Passivation by the inorganic-rich solid electrolyte interphase(SEI),especially the LiF-rich SEI,is highly desirable to guarantee the durable lifespan of Li metal batteries(LMBs).Here,we report a diluent with the capab...Passivation by the inorganic-rich solid electrolyte interphase(SEI),especially the LiF-rich SEI,is highly desirable to guarantee the durable lifespan of Li metal batteries(LMBs).Here,we report a diluent with the capability to facilitate the formation of LiF-rich SEI while avoiding the excess consumption of Li salts.Dissimilar to most of reported inert diluents,heptafluoro-l-methoxypropane(HM) is firstly demonstrated to cooperate with the decomposition of anions to generate LiF-rich SEI via releasing Fcontaining species near Li surface.The designed electrolyte consisting of 1.8 M LiFSI in the mixture of1,2-dimethoxyethane(DME)/HM(2:1 by vol.) achieves excellent compatibility with both Li metal anodes(Coulombic efficiency~99.8%) and high-voltage cathodes(4.4 V LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811) and 4.5 V LiCoO_(2)(LCO) vs Li^(+)/Li).The 4.4 V Li(20μm)‖NMC811(2.5 mA h cm^(-2)) and 4.5 V Li(20μm)‖LCO(2.5 mA h cm^(-2)) cells achieve capacity retentions of 80% over 560 cycles and 80% over 505 cycles,respectively.Meanwhile,the anode-free pouch cell delivers an energy density of~293 W h kg^(-1)initially and retains 70% of capacity after 100 deep cycles.This work highlights the critical impact of diluent on the SEI formation,and opens up a new direction for designing desirable interfacial chemistries to enable high-performance LMBs.展开更多
Corrosion in complex coupling environments is an important issue in corrosion field, because it is difficult to take into account a large number of environment factors and their interactions. Design of Experiment(DOE)...Corrosion in complex coupling environments is an important issue in corrosion field, because it is difficult to take into account a large number of environment factors and their interactions. Design of Experiment(DOE) can present a methodology to deal with this difficulty, although DOE is not commonly spread in corrosion field. Thus, modeling corrosion of Ni-Cr-Mo-V steel in deep sea environment was performed in order to provide example demonstrating the advantage of DOE. In addition, an artificial neural network mapping using back-propagation method was developed for Ni-Cr-Mo-V steel such that the ANN model can be used to predict polarization curves under different complex sea environments without experimentation. Furthermore, roles of environment factors on corrosion of Ni-Cr-Mo-V steel in deep sea environment were discussed.展开更多
Isothermal oxidation behaviors of Ni–Fe(wt.%)and of the same alloy with additions of 10 and 15%Cr alloys in the air at 800℃and 900℃and their anodic behaviors in aluminum electrolysis system at 800℃were evaluated.T...Isothermal oxidation behaviors of Ni–Fe(wt.%)and of the same alloy with additions of 10 and 15%Cr alloys in the air at 800℃and 900℃and their anodic behaviors in aluminum electrolysis system at 800℃were evaluated.The composition morphologies of oxide scales were characterized by XRD,SEM,and EDS.Results show that the scales formed on Ni–Fe alloy at both temperatures consisted of an inner(Ni,Fe)Olayer and an outer FeOlayer.For Ni–Fe–10Cr alloy,an external(Ni,Fe)O/FeOlayers and an internal oxidation zone were formed at 800°C,while a continuous CrOlayer forms at the internal oxidation zone/substrate interface at 900°C.A multilayer structure oxide of CrO/(Ni,Fe,Cr)O/(Ni,Fe)O/FeOwas formed on Ni–Fe–15Cr alloy at 800°C,while at 900℃the FeObecomes discontinuous disperses in the(Ni,Fe)Olayer close to the surface.Increases in oxidation temperature or Cr content for Ni–Fe–Cr alloys promote the growth of the inner CrOlayer and simultaneously reduce FeOcontent.After 4 h of electrolysis at an anode current density of 0.25 A cm,the oxidation resistance of Ni–Fe–15Cr anode is superior to the Ni–Fe anode.展开更多
