SIBs) have been increasingly attracting attention as a sustainable alternative to lithium-ion batteries for scalable energy storage. The key to advanced SIBs relies heavily upon the development...Sodium-ion batteries (SIBs) have been increasingly attracting attention as a sustainable alternative to lithium-ion batteries for scalable energy storage. The key to advanced SIBs relies heavily upon the development of reliable anodes. In this respect, Bi2S3 has been extensively investigated because of its high capacity, tailorable morpholog, and low cost However, the common practices of incorporating carbon species to enhance the electrical conductivity and accommodate the volume change of Bi2S3 anodes so as to boost their durability for Na storage have met with limited success. Herein, we report a simple method to realize the encapsulation of Bi2S3 nanorods within three-dimensional, nitrogen-doped graphene (3DNG) frameworks, targeting flexible and active composite anodes for SIBs. The Bi2S3/ 3DNG composites displayed outstanding Na storage behavior with a high reversible capacity (649 mAh·g^-1 at 62.5 mA·g^-1) and favorable durability (307 and 200 mAh·g^-1 after 100 cycles at 125 and 312.5 mA·g^-1, respectively). In-depth characterization by in situ X-ray diffraction revealed that the intriguing Na storage process of Bi2Sa was based upon a reversible reaction. Furthermore, a full, flexible SIB cell with Na0.4MnO2 cathode and as-prepared composite anode was successfully assembled, and holds a great promise for next-generation, wearable energy storage applications.展开更多
Single atoms are the ultimate minimum size limit for catalysts. Graphene, as an exciting, ultimately thin (one atom thick) material can be imaged in a transmission electron microscope with relatively few imaging art...Single atoms are the ultimate minimum size limit for catalysts. Graphene, as an exciting, ultimately thin (one atom thick) material can be imaged in a transmission electron microscope with relatively few imaging artefacts. Here, we directly observe the behavior of single Cr atoms in graphene mono- and di-vacancies and, more importantly, at graphene edges. Similar studies at graphene edges with other elemental atoms, with the exception of Fe, show catalytic etching of graphene. Fe atoms have been shown to both etch and grow graphene. In contrast, Cr atoms are only observed to induce graphene growth. Complementary theoretical calculations illuminate the differences between Fe and Cr, and confirm single Cr atoms as superior catalysts for sp^2 carbon growth.展开更多
Although the power conversion efficiency(PCE) of CH3 NH3 PbI3-based solar cells has achieved 22.1%,which is comparable to commercialized thin-film CdTe and Cu(In,Ga)Se2 solar cells, the long-term stability is the ...Although the power conversion efficiency(PCE) of CH3 NH3 PbI3-based solar cells has achieved 22.1%,which is comparable to commercialized thin-film CdTe and Cu(In,Ga)Se2 solar cells, the long-term stability is the main obstacle for the commercialization of perovskite solar cells. Recent efforts have been made to explore alternative inorganic perovskites, which were assumed to have better stability than organic-inorganic hybrid CH3 NH3 PbI3. In this short review, we will keep up with experiments and summarize recent progresses of inorganic double halide perovskite, in particular to Cs2 AgBiBr6, Cs2 AgInCl6, Cs2 InBiBr6 and their family members. We will also share our opinions on the promise of such class of materials.展开更多
基金supported by the National Natural Science Foundation of China (51702225)the National Key Research and Development Program (2016YFA0200103)+2 种基金the Natural Science Foundation of Jiangsu Province (BK20170336)the support from Suzhou Key Laboratory for Advanced Carbon MaterialsWearable Energy Technologies, Suzhou, China。
文摘Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.
基金funding support from National Natural Science Foundation of China(grant No.11674237 and 51602211)National Key Research and Development Program of China(grant No.2016YFB0700700)+2 种基金Natural Science Foundation of Jiangsu Province of China(grant No.BK20160299)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)China Post-doctoral Foundation(grant No.7131705619).
文摘Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.
基金the National Natural Science Foundation of China(Nos.T2188101,52021006,and 52072042)the National Natural Science Foundation Youth Fund(Nos.22105006 and 52202033)+2 种基金Beijing National Laboratory for Molecular Science(No.BNLMS-CXTD-202001)the National Key R&D Program of China(Nos.2016YFA0200101,2016YFA0200103,and 2018YFA0703502)the Beijing Municipal Science&Technology Commission(Nos.Z191100000819005,Z191100000819007,and Z201100008720005).
