Topochemical transformation has emerged as a promising method for fabricating two-dimensional (2D) materials with precise control over their composition and morphology. However, the large-scale synthesis of ultrathin ...Topochemical transformation has emerged as a promising method for fabricating two-dimensional (2D) materials with precise control over their composition and morphology. However, the large-scale synthesis of ultrathin 2D materials with controllable thickness remains a tremendous challenge. Herein, we adopt an efficient topochemical synthesis strategy, employing a confined reaction space to fabricate ultrathin 2D Sn_(4)P_(3) nanosheets in large-scale. By carefully adjusting the rolling number during the processing of Sn/Al foils, we have successfully fabricated Sn_(4)P_(3) nanosheets with varied layer thicknesses, achieving a remarkable minimum thickness of two layers (~ 2.2 nm). Remarkably, the bilayer Sn_(4)P_(3) nanosheets display an exceptional initial capacity of 1088 mAh·g^(−1), nearing the theoretical value of 1230 mAh·g^(−1). Furthermore, we reveal their high-rate property as well as outstanding cyclic stability, maintaining capacity without fading more than 3000 cycles. By precisely controlling the layer thickness and ensuring nanoscale uniformity, we enhance the lithium cycling performance of Sn_(4)P_(3), marking a significant advancement in developing high-performance energy storage systems.展开更多
In this work,a novel bamboo-like carbon nanotubes@Sn4P3@carbon(BLCNTs@Sn_(4)P_(3)@C)coaxial nanotubes are designed and prepared using a newly developed hydrothermal method followed by a phophidation process.The prepar...In this work,a novel bamboo-like carbon nanotubes@Sn4P3@carbon(BLCNTs@Sn_(4)P_(3)@C)coaxial nanotubes are designed and prepared using a newly developed hydrothermal method followed by a phophidation process.The prepared Sn_(4)P_(3) nanoparticles are uniformly coated and wrapped on the one-dimensional(1D)bamboo-like CNTs,which is covered by a uniform carbon layer to form a sandwich-like structure with Sn_(4)P_(3) in between.The inner CNT and outer carbon can effectively maintain the structural stability and serve as the good electron conductors.Additionally,the outer carbon coating layer can effectively keep BLCNTs@Sn_(4)P_(3)@C nanotubes separate each other,preventing aggregation of Sn_(4)P_(3) during charge/discharge when this material is used as anode for sodium ion batteries.The anode of BLCNTs@Sn_(4)P_(3)@C shows excellent reversible capacity and a long cycling of over 2000 cycles.The unique design of coaxial nanotubes is greatly beneficial to the electrochemical performance of Sn_(4)P_(3) for sodium ion storage.展开更多
Nanostructured metal phosphides are very attractive materials in energy storage and conversion,but their applications are severely limited by complicated preparation steps,harsh conditions and large excess of highly t...Nanostructured metal phosphides are very attractive materials in energy storage and conversion,but their applications are severely limited by complicated preparation steps,harsh conditions and large excess of highly toxic phosphorus source.Here we develop a highly efficient one-step method to synthesize Sn_(4)P_(3)nanostructure based on simultaneous reduction of SnCl_(4)and PCl_(3)on mechanically activated Na surface and in situ phosphorization.The low-toxic PCl3 displays a very high phosphorizing efficiency(100%).Furthermore,this simple method is powerful to control phosphide size.Ultrafine Sn_(4)P_(3)nanocrystals(<5 nm)supported on carbon sheets(Sn_(4)P_(3)/C)are obtained,which is due to the unique bottom-up surface-limited reaction.As the anode material for sodium/lithium ion batteries(SIBs/LIBs),the Sn_(4)P_(3)/C shows profound sodiation/lithiation extents,good phase-conversion reversibility,excellent rate performance and long cycling stability,retaining high capacities of 420 mAh/g for SIBs and 760 mAh/g for LIBs even after 400 cycles at 1.0 A/g.Combining simple and efficient preparation,low-toxic and high-efficiency phosphorus source and good control of nanosize,this method is very promising for low-cost and scalable preparation of high-performance Sn_(4)P_(3)anode.展开更多
