A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of allo...A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, electron probe microanalyzer （EPMA）, X-ray photoelectron spectroscopy （XPS）, inductively coupled plasma atomic emission spectrometry （ICP）, cyclic voltammetry （CV）, and galvanostatic charge/discharge （GC） measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.展开更多
The formation of solid electrolyte interphase(SEI) and ion intercalation are two key processes in rechargeable batteries, which need to be explored under dynamic operating conditions. In this work, both planar and san...The formation of solid electrolyte interphase(SEI) and ion intercalation are two key processes in rechargeable batteries, which need to be explored under dynamic operating conditions. In this work, both planar and sandwich model lithium batteries consisting of Li metal | ionic liquid electrolyte | graphite electrode have been constructed and investigated by a series of in situ surface analysis platforms including atomic force microscopy, Raman and X-ray photoelectron spectroscopy. It is found that the choice of electrolyte, including the concentration and contents, has a profound effect on the SEI formation and evolution, and the subsequent ion intercalation. A smooth and compact SEI is preferably produced in highconcentration electrolytes, with FSI^(-) salt superior to TFSI^(-) salt, facilitating the lithiation/delithiation to achieve high capacity and excellent cycle stability, while suppressing the co-intercalation of electrolyte solvent ions. The innovative research scenario of well-defined model batteries in combination with multiple genuinely in situ surface analysis methods presented herein leads to insightful results, which provide valuable strategies for the rational design and optimization of practical batteries, and energy storage devices in general.展开更多
Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Here...Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Herein,the cation intercalation and ion-exchange were well employed to achieve a K+and Ca2+intercalated V2CTxMXene.A larger interlayer distance and low F surface terminations were thereof obtained,which accelerates the ion transport and promotes the delicate surface of V2CTx MXene.As a result,a package of enhanced capacity,rate performance and cyclability can be achieved.Furthermore,the ion exchange approach can be extended to other 2 D layered materials,and both the interlayer control and the surface modification will be achieved.展开更多
Inspired by a well-known architecture notion that load-bearing walls enable maintaining a highly-stable multiple-floored building,superior advantages are afforded via fabricating the NH_(4)+ions pre-intercalated Mo_(2...Inspired by a well-known architecture notion that load-bearing walls enable maintaining a highly-stable multiple-floored building,superior advantages are afforded via fabricating the NH_(4)+ions pre-intercalated Mo_(2)CT_(x) MXene(Mo_(2)CT_(x)-N)in a mixed solution of NH_(4)F and HCl via a simple one-step hydrothermal method.As a result of the synergistic effects of pillared structure,immobilizing-F groups and unlocking Mo-based redox,the Mo_(2)CT_(x)-N remarkably delivered a reversible capacity of 384.6 mAh ^(g-1) at 200 mA g^(-1) after 100 cycles.Our work lays a foundation for fully packaging its optimal performance via carding and architecting the chemistry of the MXene layers and between them.展开更多
The intercalation of foreign species into MXene, as an approach of tuning the interlayer environment, is employed to improve electrochemical ion storage behaviors. Herein, to understand the effect of confined ions by ...The intercalation of foreign species into MXene, as an approach of tuning the interlayer environment, is employed to improve electrochemical ion storage behaviors. Herein, to understand the effect of confined ions by the MXene layers on the performance of electrochemical energy storage, Zn^(2+) ions were employed to intercalate into MXene via an electrochemical technique. Zn^(2+) ions induced a shrink of the adjacent MXene layers. Meaningfully, a higher capacity of lithium ion storage was obtained after Zn^(2+) preintercalation. In order to explore the roles of the intercalated Zn^(2+) ions, the structural evolution, and the electronic migration among Zn, Ti and the surface termination were investigated to trace the origination of the higher Li^(+) storage capacity. The pre-intercalated Zn^(2+) ions lost electrons, meanwhile Ti of MXene obtained electrons. Moreover, a low-F surface functional groups was achieved. Contrary to the first shrink, after 200 cycles, a larger interlayer distance was monitored, this can accelerate the ion transport and offer a larger expansile space for lithium storage. This may offer a guidance to understand the roles of the confined ion by two-dimensional(2D) layered materials.展开更多