文摘Recently,graphene has drawn considerable attention in the field of electronics,owing to its favorable conductivity and high carrier mobility.Crucial to the industrialization of graphene is its high-quality microfabrication via chemical vapor deposition.However,many problems remain in its preparation,such as the not fully understood cracking mechanism of the carbon source,the mechanism of its substrate oxidation,and insufficient defect repair theory.To help close this capability gap,this study leverages density functional theory to explore the role of O in graphene growth.The effects of Cu substrate oxidation on carbon source cracking,nucleation barriers,crystal nucleus growth,and defect repairs are discussed.OCu was found to reduce energy change during dehydrogenation,rendering the process easier.Moreover,the adsorbed O in graphene or its Cu substrate can promote defect repair and edge growth.
基金the National Key R&D Program of China(Nos.2019YFA0708201 and 2019YFA0708204)the National Natural Science Foundation of China(Nos.T2188101,61527814,and 22179089)+3 种基金the Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXTD-202001)the Beijing Municipal Science and Technology Planning Project(No.Z191100000819004)the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20211503)the Suzhou Science and Technology Project-Prospective Application Research Program(No.SYG202038).
文摘Gaseous promotors have readily been adopted during the direct synthesis of graphene over insulators to enhance the growth quality and/or boost the growth rate.The understanding of the real functions of carbon-containing promotors has still remained elusive.In this study,we identify the critical roles of a representative CO_(2)promotor played in the direct growth of graphene.The comparative experimental trials validate CO_(2)as an effective modulator to decrease graphene nucleation density,improve growth kinetics,mitigate adlayer formation.The first-principles calculations illustrate that the generation of gas-phase OH species in CO_(2)-assisted system helps decrease the energy barriers of CH4 decomposition and carbon attachment to the growth front,which might be the key factor to allow high-quality direct growth.Such a CO_(2)-promoted strategy enables the conformal coating of graphene film over curved insulators,where the sheet resistance of grown graphene on quartz reaches as low as 1.26 kΩ·sq^(−1)at an optical transmittance of~95.8%.The fabricated endoscope lens based on our conformal graphene harvests an apoptosis of 82.8%for noninvasive thermal therapy.The work presented here is expected to motivate further investigations in the controllable growth of high-quality graphene on insulating substrates.
基金the National Natural Science Foundation of China(No.T2188101)the Beijing National Laboratory for Molecular Science(No.BNLMS-CXTD-202001).
文摘Carbon source precursor is a critical factor governing chemical vapor deposition growth of graphene films.Methane(CH4),has been the most commonly used precursor in the last decade,but it presents challenges in terms of decomposition efficiency and growth rate.Here we thoroughly evaluated acetylene(C2H_(2)),a precursor that is probably for providing carbon dimer(C2)species,for fast growth of large-scale graphene films.We find that the graphene growth behaviors fueled by C2H_(2) exhibit unconventional localized growth behavior with significant advantages in terms of high growth rate,which mainly ascribe to the as-decomposed C2 species.Therefore,a C2-fueled scanning growth strategy is proposed,and the fast scanning growth rate of 40 cm/min was experimentally demonstrated.This growth strategy is compatible with the approach of unidirectional growth of single-crystal graphene films,and the as-grown graphene films are of high-quality.This work demonstrates a reliable and promising strategy for the rapid synthesis of high-quality graphene film and may pave the avenue to cost-effective mass production of graphene materials in the roll-to-roll system.
基金This work was supported by the National Natural Science Foundation of China(No.51702225)the National Key Research and Development Program(No.2016YFA0200103)Natural Science Foundation of Jiangsu Province(No.BK20170336).C.L.,乙乙L.,Z.X.,H.N.C.,Y.Z.S.,L.H.Y.,W.J.Y.,J.Y.S.,and Z.F.L.acknowledge the support from Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies,Suzhou,China.