The potential application of high-capacity Sn_(4)P_(3)anode for potassium-ion batteries(PIBs)is hindered by the poor cycle stability mainly rooted from the huge volume changes upon cycling and low electronic conduc-ti...The potential application of high-capacity Sn_(4)P_(3)anode for potassium-ion batteries(PIBs)is hindered by the poor cycle stability mainly rooted from the huge volume changes upon cycling and low electronic conduc-tivity.To address the above issues,sandwich-like struc-tured Sn_(4)P_(3)/Ti_(3)C_(2)T_(x)was designed and synthesized as anode material for PIBs.As a result,Sn_(4)P_(3)/Ti_(3)C_(2)T_(x)pre-sents superior cycle stability(retains a capacity of 103.2 mAh·g^(-1)even after 300 cycles at 1000 mA·g^(-1))and rate capability(delivers 60.7 mAh·g^(-1)at high current density of 2000 mA·g^(-1)).The excellent electrochemical perfor-mance of sandwich-like structured Sn_(4)P_(3)/Ti_(3)C_(2)Tx is orig-inated from the synergistic effect between Sn_(4)P_(3)and Ti_(3)C_(2)T_(x),where Ti_(3)C_(2)T_(x)acts as a conductive matrix to facilitate electron transfer and buffer the volume change of Sn_(4)P_(3)particles upon cycling,while Sn_(4)P_(3)serves as pillars to prevent the collapse and stacking of Ti_(3)C_(2)T_(x)sheets.Moreover,significant capacitive contribution is demonstrated as a major contributor to the excellent rate capability.展开更多
Tin phosphide(Sn_(4)P_(3))is a promising anode material for sodium-ion batteries because of its relatively large theoretical capacity,appropriate Na^(+) alloying potential,and good cyclic stability.Herein,the Sn_(4)P_...Tin phosphide(Sn_(4)P_(3))is a promising anode material for sodium-ion batteries because of its relatively large theoretical capacity,appropriate Na^(+) alloying potential,and good cyclic stability.Herein,the Sn_(4)P_(3) embedded into a carbon matrix with good rate performance and long cycle life is reported.The Sn_(4)P_(3)-C composite exhibits excellent rate performance(540 mAh g^(-1) at 5 A g^(-1))and the highest reversible capacity(844 mAh g^(-1) at 0.5 A ^(g-1))among Sn4P3-based anodes reported so far.Its reversible capacity is as high as 705 mAh g^(-1) even after 100 cycles at 0.5 A g^(-1).Besides,its initial Coulomb efficiency can reach 85.6%,with the average Coulomb efficiency exceeding 99.75%from the 3rd to 100th cycles.Na_(2)C_(6)O_(6) is firstly used as a cathode when Sn_(4)P_(3) acts as anode,and the Na-Sn_(4)P_(3)-C//Na_(2)C_(6)O_(6) full cell shows excellent electrochemical performance.These results demonstrate that the Sn_(4)P_(3)-C composite prepared in this work displays high-rate capability and superior cyclic performance,and thus is a potential anode for sodium ion batteries.展开更多
Sodium-ion capacitors(NICs)trigger considerable attention due to their higher specific energy than electrical double-layer capacitors(EDLCs)at comparable specific power.However,the presodiation process of the anodic h...Sodium-ion capacitors(NICs)trigger considerable attention due to their higher specific energy than electrical double-layer capacitors(EDLCs)at comparable specific power.However,the presodiation process of the anodic host is extremely crucial for the construction of high-performance NICs.Herein,a positive EDL electrode containing activated carbon(AC)mixed with sodium cyanide(NaCN)as a sacrificial material was electrochemically oxidized to presodiate a Sn_(4)P_(3) anodic host buffered by hard carbon(HC).The oxidation of CN-occurred ca.2.9 V vs.Na/Na+and finished by a short region of linearly increasing potential with a total capacity close to the theoretical value of 547 mAh g^(-1).The operando electrochemical mass spectrometry(EMS)analysis of the atmosphere in the cell together with the internal pressure measurements realized during the galvanostatic oxidation of a YP80F-NaCN electrode demonstrate that the process occurs without any gas evolution.A precursor cell of an NIC was constructed in a pouch with YP80FNaCN and HC/Sn_(4)P_(3) electrodes.After the oxidative sodium transfer from NaCN to HC/Sn_(4)P_(3),the realized YP80F//Nax(HC/Sn_(4)P_(3))NIC demonstrated a discharge capacitance retention higher than 80%for 8900 cycles in the voltage range from 2.0 to 3.8 V.The infrared analysis of the anode obtained by the herein described transfer process detected polycyanogen,which stabilizes the electrode structure during cycling,and thereof is at the origin of the enhanced life span of the NIC.展开更多
基金supported partially by project of the National Natural Science Foundation of China(Nos.52102203 and 51972110)Beijing Science and Technology Project(No.Z211100004621010)+4 种基金Beijing Natural Science Foundation(No.2222076)State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(No.LAPS202114)Huaneng Group Headquarters Science and Technology Project(No.HNKJ20-H88)2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education,the Fundamental Research Funds for the Central Universities(No.2024MS082)the NCEPU “Double First- Class” Program.