With the development of stable alkali metal anodes,V_(2)O_(5) is gaining traction as a cathode material due to its high theoretical capacity and the ability to intercalate Li,Na and K ions.Herein,we report a method fo...With the development of stable alkali metal anodes,V_(2)O_(5) is gaining traction as a cathode material due to its high theoretical capacity and the ability to intercalate Li,Na and K ions.Herein,we report a method for synthesizing structured orthorhombic V_(2)O_(5) microspheres and investigate Li intercalation/deintercalation into this material.For industry adoption,the electrochemical behavior of V_(2)O_(5) as well as structural and phase transformation attributing to Li intercalation reaction must be further investigated.Our synthesized V_(2)O_(5) microspheres consisted of small primary particles that were strongly joined together and exhibited good cycle stability and rate capability,triggered by reversible volume change and rapid Li ion diffusion.In addition,the reversibility of phase transformation(a,e,d,c and xLixV_(2)O_(5))and valence state evolution(5+,4+,and 3.5+)during intercalation/de-intercalation were studied via in-situ X-ray powder diffraction and X-ray absorption near edge structure analyses.展开更多
Chemical oxidation and metal intercalation of natural graphite was utilized to increase the capacity and enhance the cycle property of graphite anodes in lithium ion batteries.
MXene is a new intercalation pseudocapacitive electrode material for supercapacitor application.Intensifying fast ion diffusion is significantly essential for MXene to achieve excellent electrochemical performance.The...MXene is a new intercalation pseudocapacitive electrode material for supercapacitor application.Intensifying fast ion diffusion is significantly essential for MXene to achieve excellent electrochemical performance.The expansion of interlayer void by traditional spontaneous species intercalation always leads to a slight increase in capacitance due to the existence of species sacrificing the smooth diffusion of electrolyte ions.Herein,an effective intercalation-deintercalation interlayer design strategy is proposed to help MXene achieve higher capacitance.Electrochemical cation intercalation leads to the expansion of interlayer space.After electrochemical cation extraction,intercalated cations are deintercalated mostly,leaving a small number of cations trapped in the interlayer silt and serving as pillars to maintain the interlayer space,offering an open,unobstructed interlayer space for better ion migration and storage.Also,a preferred surface with more-O terminations for redox reaction is created due to the reaction between cations and-OH terminations.As a result,the processed MXene delivers a much improved capacitance compared to that of the original Ti_(3)C_(2)T_(x)electrode(T stands for the surface termination groups,such as-OH,-F,and-O).This study demonstrates an improvement of electrochemical performance of MXene electrodes by controlling the interlayer structure and surface chemistry.展开更多
Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 was prepared by wet chemical route. The phase,surface morphology,and electrochemical properties of the prepared powders were characterized by X-ray diffraction,scanning electron mi...Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 was prepared by wet chemical route. The phase,surface morphology,and electrochemical properties of the prepared powders were characterized by X-ray diffraction,scanning electron micrograph,and galvanostatic charge-discharge experiments. Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 has similar X-ray diffraction patterns as LiMn2O4. The corner and border of Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 particles are not as clear as the uncoated one. The two powders show similar values of l...展开更多