文摘Tin-based compounds are deemed as suitable anode candidates affording promising sodium-ion storages for rechargeable batteries andhybrid capacitors.However,synergistically tailoring the electrical conductivity and structural stability of tin-based anodes to attain durablesodium-ion storages remains challenging to date for its practical applications.Herein,metal-organic framework(MOF)derived SnSe/C wrappedwithin nitrogen-doped graphene(NG@SnSe/C)is designed targeting durable sodium-ion storage.NG@SnSe/C possesses favorable electricalconductivity and structure stability due to the"inner"carbon framework from the MOF thermal treatment and"outer"graphitic cage from thedirect chemical vapor deposition synthesis.Consequently,NG@SnSe/C electrode can obtain a high reversible capacity of 650 mAh·g^-1 at 0.05 A·g^1,a favorable rate performance of 287.8 mAh·g^1 at 5 A·g^1 and a superior cycle stability with a negligible capacity decay of 0.016%percycle over 3,200 cycles at 0.4 A·g^1.Theoretical calculations reveal that the nitrogen-doping in graphene can stabilize the NG@SnSe/Cstructure and improve the electrical conductivity.The reversible Na-ion storage mechanism of SnSe is further investigated by in-situ X-raydiffraction/ex-s/tu transmission electron microscopy.Furthermore,assembled sodium-ion hybrid capacitor full-cells comprising our NG@SnSe/Canode and an active carbon cathode harvest a high energy/power density of 115.5 Wh·kg^-1/5,742 W·kg^-1,holding promise for next-generationen ergy storages.
文摘Sodium-ion batteries (SIBs) have been increasingly attracting attention as a sustainable alternative to lithium-ion batteries for scalable energy storage. The key to advanced SIBs relies heavily upon the development of reliable anodes. In this respect, Bi2S3 has been extensively investigated because of its high capacity, tailorable morpholog, and low cost However, the common practices of incorporating carbon species to enhance the electrical conductivity and accommodate the volume change of Bi2S3 anodes so as to boost their durability for Na storage have met with limited success. Herein, we report a simple method to realize the encapsulation of Bi2S3 nanorods within three-dimensional, nitrogen-doped graphene (3DNG) frameworks, targeting flexible and active composite anodes for SIBs. The Bi2S3/ 3DNG composites displayed outstanding Na storage behavior with a high reversible capacity (649 mAh·g^-1 at 62.5 mA·g^-1) and favorable durability (307 and 200 mAh·g^-1 after 100 cycles at 125 and 312.5 mA·g^-1, respectively). In-depth characterization by in situ X-ray diffraction revealed that the intriguing Na storage process of Bi2Sa was based upon a reversible reaction. Furthermore, a full, flexible SIB cell with Na0.4MnO2 cathode and as-prepared composite anode was successfully assembled, and holds a great promise for next-generation, wearable energy storage applications.
基金The following are gratefully acknowledged. The National Natural Science Foundation of China (No. 51672181), the National Science Center for the financial support within the frame of the Sonata Program (No. 2014/13/D/ST5/02853) and the Opus program (No. 2015/19/B/ST5/03399).
文摘Single atoms are the ultimate minimum size limit for catalysts. Graphene, as an exciting, ultimately thin (one atom thick) material can be imaged in a transmission electron microscope with relatively few imaging artefacts. Here, we directly observe the behavior of single Cr atoms in graphene mono- and di-vacancies and, more importantly, at graphene edges. Similar studies at graphene edges with other elemental atoms, with the exception of Fe, show catalytic etching of graphene. Fe atoms have been shown to both etch and grow graphene. In contrast, Cr atoms are only observed to induce graphene growth. Complementary theoretical calculations illuminate the differences between Fe and Cr, and confirm single Cr atoms as superior catalysts for sp^2 carbon growth.
文摘Although the power conversion efficiency(PCE) of CH3 NH3 PbI3-based solar cells has achieved 22.1%,which is comparable to commercialized thin-film CdTe and Cu(In,Ga)Se2 solar cells, the long-term stability is the main obstacle for the commercialization of perovskite solar cells. Recent efforts have been made to explore alternative inorganic perovskites, which were assumed to have better stability than organic-inorganic hybrid CH3 NH3 PbI3. In this short review, we will keep up with experiments and summarize recent progresses of inorganic double halide perovskite, in particular to Cs2 AgBiBr6, Cs2 AgInCl6, Cs2 InBiBr6 and their family members. We will also share our opinions on the promise of such class of materials.