A novel metal-enamel interlocking coating was designed and prepared in situ by co-deposition of Ni-enamel composite layer and subsequent air spray of enamel with 10 wt% nanoscale Ni. During the firing process, the ext...A novel metal-enamel interlocking coating was designed and prepared in situ by co-deposition of Ni-enamel composite layer and subsequent air spray of enamel with 10 wt% nanoscale Ni. During the firing process, the external enamel layer was melted and jointed with the enamel particles at the upper part of the Ni-plating layer to form the enamel pegs. Thermal shock tests of pure enamel, enamel with 10 wt% Ni composite and metal-enamel interlocking coatings were conducted at 600 °C in water and static air. The results indicated that the metal-enamel interlocking showed superior thermal shock resistance to both pure enamel and enamel with 10 wt% Ni composite coatings. The enhanced performance was mainly attributed to the advantageous effects of mechanical interlocking of the enamel pegs formed at the enamel/Ni-plating interface. Meanwhile, during thermal shock test, big clusters formed by nanoscale Ni agglomerations were oxidised to be a Ni/NiO core–shell structure while small single nanoscale Ni grains were oxidised completely, which both improved the thermal shock resistance of enamel coating significantly.展开更多
The performance degradation mechanism of ceramic fuel cell with NCAL(Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2))as symmetrical electrode and GDC as electrolyte in H2 is investigated.It is found that under the condition of 550◦...The performance degradation mechanism of ceramic fuel cell with NCAL(Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2))as symmetrical electrode and GDC as electrolyte in H2 is investigated.It is found that under the condition of 550◦C and constant current density of 0.2 A⋅cm^(-2),the output voltage of the cell is about 1.005 V in the initial 10 h and remains relatively stable.After 10 h,the voltage of the cell began to decrease gradually,and by 50 h,the voltage had decreased to 0.522 V.The results testing electrochemical performance of the cell and characterizing the cell materials before and after test using SEM,TOF-SIMS and FTIR indicate that the distribution of Li_(2)O/LiOH/Li_(2)CO_(3)compounds generated from NCAL anode in the cell plays a vital role in significantly improving the ionic conductivity of electrolyte and gas tightness of the cell.The dynamic migration of molten salt destroyed the continuity of molten salt in the cell,which in turn adversely impacted the ionic conductivity of electrolyte,gas tightness of the cell,and electrochemical reactions on both sides of the cathode and anode.These finally lead to the degradation of the cell performance.展开更多
Previous studies have found that the ceramic fuel cell using Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2)(NCAL)symmetrical electrode has obtained very good power generation performance in the temperature range of 450 to 550℃.Pr...Previous studies have found that the ceramic fuel cell using Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2)(NCAL)symmetrical electrode has obtained very good power generation performance in the temperature range of 450 to 550℃.Previous studies have pointed out that after being reduced by H2,NCAL anode will produce LiOH/Li2CO3 mixture and diffuse into the electrolyte,which results in the high ionic conductivity of the cell.In this study,the chemical reactivity of different oxide electrolytes such as CeO_(2),TiO_(2),ZrO_(2)and YSZ with LiOH and/or Li2CO3 and their effects on the electrochemical performance of the cell were studied.It is found that at 550◦C,only the open circuit voltage(OCV)of the cell using CeO_(2)as electrolyte can remain stable,and the maximum power density(MPD)of the CeO_(2)electrolyte cell reaches 599.6 mW⋅cm^(−2).The OCV of the cells with TiO_(2),ZrO_(2)and YSZ as electrolyte increased to the highest value within a few minutes,and the MPD of the cells was only more than 12 mW⋅cm^(−2).XRD,FT-IR,SEM-EDS and ICP-OES results indicate that the LiOH/Li2CO3 mixture diffuses into TiO_(2),ZrO_(2)and YSZ electrolytes and reacts with three oxides to produce Li2TiO3 and Li2ZrO3,respectively,which results in the low performance of the cell.展开更多