FeCI3-intercalated graphite intercalation compounds (GICs) with high reversible capacity and high volumetric energy density are attractive anode material alternatives of commercial graphite. However, the rapid capacit...FeCI3-intercalated graphite intercalation compounds (GICs) with high reversible capacity and high volumetric energy density are attractive anode material alternatives of commercial graphite. However, the rapid capacity decay, which was induced by chloride dissolution and shuttling issues, hindered their practical application. To address this problem, here, we introduce flake-like Fe2O3 species with inherently polar surface on the edge of FeCl3 -intercalated GICs through microwave-assisted transformation of a fraction of FeCl3 component. Theoretical simulations and physical/electrochemical studies demonstrate that the introduced Fe2O3 component can afford sufficient polar active sites for chemically bonding the soluble FeCl3 and LiCl species based on the polar-polar interaction mechanism, further inhibiting the outward diffusion of the chlorides and immobilizing them within the GIC material. In a lithium ion cell, the FeCl3 -intercalated GIC with a suitable Fe2O3 content shows remarkably improved cycling stability with a high reversible capacity of 1,041 mAh·g^-1 at a current density of 200 mA·g^-1. Capacity retention of 91 % is achieved at a high current density of 1,000 mA·g^-1 over 300 cycles. This work opens up the new prospect for immobilizing chlorides by introducing inorganic species in GIC for long-cycle electrochemical batteries.展开更多
Weak ion diffusion and electron transport due to limited interlayer spacing and poor electrical conductivity have been identified as critical roadbacks for fast and abundant energy storage of both MoS2-based lithium i...Weak ion diffusion and electron transport due to limited interlayer spacing and poor electrical conductivity have been identified as critical roadbacks for fast and abundant energy storage of both MoS2-based lithium ion batteries (LIBs) and sodium ion batteries (SIBs). In this work, MoS2 porous-hollow nanorods (MoS2/m-C800) have been designed and synthesized via an annealing-followed chemistry-intercalated strategy to solve the two issues. They are uniformly assembled from ultrathin MoS2 nanosheets, deviated to the rod-axis direction, with expanded interlayer spacing due to alternate intercalation of N-doped carbon monolayers between the adjacent MoS2 monolayers. Electrochemical studies of the MoS2/m-C800 sample, as an anode of LIBs, demonstrate that the superstructure can deliver a reversible discharge capacity of 1,170 mAh·g^-1 after 100 cycles at 0.2 A·g^-1 and maintain a reversible capacity of 951 mAh·g^-1 at 1.25 A·g^-1 after 350 cycles. While for SIBs, the superstructure also delivers a reversible discharge capacity of 350 mAh·g^-1 at 0.5 A-g-1 after 500 cycles and exhibits superior rate capacity of 238 mAh·g^-1 at 15 A·g^-1 .The excellent electrochemical performance is closely related with the hierarchical superstructures, including expanded interlayer spacing, alternate intercalation of carbon monolayers and mesoporous feature, which effectively reduce ion diffusion barrier, shorten ion diffusion paths and improve electrical conductivity.展开更多
Two expressions are introduced to calculate the lithium ion diffusion coefficients in graphite anode as a function of potentials when potentiostatic intermittent titration technique(PITT) is used. The lithium ion diff...Two expressions are introduced to calculate the lithium ion diffusion coefficients in graphite anode as a function of potentials when potentiostatic intermittent titration technique(PITT) is used. The lithium ion diffusion coefficients in graphite derived from effective surface area, which is measured by electrochemical method, are more reliable than those derived simply from radius of graphite particles(calculated from equation (3) and equation (2) respectively). The curves of dQ/dE vs E demonstrate that there are three reversible phase transitions during intercalation or deintercalation of lithium ion in graphite. In the vicinity of the potentials where phase transitions take place, the lithium ion diffusion coefficients in graphite material have three minima in the potential range 10～ 600 mV.展开更多
基金the National Nature Science Foundation of China (Nos. 50771046 and 20373016) the Natural Science Foundation of Guangdong Province (No. 05200534)the Key Projects of Guangdong Province and Guangzhou City, China (Nos. 2006A10704003 and 2006Z3-D2031)
文摘A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, electron probe microanalyzer （EPMA）, X-ray photoelectron spectroscopy （XPS）, inductively coupled plasma atomic emission spectrometry （ICP）, cyclic voltammetry （CV）, and galvanostatic charge/discharge （GC） measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.