文摘Topochemical transformation has emerged as a promising method for fabricating two-dimensional (2D) materials with precise control over their composition and morphology. However, the large-scale synthesis of ultrathin 2D materials with controllable thickness remains a tremendous challenge. Herein, we adopt an efficient topochemical synthesis strategy, employing a confined reaction space to fabricate ultrathin 2D Sn_(4)P_(3) nanosheets in large-scale. By carefully adjusting the rolling number during the processing of Sn/Al foils, we have successfully fabricated Sn_(4)P_(3) nanosheets with varied layer thicknesses, achieving a remarkable minimum thickness of two layers (~ 2.2 nm). Remarkably, the bilayer Sn_(4)P_(3) nanosheets display an exceptional initial capacity of 1088 mAh·g^(−1), nearing the theoretical value of 1230 mAh·g^(−1). Furthermore, we reveal their high-rate property as well as outstanding cyclic stability, maintaining capacity without fading more than 3000 cycles. By precisely controlling the layer thickness and ensuring nanoscale uniformity, we enhance the lithium cycling performance of Sn_(4)P_(3), marking a significant advancement in developing high-performance energy storage systems.
基金supported by National Natural Science Foundation of China(51772051,51872071)Natural Science Foundation of Guangdong Province(2016A030310127)+3 种基金Support Funding for Innovation Projects for Overseas Students in Anhui Province(2020LCX031)supported by the Foundation of High-level Talents(GB200902-30,No.196100041018)the Foundation of Regular Research Team(TDYB2019007,No.196100043028)the Foundation of Doctor'sWorkstation of MCNAIR NEW POWER CO.,LTD(GC200104-40,No.186100030017)at Dongguan University of Technology.
文摘In this work,a novel bamboo-like carbon nanotubes@Sn4P3@carbon(BLCNTs@Sn_(4)P_(3)@C)coaxial nanotubes are designed and prepared using a newly developed hydrothermal method followed by a phophidation process.The prepared Sn_(4)P_(3) nanoparticles are uniformly coated and wrapped on the one-dimensional(1D)bamboo-like CNTs,which is covered by a uniform carbon layer to form a sandwich-like structure with Sn_(4)P_(3) in between.The inner CNT and outer carbon can effectively maintain the structural stability and serve as the good electron conductors.Additionally,the outer carbon coating layer can effectively keep BLCNTs@Sn_(4)P_(3)@C nanotubes separate each other,preventing aggregation of Sn_(4)P_(3) during charge/discharge when this material is used as anode for sodium ion batteries.The anode of BLCNTs@Sn_(4)P_(3)@C shows excellent reversible capacity and a long cycling of over 2000 cycles.The unique design of coaxial nanotubes is greatly beneficial to the electrochemical performance of Sn_(4)P_(3) for sodium ion storage.
基金support from the National Natural Science Foundation of China(Nos.51972075 and 51772059)the Natural Science Foundation of Heilongjiang Province(No.ZD2019E004)the Fundamental Research funds for the Central Universities.
文摘Nanostructured metal phosphides are very attractive materials in energy storage and conversion,but their applications are severely limited by complicated preparation steps,harsh conditions and large excess of highly toxic phosphorus source.Here we develop a highly efficient one-step method to synthesize Sn_(4)P_(3)nanostructure based on simultaneous reduction of SnCl_(4)and PCl_(3)on mechanically activated Na surface and in situ phosphorization.The low-toxic PCl3 displays a very high phosphorizing efficiency(100%).Furthermore,this simple method is powerful to control phosphide size.Ultrafine Sn_(4)P_(3)nanocrystals(<5 nm)supported on carbon sheets(Sn_(4)P_(3)/C)are obtained,which is due to the unique bottom-up surface-limited reaction.As the anode material for sodium/lithium ion batteries(SIBs/LIBs),the Sn_(4)P_(3)/C shows profound sodiation/lithiation extents,good phase-conversion reversibility,excellent rate performance and long cycling stability,retaining high capacities of 420 mAh/g for SIBs and 760 mAh/g for LIBs even after 400 cycles at 1.0 A/g.Combining simple and efficient preparation,low-toxic and high-efficiency phosphorus source and good control of nanosize,this method is very promising for low-cost and scalable preparation of high-performance Sn_(4)P_(3)anode.