基金supported by the National Natural Science Foundation of China(22072134,22161142017,and U21A2081)the Natural Science Foundation of Zhejiang Province(LZ21B030002)+2 种基金the Fundamental Research Funds for the Zhejiang Provincial Universities(2021XZZX010)the Fundamental Research Funds for the Central Universities(2021FZZX001-09)“Hundred Talents Program” of Zhejiang University。
文摘Passivation by the inorganic-rich solid electrolyte interphase(SEI),especially the LiF-rich SEI,is highly desirable to guarantee the durable lifespan of Li metal batteries(LMBs).Here,we report a diluent with the capability to facilitate the formation of LiF-rich SEI while avoiding the excess consumption of Li salts.Dissimilar to most of reported inert diluents,heptafluoro-l-methoxypropane(HM) is firstly demonstrated to cooperate with the decomposition of anions to generate LiF-rich SEI via releasing Fcontaining species near Li surface.The designed electrolyte consisting of 1.8 M LiFSI in the mixture of1,2-dimethoxyethane(DME)/HM(2:1 by vol.) achieves excellent compatibility with both Li metal anodes(Coulombic efficiency~99.8%) and high-voltage cathodes(4.4 V LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811) and 4.5 V LiCoO_(2)(LCO) vs Li^(+)/Li).The 4.4 V Li(20μm)‖NMC811(2.5 mA h cm^(-2)) and 4.5 V Li(20μm)‖LCO(2.5 mA h cm^(-2)) cells achieve capacity retentions of 80% over 560 cycles and 80% over 505 cycles,respectively.Meanwhile,the anode-free pouch cell delivers an energy density of~293 W h kg^(-1)initially and retains 70% of capacity after 100 deep cycles.This work highlights the critical impact of diluent on the SEI formation,and opens up a new direction for designing desirable interfacial chemistries to enable high-performance LMBs.
基金the financial support of the National Natural Science Foundation of China(No.51371182)the National Program for the Young Top-notch Professionals and the Fundamental Research Funds for the Central Universities(N170205002)
文摘Corrosion in complex coupling environments is an important issue in corrosion field, because it is difficult to take into account a large number of environment factors and their interactions. Design of Experiment(DOE) can present a methodology to deal with this difficulty, although DOE is not commonly spread in corrosion field. Thus, modeling corrosion of Ni-Cr-Mo-V steel in deep sea environment was performed in order to provide example demonstrating the advantage of DOE. In addition, an artificial neural network mapping using back-propagation method was developed for Ni-Cr-Mo-V steel such that the ANN model can be used to predict polarization curves under different complex sea environments without experimentation. Furthermore, roles of environment factors on corrosion of Ni-Cr-Mo-V steel in deep sea environment were discussed.
基金supported by National Natural Science Foundation of China(No.51571059)。
文摘Isothermal oxidation behaviors of Ni–Fe(wt.%)and of the same alloy with additions of 10 and 15%Cr alloys in the air at 800℃and 900℃and their anodic behaviors in aluminum electrolysis system at 800℃were evaluated.The composition morphologies of oxide scales were characterized by XRD,SEM,and EDS.Results show that the scales formed on Ni–Fe alloy at both temperatures consisted of an inner(Ni,Fe)Olayer and an outer FeOlayer.For Ni–Fe–10Cr alloy,an external(Ni,Fe)O/FeOlayers and an internal oxidation zone were formed at 800°C,while a continuous CrOlayer forms at the internal oxidation zone/substrate interface at 900°C.A multilayer structure oxide of CrO/(Ni,Fe,Cr)O/(Ni,Fe)O/FeOwas formed on Ni–Fe–15Cr alloy at 800°C,while at 900℃the FeObecomes discontinuous disperses in the(Ni,Fe)Olayer close to the surface.Increases in oxidation temperature or Cr content for Ni–Fe–Cr alloys promote the growth of the inner CrOlayer and simultaneously reduce FeOcontent.After 4 h of electrolysis at an anode current density of 0.25 A cm,the oxidation resistance of Ni–Fe–15Cr anode is superior to the Ni–Fe anode.
