Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),a...Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.展开更多
A La_(0.5)Ba_(0.5)MnO_(3-δ) oxide was prepared using the sol-gel technique.Instead of a pure phase,La_(0.5)Ba_(0.5)MnO_(3-δ) was discovered to be a combination of La_(0.7)Ba_(0.3)MnO_(3-δ) and BaMnO_(3).The in-situ...A La_(0.5)Ba_(0.5)MnO_(3-δ) oxide was prepared using the sol-gel technique.Instead of a pure phase,La_(0.5)Ba_(0.5)MnO_(3-δ) was discovered to be a combination of La_(0.7)Ba_(0.3)MnO_(3-δ) and BaMnO_(3).The in-situ production of La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites enhanced the oxygen vacancy(Vo)formation compared to single-phase La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3),providing potential benefits as a cathode for fuel cells.Subsequently,La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites were utilized as the cathode for proton-conducting solid oxide fuel cells(H-SOFCs),which significantly improved cell performance.At 700 C,H-SOFC with a La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposite cathode achieved the highest power density(1504 mW·cm^(-2))yet recorded for H-SOFCs with manganate cathodes.This performance was much greater than that of single-phase La_(0.7)Ba_(0.3)MnO_(3-δ)or BaMnO_(3) cathode cells.In addition,the cell demonstrated excellent working stability.First-principles calculations indicated that the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface was crucial for the enhanced cathode performance.The oxygen reduction reaction(ORR)free energy barrier was significantly lower at the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface than that at the La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3) surfaces,which explained the origin of high performance and gave a guide for the construction of novel cathodes for H-SOFCs.展开更多
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode material doped with Ti and La co-doping were synthesized through a solid-state method.The bi-functions of the Ti and La co-doping is realized.On the one hand,the stability o...Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode material doped with Ti and La co-doping were synthesized through a solid-state method.The bi-functions of the Ti and La co-doping is realized.On the one hand,the stability of the LiNi_(0.5)Mn_(1.5)O_(4)crystal structure is enhanced and the Mn3t interference inside the material is reduced by the Ti doping.On the other hand,the co-doped La contributes to the formation of Li_(0.5)La_(0.5)TiO_(3)(LLTO)superionic conductor incorporated in the bulk LiNi_(0.5)Mn_(1.5)O_(4)phase,thereby enhancing the Li diffusion.With the help of XRD,FTIR,SEM and STEM techniques,La and Ti in the crystallographic structure and the dispersion of the LLTO superionic conductor in the bulk LNMO spinel are discussed.At the optimized molar ratio of 20:1 between LNMO and LLTO,the composite exhibits the best electrochemical performances in terms of the reversible capacity,rate capability and cycling stability.The lithium ion diffusion coefficient in the bulk LNMO phase is tripled by the LLTO superionic conductor incorporation.展开更多
Lithium-ion batteries(LIBs)are widely used in portable consumer electronics,clean energy storage,and electric vehicle applications.However,challenges exist for LIBs,including high costs,safety issues,limited Li resour...Lithium-ion batteries(LIBs)are widely used in portable consumer electronics,clean energy storage,and electric vehicle applications.However,challenges exist for LIBs,including high costs,safety issues,limited Li resources,and manufacturingrelated pollution.In this paper,a novel manganese-based lithium-ion battery with a LiNi_(0.5)Mn_(1.5)O_(4) ‖ Mn_(3)O_(4) structure is reported that is mainly composed of environmental friendly manganese compounds,where Mn_(3)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) (LNMO)are adopted as the anode and cathode materials,respectively.The proposed structure improves battery safety and reduce costs compared with current battery technology,provides comparable energy density with that of traditional graphite-based batteries.First,the characteristics and the electrochemical performances of the Mn_(3)O_(4) anode and the LNMO cathode are investigated separately against Li metal in half cell configurations,with promising performances being demonstrated by both electrodes.Then,a full cell structure with Mn_(3)O_(4) against LNMO is constructed that provides an average discharge voltage of 3.5 V and an initial specific capacity of 86.2 mA;h;g−1.More importantly,the electrochemical performance of the LNMO‖ Mn_(3)O_(4) full cell and its possible decay mechanisms are discussed systemically;and efficient strategies are proposed to further improve both the electrochemical performance of Mn_(3)O_(4) and the stability of LNMO.展开更多
基金the National Natural Science Foundation of China(12102328)for supporting this work。
文摘Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.
