This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_...This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.展开更多
Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), ...Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.展开更多
P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) was synthesized by a facile sol−gel method,and the effect of calcination temperature on the structure,morphology and electrochemical performance of samples was investigated.The re...P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) was synthesized by a facile sol−gel method,and the effect of calcination temperature on the structure,morphology and electrochemical performance of samples was investigated.The results show that the sample obtained at 900℃ is pure P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) phase with good crystallization,which consists of hexagon plate-shaped particles with the size and thickness of 2−4μm and 200−400 nm,respectively.The sample exhibits an initial specific discharge capacity of 243 mA·h/g at a current density of 26 mA/g with good cycling stability.The high specific capacity indicates that P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) is a promising cathode material for sodiumion batteries.展开更多
LiNi1/3Co1/3Mn1/3O2 was coated with uniform nano-sized AlF3 layer by chemical precipitation method to improve its rate capability.The samples were characterized by X-ray diffractometry (XRD),transmission electron micr...LiNi1/3Co1/3Mn1/3O2 was coated with uniform nano-sized AlF3 layer by chemical precipitation method to improve its rate capability.The samples were characterized by X-ray diffractometry (XRD),transmission electron microscopy (TEM),energy dispersive spectroscopy (EDS),charge-discharge cycling,cyclic voltammetry (CV),and electrochemical impedance spectroscopy (EIS).Uniform coated layer with a thickness of about 3 nm was observed on the surface of LiNi1/3Co1/3Mn1/3O2 particle by TEM.At 0.5C and 2C rates,1.5% (mass fraction) AlF3-coated LiNi1/3Co1/3Mn1/3O2/Li in 2.8-4.3 V versus Li/Li+ after 80 cycles showed less than 3% of capacity fading,while those of the bare one were 16.5% and 45.9%,respectively.At 5C rate,the capacity retention of the coated sample after 50 cycles maintained 91.4% of the initial discharge capacity,while that of the bare one decreased to 52.6%.EIS result showed that a little change of charge transfer resistance of the coated sample resulting from uniform thin AlF3 layer was proposed as the main reason why its rate capability was improved obviously.CV result further indicated a greater reversibility for the electrode processes and better electrochemical performance of AlF3-coated layer.展开更多
Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibri...Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.展开更多
In order to confirm the optimal Li content of Li-rich Mn-based cathode materials(a fixed mole ratio of Mn to Ni to Co is0.6:0.2:0.2),Li1+x(Mn0.6Ni0.2Co0.2)1-xO2(x=0,0.1,0.2,0.3)composites were obtained,which had a typ...In order to confirm the optimal Li content of Li-rich Mn-based cathode materials(a fixed mole ratio of Mn to Ni to Co is0.6:0.2:0.2),Li1+x(Mn0.6Ni0.2Co0.2)1-xO2(x=0,0.1,0.2,0.3)composites were obtained,which had a typical layered structure with R3m and C2/m space group observed from X-ray powder diffraction(XRD).Electron microscopy micrograph(SEM)reveals that the particle sizes in the range of0.4-1.1μm increase with an increase of x value.Li1.2(Mn0.6Ni0.2Co0.2)0.8O2sample delivers a larger initial discharge capacity of275.7mA·h/g at the current density of20mA/g in the potential range of2.0-4.8V,while Li1.1(Mn0.6Ni0.2Co0.2)0.9O2shows a better cycle performance with a capacity retention of93.8%at0.2C after50cycles,showing better reaction kinetics of lithium ion insertion and extraction.展开更多
WS_(2)with layered graphite-like structure as anode for sodium ion batteries has high specific capacity.However,the poor cycling performance and rate capability of WS_(2)caused by the low electronic conductivity and s...WS_(2)with layered graphite-like structure as anode for sodium ion batteries has high specific capacity.However,the poor cycling performance and rate capability of WS_(2)caused by the low electronic conductivity and structure changes during cycles inhibit its practical application.Herein,metallic phase(1T)W_(x)Mo_(1−x)S2(x=1,0.9,0.8 and 0.6)with high electronic conductivity and expanded interlayer spacing of 0.95 nm was directly prepared via a simple hydrothermal method.Specially,1T W_(0.9)Mo_(0.1)S_(2)as anode for sodium ion batteries displays high capacities of 411 mAh g^(-1)at 0.1 A g^(-1)after 180 cycles and 262 mAh g^(-1)at 1 A g^(-1)after 280 cycles and excellent rate capability(245 mAh g^(-1)at 5 A g^(-1)).The full cell based on Na_(3)V_(2)(PO_(4))_(2)O_(2)F/C cathode and 1T W_(0.9)Mo_(0.1)S_(2)anode also exhibits high capacity and good cycling performance.The irreversible electrochemical reaction of 1T W_(0.9)Mo_(0.1)S_(2)with Na ions during first few cycles results in the main products of W-Mo alloy and S.The strong adsorption of W-Mo alloy with polysulfides can effectively suppress the dissolution and shuttle effect of polysulfides,which ensures the excellent cycling performance of 1T W_(0.9)Mo_(0.1)S_(2).展开更多