基金financially supported by the Excellent Youth Foundation of Liaoning Province(No.2019-YQ-03)the CNPC Science and Technology Development Project(Nos.2019B4013 and 2019A-3911)+2 种基金the National Key R&D Program of China(Nos.2019YFF0217500 and 2016ZX05022-055)the Science Fund for Distinguished Young Scholars of Shaanxi Provincethe Ministry of Industry and Information Technology Project(No.MJ-2017-J-99)。
文摘A novel metal-enamel interlocking coating was designed and prepared in situ by co-deposition of Ni-enamel composite layer and subsequent air spray of enamel with 10 wt% nanoscale Ni. During the firing process, the external enamel layer was melted and jointed with the enamel particles at the upper part of the Ni-plating layer to form the enamel pegs. Thermal shock tests of pure enamel, enamel with 10 wt% Ni composite and metal-enamel interlocking coatings were conducted at 600 °C in water and static air. The results indicated that the metal-enamel interlocking showed superior thermal shock resistance to both pure enamel and enamel with 10 wt% Ni composite coatings. The enhanced performance was mainly attributed to the advantageous effects of mechanical interlocking of the enamel pegs formed at the enamel/Ni-plating interface. Meanwhile, during thermal shock test, big clusters formed by nanoscale Ni agglomerations were oxidised to be a Ni/NiO core–shell structure while small single nanoscale Ni grains were oxidised completely, which both improved the thermal shock resistance of enamel coating significantly.
基金supported by the National Natural Science Foundation of China(No.21978044).
文摘The performance degradation mechanism of ceramic fuel cell with NCAL(Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2))as symmetrical electrode and GDC as electrolyte in H2 is investigated.It is found that under the condition of 550◦C and constant current density of 0.2 A⋅cm^(-2),the output voltage of the cell is about 1.005 V in the initial 10 h and remains relatively stable.After 10 h,the voltage of the cell began to decrease gradually,and by 50 h,the voltage had decreased to 0.522 V.The results testing electrochemical performance of the cell and characterizing the cell materials before and after test using SEM,TOF-SIMS and FTIR indicate that the distribution of Li_(2)O/LiOH/Li_(2)CO_(3)compounds generated from NCAL anode in the cell plays a vital role in significantly improving the ionic conductivity of electrolyte and gas tightness of the cell.The dynamic migration of molten salt destroyed the continuity of molten salt in the cell,which in turn adversely impacted the ionic conductivity of electrolyte,gas tightness of the cell,and electrochemical reactions on both sides of the cathode and anode.These finally lead to the degradation of the cell performance.
基金the National Natural Science Foundation of China(No.21978044,No.51834004)。
文摘Previous studies have found that the ceramic fuel cell using Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2)(NCAL)symmetrical electrode has obtained very good power generation performance in the temperature range of 450 to 550℃.Previous studies have pointed out that after being reduced by H2,NCAL anode will produce LiOH/Li2CO3 mixture and diffuse into the electrolyte,which results in the high ionic conductivity of the cell.In this study,the chemical reactivity of different oxide electrolytes such as CeO_(2),TiO_(2),ZrO_(2)and YSZ with LiOH and/or Li2CO3 and their effects on the electrochemical performance of the cell were studied.It is found that at 550◦C,only the open circuit voltage(OCV)of the cell using CeO_(2)as electrolyte can remain stable,and the maximum power density(MPD)of the CeO_(2)electrolyte cell reaches 599.6 mW⋅cm^(−2).The OCV of the cells with TiO_(2),ZrO_(2)and YSZ as electrolyte increased to the highest value within a few minutes,and the MPD of the cells was only more than 12 mW⋅cm^(−2).XRD,FT-IR,SEM-EDS and ICP-OES results indicate that the LiOH/Li2CO3 mixture diffuses into TiO_(2),ZrO_(2)and YSZ electrolytes and reacts with three oxides to produce Li2TiO3 and Li2ZrO3,respectively,which results in the low performance of the cell.