基金financially supported by the National Natural Science Foundation of China (No. 52100084)Shenzhen Natural Science Fund (No. GXWD2020123015542700320200824094017001)
文摘The potential application of high-capacity Sn_(4)P_(3)anode for potassium-ion batteries(PIBs)is hindered by the poor cycle stability mainly rooted from the huge volume changes upon cycling and low electronic conduc-tivity.To address the above issues,sandwich-like struc-tured Sn_(4)P_(3)/Ti_(3)C_(2)T_(x)was designed and synthesized as anode material for PIBs.As a result,Sn_(4)P_(3)/Ti_(3)C_(2)T_(x)pre-sents superior cycle stability(retains a capacity of 103.2 mAh·g^(-1)even after 300 cycles at 1000 mA·g^(-1))and rate capability(delivers 60.7 mAh·g^(-1)at high current density of 2000 mA·g^(-1)).The excellent electrochemical perfor-mance of sandwich-like structured Sn_(4)P_(3)/Ti_(3)C_(2)Tx is orig-inated from the synergistic effect between Sn_(4)P_(3)and Ti_(3)C_(2)T_(x),where Ti_(3)C_(2)T_(x)acts as a conductive matrix to facilitate electron transfer and buffer the volume change of Sn_(4)P_(3)particles upon cycling,while Sn_(4)P_(3)serves as pillars to prevent the collapse and stacking of Ti_(3)C_(2)T_(x)sheets.Moreover,significant capacitive contribution is demonstrated as a major contributor to the excellent rate capability.
基金supported by the Elements Strategy Initiative for Catalysts and Batteries,MEXT,Japan(Grant Number JPMXP0112101003).
文摘Tin phosphide(Sn_(4)P_(3))is a promising anode material for sodium-ion batteries because of its relatively large theoretical capacity,appropriate Na^(+) alloying potential,and good cyclic stability.Herein,the Sn_(4)P_(3) embedded into a carbon matrix with good rate performance and long cycle life is reported.The Sn_(4)P_(3)-C composite exhibits excellent rate performance(540 mAh g^(-1) at 5 A g^(-1))and the highest reversible capacity(844 mAh g^(-1) at 0.5 A ^(g-1))among Sn4P3-based anodes reported so far.Its reversible capacity is as high as 705 mAh g^(-1) even after 100 cycles at 0.5 A g^(-1).Besides,its initial Coulomb efficiency can reach 85.6%,with the average Coulomb efficiency exceeding 99.75%from the 3rd to 100th cycles.Na_(2)C_(6)O_(6) is firstly used as a cathode when Sn_(4)P_(3) acts as anode,and the Na-Sn_(4)P_(3)-C//Na_(2)C_(6)O_(6) full cell shows excellent electrochemical performance.These results demonstrate that the Sn_(4)P_(3)-C composite prepared in this work displays high-rate capability and superior cyclic performance,and thus is a potential anode for sodium ion batteries.
基金the Foundation for Polish Science(FNP)for funding the HYCAP project(research grant TEAM TECH/POIR.04.04.00-00-3D6F/16-00)carried out within the TEAM TECH program co-financed by the European Union under the European Regional Development Fund。
文摘Sodium-ion capacitors(NICs)trigger considerable attention due to their higher specific energy than electrical double-layer capacitors(EDLCs)at comparable specific power.However,the presodiation process of the anodic host is extremely crucial for the construction of high-performance NICs.Herein,a positive EDL electrode containing activated carbon(AC)mixed with sodium cyanide(NaCN)as a sacrificial material was electrochemically oxidized to presodiate a Sn_(4)P_(3) anodic host buffered by hard carbon(HC).The oxidation of CN-occurred ca.2.9 V vs.Na/Na+and finished by a short region of linearly increasing potential with a total capacity close to the theoretical value of 547 mAh g^(-1).The operando electrochemical mass spectrometry(EMS)analysis of the atmosphere in the cell together with the internal pressure measurements realized during the galvanostatic oxidation of a YP80F-NaCN electrode demonstrate that the process occurs without any gas evolution.A precursor cell of an NIC was constructed in a pouch with YP80FNaCN and HC/Sn_(4)P_(3) electrodes.After the oxidative sodium transfer from NaCN to HC/Sn_(4)P_(3),the realized YP80F//Nax(HC/Sn_(4)P_(3))NIC demonstrated a discharge capacitance retention higher than 80%for 8900 cycles in the voltage range from 2.0 to 3.8 V.The infrared analysis of the anode obtained by the herein described transfer process detected polycyanogen,which stabilizes the electrode structure during cycling,and thereof is at the origin of the enhanced life span of the NIC.