A new lithium ion battery cathode material, composite oxide LiNi y Co z Mn 1- y-z O 2, was synthesized. The structure and physical properties of the material, including composition, distribution of size, density and s...A new lithium ion battery cathode material, composite oxide LiNi y Co z Mn 1- y-z O 2, was synthesized. The structure and physical properties of the material, including composition, distribution of size, density and specific surface area, were discussed. The characteristic of charge and discharge, reversible specific capacity and cycle property were also studied. The relationship between the structure and properties of the composite oxides was explored. The results show that the composite oxide with a reasonable composition is beneficial to the improvement and enhancement of the properties.展开更多
Mg3（PO4）2-coated Li1.05Ni1/3Mn1/33Co1/3O2 cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning e...Mg3（PO4）2-coated Li1.05Ni1/3Mn1/33Co1/3O2 cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, cyclic voltammetry（CV）, electrochemical impedance spectroscopy（EIS）, charge/discharge cycling and differential scanning calorimeter （DSC）. SEM analysis shows that Mg3（PO4）2-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg3（PO4）2-coating powder is homogeneous and has better layered structure than the bare one. Mg3（PO4）2-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg3（PO4）2-coated sample at 55 ℃ was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg3（PO4）2-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells： the Mg3（PO4）2 coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li1.05Ni1/3Mn1/3Co1/3O2.展开更多
基金financially supported by the Scientific and Technological Plan Projects of Guangzhou City(202103040001)。
文摘This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.
基金supported by the National Natural Science Foundation of China(Nos.51874196,51674164)the Program for Professor of Special Appointment at the Shanghai Institutions of Higher Learning,China(No.TP2020032)+2 种基金the Iron and Steel Joint Research Fund of the National Natural Science Foundation of China and China Baowu Steel Group Corp.Ltd.(No.U1860203)the Independent Research and Development Project of State Key Laboratory of Advanced Special Steel,Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University,China(No.SKLASS 2021-Z03)the Science and Technology Commission of Shanghai Municipality,China(Nos.21DZ1208900,19DZ2270200,20511107700)。
基金supported by the National Key Project for Basic Research of China (No. 2005CB623605)the National Natural Science Foundation of China (No. 11074039)the National Science Foundation for Young Scholars (No.11004032)
文摘Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.
基金the financial supports from the Natural Science Foundation of Hunan Province,China(No.2020JJ5102)the Scientific Research Fund of Hunan Provincial Education Department,China(No.19A111).
文摘P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) was synthesized by a facile sol−gel method,and the effect of calcination temperature on the structure,morphology and electrochemical performance of samples was investigated.The results show that the sample obtained at 900℃ is pure P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) phase with good crystallization,which consists of hexagon plate-shaped particles with the size and thickness of 2−4μm and 200−400 nm,respectively.The sample exhibits an initial specific discharge capacity of 243 mA·h/g at a current density of 26 mA/g with good cycling stability.The high specific capacity indicates that P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) is a promising cathode material for sodiumion batteries.
基金Project(50542004) supported by the National Natural Science Foundation of ChinaProject(1960-71131100017) supported by Graduate Degree Thesis Innovation Foundation of Central South University,China
文摘LiNi1/3Co1/3Mn1/3O2 was coated with uniform nano-sized AlF3 layer by chemical precipitation method to improve its rate capability.The samples were characterized by X-ray diffractometry (XRD),transmission electron microscopy (TEM),energy dispersive spectroscopy (EDS),charge-discharge cycling,cyclic voltammetry (CV),and electrochemical impedance spectroscopy (EIS).Uniform coated layer with a thickness of about 3 nm was observed on the surface of LiNi1/3Co1/3Mn1/3O2 particle by TEM.At 0.5C and 2C rates,1.5% (mass fraction) AlF3-coated LiNi1/3Co1/3Mn1/3O2/Li in 2.8-4.3 V versus Li/Li+ after 80 cycles showed less than 3% of capacity fading,while those of the bare one were 16.5% and 45.9%,respectively.At 5C rate,the capacity retention of the coated sample after 50 cycles maintained 91.4% of the initial discharge capacity,while that of the bare one decreased to 52.6%.EIS result showed that a little change of charge transfer resistance of the coated sample resulting from uniform thin AlF3 layer was proposed as the main reason why its rate capability was improved obviously.CV result further indicated a greater reversibility for the electrode processes and better electrochemical performance of AlF3-coated layer.