基金financially supported by the National Key R&D Program of China(No.2016YFA0200200)the National Natural Science Foundation of China(Nos.21688102 and 21825203)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17020000)。
文摘The formation of solid electrolyte interphase(SEI) and ion intercalation are two key processes in rechargeable batteries, which need to be explored under dynamic operating conditions. In this work, both planar and sandwich model lithium batteries consisting of Li metal | ionic liquid electrolyte | graphite electrode have been constructed and investigated by a series of in situ surface analysis platforms including atomic force microscopy, Raman and X-ray photoelectron spectroscopy. It is found that the choice of electrolyte, including the concentration and contents, has a profound effect on the SEI formation and evolution, and the subsequent ion intercalation. A smooth and compact SEI is preferably produced in highconcentration electrolytes, with FSI^(-) salt superior to TFSI^(-) salt, facilitating the lithiation/delithiation to achieve high capacity and excellent cycle stability, while suppressing the co-intercalation of electrolyte solvent ions. The innovative research scenario of well-defined model batteries in combination with multiple genuinely in situ surface analysis methods presented herein leads to insightful results, which provide valuable strategies for the rational design and optimization of practical batteries, and energy storage devices in general.
基金financial support provided by the National Natural Science Foundation of China(No.51932005)Liao Ning Revitalization Talents Program(XLYC1807175)+4 种基金the Joint Research Fund Liaoning Shenyang National Laboratory for Materials Science(SYNL)(20180510047)the Research Fund of SYNL(L2019F38)the Youth Innovation Promotion Association CAS(2015152)the Program for the Development of Science and Technology of Jilin Province(No.20190201309JC)the Project of Development and Reform Commission of Jilin Province(No.2019C042-1)。
文摘Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Herein,the cation intercalation and ion-exchange were well employed to achieve a K+and Ca2+intercalated V2CTxMXene.A larger interlayer distance and low F surface terminations were thereof obtained,which accelerates the ion transport and promotes the delicate surface of V2CTx MXene.As a result,a package of enhanced capacity,rate performance and cyclability can be achieved.Furthermore,the ion exchange approach can be extended to other 2 D layered materials,and both the interlayer control and the surface modification will be achieved.
基金Supported by the National Natural Science Foundation of China(51932003,51872115)2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(20200801001GH)+1 种基金the Science and Technology Research Project of Education Department of Jilin Province(JJKH20210453KJ,JJKH20210449KJ)the Joint Research Fund of Key Laboratory of Functional Materials Physics and Chemistry(Jilin Normal University)Ministry of Education(202101)。
文摘Inspired by a well-known architecture notion that load-bearing walls enable maintaining a highly-stable multiple-floored building,superior advantages are afforded via fabricating the NH_(4)+ions pre-intercalated Mo_(2)CT_(x) MXene(Mo_(2)CT_(x)-N)in a mixed solution of NH_(4)F and HCl via a simple one-step hydrothermal method.As a result of the synergistic effects of pillared structure,immobilizing-F groups and unlocking Mo-based redox,the Mo_(2)CT_(x)-N remarkably delivered a reversible capacity of 384.6 mAh ^(g-1) at 200 mA g^(-1) after 100 cycles.Our work lays a foundation for fully packaging its optimal performance via carding and architecting the chemistry of the MXene layers and between them.
基金supported by the Development Plan of Science and Technology of Jilin Province (20190201309JC,YDZJ202101ZYTS187)the Project of Development and Reform Commission of Jilin Provinve (2019C042-1)+3 种基金the Science and Technology Research Project of Education Department of Jilin Province(JJKH20210453KJ, JJKH20210449KJ)the National Natural Science Foundation of China (51932005)the Liaoning Revitalization Talents Program (XLYC1807175)the Research Fund of Shenyang National Laboratory for Materials Science。
文摘The intercalation of foreign species into MXene, as an approach of tuning the interlayer environment, is employed to improve electrochemical ion storage behaviors. Herein, to understand the effect of confined ions by the MXene layers on the performance of electrochemical energy storage, Zn^(2+) ions were employed to intercalate into MXene via an electrochemical technique. Zn^(2+) ions induced a shrink of the adjacent MXene layers. Meaningfully, a higher capacity of lithium ion storage was obtained after Zn^(2+) preintercalation. In order to explore the roles of the intercalated Zn^(2+) ions, the structural evolution, and the electronic migration among Zn, Ti and the surface termination were investigated to trace the origination of the higher Li^(+) storage capacity. The pre-intercalated Zn^(2+) ions lost electrons, meanwhile Ti of MXene obtained electrons. Moreover, a low-F surface functional groups was achieved. Contrary to the first shrink, after 200 cycles, a larger interlayer distance was monitored, this can accelerate the ion transport and offer a larger expansile space for lithium storage. This may offer a guidance to understand the roles of the confined ion by two-dimensional(2D) layered materials.