基金supported by the National Natural Science Foundation of China(Grant Nos.52272216 and 51972183)the Hundred Youth Talents Program of Hunan,and the Startup Funding for Talents at University of South Chinathe support from the Hunan University Student Innovation and Entrepreneurship Training Program(Grant No.S202210555343)。
文摘A La_(0.5)Ba_(0.5)MnO_(3-δ) oxide was prepared using the sol-gel technique.Instead of a pure phase,La_(0.5)Ba_(0.5)MnO_(3-δ) was discovered to be a combination of La_(0.7)Ba_(0.3)MnO_(3-δ) and BaMnO_(3).The in-situ production of La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites enhanced the oxygen vacancy(Vo)formation compared to single-phase La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3),providing potential benefits as a cathode for fuel cells.Subsequently,La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposites were utilized as the cathode for proton-conducting solid oxide fuel cells(H-SOFCs),which significantly improved cell performance.At 700 C,H-SOFC with a La_(0.7)Ba_(0.3)MnO_(3-δ)+BaMnO_(3) nanocomposite cathode achieved the highest power density(1504 mW·cm^(-2))yet recorded for H-SOFCs with manganate cathodes.This performance was much greater than that of single-phase La_(0.7)Ba_(0.3)MnO_(3-δ)or BaMnO_(3) cathode cells.In addition,the cell demonstrated excellent working stability.First-principles calculations indicated that the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface was crucial for the enhanced cathode performance.The oxygen reduction reaction(ORR)free energy barrier was significantly lower at the La_(0.7)Ba_(0.3)MnO_(3-δ)/BaMnO_(3) interface than that at the La_(0.7)Ba_(0.3)MnO_(3-δ) or BaMnO_(3) surfaces,which explained the origin of high performance and gave a guide for the construction of novel cathodes for H-SOFCs.
基金supported by the National Natural Science Foundation of China (52272216 and 51972183)the Hundred Youth Talents Program of Hunan and the Startup Funding for Talents at the University of South China。
基金This work is financially supported by the National Natural Science Foundation of China(NSFC,contract no.21875154 and 21473120)The authors also thank the Ministry of Science and Technology of the People's Republic of China,China(Contract No.2015AA034601).
文摘Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode material doped with Ti and La co-doping were synthesized through a solid-state method.The bi-functions of the Ti and La co-doping is realized.On the one hand,the stability of the LiNi_(0.5)Mn_(1.5)O_(4)crystal structure is enhanced and the Mn3t interference inside the material is reduced by the Ti doping.On the other hand,the co-doped La contributes to the formation of Li_(0.5)La_(0.5)TiO_(3)(LLTO)superionic conductor incorporated in the bulk LiNi_(0.5)Mn_(1.5)O_(4)phase,thereby enhancing the Li diffusion.With the help of XRD,FTIR,SEM and STEM techniques,La and Ti in the crystallographic structure and the dispersion of the LLTO superionic conductor in the bulk LNMO spinel are discussed.At the optimized molar ratio of 20:1 between LNMO and LLTO,the composite exhibits the best electrochemical performances in terms of the reversible capacity,rate capability and cycling stability.The lithium ion diffusion coefficient in the bulk LNMO phase is tripled by the LLTO superionic conductor incorporation.
基金support provided by the National Natural Science Foundation of China(NSFC)(Nos.51602058,51702103)the Special Support Plan for High-Level Talents of Guangdong Province(No.2017TQ04N840)the Science and Technology Planning Project of Guangdong Province(Nos.2017A010103011,2017A030313081).
文摘Lithium-ion batteries(LIBs)are widely used in portable consumer electronics,clean energy storage,and electric vehicle applications.However,challenges exist for LIBs,including high costs,safety issues,limited Li resources,and manufacturingrelated pollution.In this paper,a novel manganese-based lithium-ion battery with a LiNi_(0.5)Mn_(1.5)O_(4) ‖ Mn_(3)O_(4) structure is reported that is mainly composed of environmental friendly manganese compounds,where Mn_(3)O_(4) and LiNi_(0.5)Mn_(1.5)O_(4) (LNMO)are adopted as the anode and cathode materials,respectively.The proposed structure improves battery safety and reduce costs compared with current battery technology,provides comparable energy density with that of traditional graphite-based batteries.First,the characteristics and the electrochemical performances of the Mn_(3)O_(4) anode and the LNMO cathode are investigated separately against Li metal in half cell configurations,with promising performances being demonstrated by both electrodes.Then,a full cell structure with Mn_(3)O_(4) against LNMO is constructed that provides an average discharge voltage of 3.5 V and an initial specific capacity of 86.2 mA;h;g−1.More importantly,the electrochemical performance of the LNMO‖ Mn_(3)O_(4) full cell and its possible decay mechanisms are discussed systemically;and efficient strategies are proposed to further improve both the electrochemical performance of Mn_(3)O_(4) and the stability of LNMO.