基金financially supported by the National Natural Science Foundation of China(No.51904250)the China Postdoctoral Science Foundation(No.2021M692254)+2 种基金the Sichuan Science and Technology Program(No.2022YFG0098)the Fundamental Research Funds for the Central Universities(Nos.2021CDSN-02,2022SCU12002,2022CDZG-17,2022CDSN-08,2022CDZG-9)the Hohhot Science and Technology Program(No.2023-Jie Bang Gua Shuai-Gao-3)。
文摘Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.
基金Project(21473258) supported by the National Natural Science Foundation of ChinaProject(13JJ1004) supported by Distinguished Young Scientists of Hunan Province,ChinaProject(NCET-11-0513) supported by Program for the New Century Excellent Talents in University,China
文摘In order to confirm the optimal Li content of Li-rich Mn-based cathode materials(a fixed mole ratio of Mn to Ni to Co is0.6:0.2:0.2),Li1+x(Mn0.6Ni0.2Co0.2)1-xO2(x=0,0.1,0.2,0.3)composites were obtained,which had a typical layered structure with R3m and C2/m space group observed from X-ray powder diffraction(XRD).Electron microscopy micrograph(SEM)reveals that the particle sizes in the range of0.4-1.1μm increase with an increase of x value.Li1.2(Mn0.6Ni0.2Co0.2)0.8O2sample delivers a larger initial discharge capacity of275.7mA·h/g at the current density of20mA/g in the potential range of2.0-4.8V,while Li1.1(Mn0.6Ni0.2Co0.2)0.9O2shows a better cycle performance with a capacity retention of93.8%at0.2C after50cycles,showing better reaction kinetics of lithium ion insertion and extraction.
基金the support from the National Science Foundation of China(22179071,51772169,51802261,52072217)the Major Technological Innovation Project of Hubei Science and Technology Department(2019AAA164)supported by the Research Project of Education Department of Hubei Province(D20191202)。
文摘WS_(2)with layered graphite-like structure as anode for sodium ion batteries has high specific capacity.However,the poor cycling performance and rate capability of WS_(2)caused by the low electronic conductivity and structure changes during cycles inhibit its practical application.Herein,metallic phase(1T)W_(x)Mo_(1−x)S2(x=1,0.9,0.8 and 0.6)with high electronic conductivity and expanded interlayer spacing of 0.95 nm was directly prepared via a simple hydrothermal method.Specially,1T W_(0.9)Mo_(0.1)S_(2)as anode for sodium ion batteries displays high capacities of 411 mAh g^(-1)at 0.1 A g^(-1)after 180 cycles and 262 mAh g^(-1)at 1 A g^(-1)after 280 cycles and excellent rate capability(245 mAh g^(-1)at 5 A g^(-1)).The full cell based on Na_(3)V_(2)(PO_(4))_(2)O_(2)F/C cathode and 1T W_(0.9)Mo_(0.1)S_(2)anode also exhibits high capacity and good cycling performance.The irreversible electrochemical reaction of 1T W_(0.9)Mo_(0.1)S_(2)with Na ions during first few cycles results in the main products of W-Mo alloy and S.The strong adsorption of W-Mo alloy with polysulfides can effectively suppress the dissolution and shuttle effect of polysulfides,which ensures the excellent cycling performance of 1T W_(0.9)Mo_(0.1)S_(2).
文摘A new lithium ion battery cathode material, composite oxide LiNi y Co z Mn 1- y-z O 2, was synthesized. The structure and physical properties of the material, including composition, distribution of size, density and specific surface area, were discussed. The characteristic of charge and discharge, reversible specific capacity and cycle property were also studied. The relationship between the structure and properties of the composite oxides was explored. The results show that the composite oxide with a reasonable composition is beneficial to the improvement and enhancement of the properties.
基金Funded by the National Natural Science Foundation of China (No. 20273047)
文摘Mg3（PO4）2-coated Li1.05Ni1/3Mn1/33Co1/3O2 cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, cyclic voltammetry（CV）, electrochemical impedance spectroscopy（EIS）, charge/discharge cycling and differential scanning calorimeter （DSC）. SEM analysis shows that Mg3（PO4）2-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg3（PO4）2-coating powder is homogeneous and has better layered structure than the bare one. Mg3（PO4）2-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg3（PO4）2-coated sample at 55 ℃ was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg3（PO4）2-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells： the Mg3（PO4）2 coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li1.05Ni1/3Mn1/3Co1/3O2.