基金supported by both the Technology Innovation Program(20004958,Development of ultra-high performance supercapacitor and high power module)funded by the Ministry of Trade,Industry and Energy(MOTIE)the R&D Convergence Program(CAP-15-02-KBSI)of the National Research Council of Science&Technology,Republic of Korea。
文摘With the development of stable alkali metal anodes,V_(2)O_(5) is gaining traction as a cathode material due to its high theoretical capacity and the ability to intercalate Li,Na and K ions.Herein,we report a method for synthesizing structured orthorhombic V_(2)O_(5) microspheres and investigate Li intercalation/deintercalation into this material.For industry adoption,the electrochemical behavior of V_(2)O_(5) as well as structural and phase transformation attributing to Li intercalation reaction must be further investigated.Our synthesized V_(2)O_(5) microspheres consisted of small primary particles that were strongly joined together and exhibited good cycle stability and rate capability,triggered by reversible volume change and rapid Li ion diffusion.In addition,the reversibility of phase transformation(a,e,d,c and xLixV_(2)O_(5))and valence state evolution(5+,4+,and 3.5+)during intercalation/de-intercalation were studied via in-situ X-ray powder diffraction and X-ray absorption near edge structure analyses.
文摘Chemical oxidation and metal intercalation of natural graphite was utilized to increase the capacity and enhance the cycle property of graphite anodes in lithium ion batteries.
基金The work reported here was supported by the National Natural Science Foundation of China(Nos.52072196,52002199,52002200,52071171,and 52102106)Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09)+4 种基金Natural Science Foundation of Shandong Province(Nos.ZR2019BEM042 and ZR2020QE063)the Innovation and Technology Program of Shandong Province(No.2020KJA004)the Open Project of Chemistry Department of Qingdao University of Science and Technology(No.QUSTHX201813)the Taishan Scholars Program of Shandong Province(No.ts201511034),China Postdoctoral Science Foundation(No.2020M683450),the Guangdong Basic and Applied Basic Research Foundation(Nos.2019A1515110933,2019A1515110554,2020A1515111086,and 2020A1515110219)the Innovation Pilot Project of Integration of Science,Education and Industry of Shandong Province(No.2020KJCCG04)。
文摘MXene is a new intercalation pseudocapacitive electrode material for supercapacitor application.Intensifying fast ion diffusion is significantly essential for MXene to achieve excellent electrochemical performance.The expansion of interlayer void by traditional spontaneous species intercalation always leads to a slight increase in capacitance due to the existence of species sacrificing the smooth diffusion of electrolyte ions.Herein,an effective intercalation-deintercalation interlayer design strategy is proposed to help MXene achieve higher capacitance.Electrochemical cation intercalation leads to the expansion of interlayer space.After electrochemical cation extraction,intercalated cations are deintercalated mostly,leaving a small number of cations trapped in the interlayer silt and serving as pillars to maintain the interlayer space,offering an open,unobstructed interlayer space for better ion migration and storage.Also,a preferred surface with more-O terminations for redox reaction is created due to the reaction between cations and-OH terminations.As a result,the processed MXene delivers a much improved capacitance compared to that of the original Ti_(3)C_(2)T_(x)electrode(T stands for the surface termination groups,such as-OH,-F,and-O).This study demonstrates an improvement of electrochemical performance of MXene electrodes by controlling the interlayer structure and surface chemistry.
基金the National Natural Science Foundation of China (No. 20873054)the Scientific Research Fund of Hunan Provincial Education Department, China (No. 07B060).
文摘Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 was prepared by wet chemical route. The phase,surface morphology,and electrochemical properties of the prepared powders were characterized by X-ray diffraction,scanning electron micrograph,and galvanostatic charge-discharge experiments. Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 has similar X-ray diffraction patterns as LiMn2O4. The corner and border of Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 particles are not as clear as the uncoated one. The two powders show similar values of l...
基金the National Natural Science Foundation of China (No.51502086)Natural Science Foundation of Hunan Province (No.2018JJ3042)Hunan Province Science and Technology Plan Projects (No.2017TP1009).
文摘FeCI3-intercalated graphite intercalation compounds (GICs) with high reversible capacity and high volumetric energy density are attractive anode material alternatives of commercial graphite. However, the rapid capacity decay, which was induced by chloride dissolution and shuttling issues, hindered their practical application. To address this problem, here, we introduce flake-like Fe2O3 species with inherently polar surface on the edge of FeCl3 -intercalated GICs through microwave-assisted transformation of a fraction of FeCl3 component. Theoretical simulations and physical/electrochemical studies demonstrate that the introduced Fe2O3 component can afford sufficient polar active sites for chemically bonding the soluble FeCl3 and LiCl species based on the polar-polar interaction mechanism, further inhibiting the outward diffusion of the chlorides and immobilizing them within the GIC material. In a lithium ion cell, the FeCl3 -intercalated GIC with a suitable Fe2O3 content shows remarkably improved cycling stability with a high reversible capacity of 1,041 mAh·g^-1 at a current density of 200 mA·g^-1. Capacity retention of 91 % is achieved at a high current density of 1,000 mA·g^-1 over 300 cycles. This work opens up the new prospect for immobilizing chlorides by introducing inorganic species in GIC for long-cycle electrochemical batteries.
基金supported by the National Natural Science Foundation of China (No.51872172)Natural Science Foundation of Shandong Province (Nos.ZR2018MEM010 and ZR2019MEM021)+1 种基金Major Research and Development Program for Public Welfare in Shandong (No.2018GGX102021)Young Scholars Program of Shandong University.
文摘Weak ion diffusion and electron transport due to limited interlayer spacing and poor electrical conductivity have been identified as critical roadbacks for fast and abundant energy storage of both MoS2-based lithium ion batteries (LIBs) and sodium ion batteries (SIBs). In this work, MoS2 porous-hollow nanorods (MoS2/m-C800) have been designed and synthesized via an annealing-followed chemistry-intercalated strategy to solve the two issues. They are uniformly assembled from ultrathin MoS2 nanosheets, deviated to the rod-axis direction, with expanded interlayer spacing due to alternate intercalation of N-doped carbon monolayers between the adjacent MoS2 monolayers. Electrochemical studies of the MoS2/m-C800 sample, as an anode of LIBs, demonstrate that the superstructure can deliver a reversible discharge capacity of 1,170 mAh·g^-1 after 100 cycles at 0.2 A·g^-1 and maintain a reversible capacity of 951 mAh·g^-1 at 1.25 A·g^-1 after 350 cycles. While for SIBs, the superstructure also delivers a reversible discharge capacity of 350 mAh·g^-1 at 0.5 A-g-1 after 500 cycles and exhibits superior rate capacity of 238 mAh·g^-1 at 15 A·g^-1 .The excellent electrochemical performance is closely related with the hierarchical superstructures, including expanded interlayer spacing, alternate intercalation of carbon monolayers and mesoporous feature, which effectively reduce ion diffusion barrier, shorten ion diffusion paths and improve electrical conductivity.
文摘Two expressions are introduced to calculate the lithium ion diffusion coefficients in graphite anode as a function of potentials when potentiostatic intermittent titration technique(PITT) is used. The lithium ion diffusion coefficients in graphite derived from effective surface area, which is measured by electrochemical method, are more reliable than those derived simply from radius of graphite particles(calculated from equation (3) and equation (2) respectively). The curves of dQ/dE vs E demonstrate that there are three reversible phase transitions during intercalation or deintercalation of lithium ion in graphite. In the vicinity of the potentials where phase transitions take place, the lithium ion diffusion coefficients in graphite material have three minima in the potential range 10～ 600 mV.
