Composite cathodes integrating Ni-rich layered oxides and oxide solid electrolytes are essential for highenergy all-solid-state lithium-ion batteries(ASSLBs),yet interfacial degradation during high-temperature co-sint...Composite cathodes integrating Ni-rich layered oxides and oxide solid electrolytes are essential for highenergy all-solid-state lithium-ion batteries(ASSLBs),yet interfacial degradation during high-temperature co-sintering(>600℃)remains a critical challenge.While surface passivation strategies mitigate reactions below 400℃,their effectiveness diminishes at elevated temperatures due to inability to counteract Li^(+)concentration gradients.Here,we introduce in situ lithium compensators,i.e.,LiOH/Li_(2)CO_(3),into NCM-LATP composite cathodes to dynamically replenish Li^(+)during co-sintering.These additives melt to form transient Li^(+)-rich phases that back-diffuse Li^(+)into NCM lattices,suppressing layered-to-rock salt transitions and stabilizing the interface.Quasi in situ XRD confirms retention of the layered structure at temperature up to 700℃,while electrochemical tests demonstrate a reversible capacity of 222.2 mA h g^(-1)—comparable to NCM before co-sintering—and an impressive 65.3% capacity retention improvement over100 cycles.In contrast,uncompensated cathodes exhibit severe degradation to 96.5 mA h g^(-1)due to Li depletion and resistive Li-Ti-O interphases.This strategy integrates sacrificial chemistry with scalable powder-mixing workflows,achieving a 93.4% reduction in interfacial impedance.By addressing Li^(+)flux homogenization and structural stability,this work provides a practical pathway toward industrialscale fabrication of high-performance ASSLBs.展开更多
Additive manufacturing(AM)offers the unique capability of directly creating three-dimensional complicated ceramic components with high process flexibility and outstanding geometry controllability.However,current ceram...Additive manufacturing(AM)offers the unique capability of directly creating three-dimensional complicated ceramic components with high process flexibility and outstanding geometry controllability.However,current ceramic AM technology is mainly limited to the creation of a single material,which falls short of meeting the multiple functional requirements under increasingly harsh service circumstances.Ceramic multi-material additive manufacturing(MMAM)technology has great potential for integrally producing multi-dimensional multi-functional components,allowing for point-by-point precision manufacturing of programmable performance/functions.However,there is a huge gap between the capabilities of the existing ceramic MMAM technology and the requirements for industrial application.In this review,we discuss and summarize the research status of ceramic MMAM technology from the perspectives of feedstock selection,printing process,post-processing,component performance,and application.Throughout the discussion,the challenges associated with ceramic MMAM such as heterogeneous material coupled printing,heterogeneous interfacial bonding,and co-sintering densification have been put forward.This review aims to bridge the gap between AM technologies and the requirements for multifunctional ceramic components by analyzing the existing limitations in ceramic MMAM and pointing out future needs.展开更多
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
Aiming at the influences of poor contact at carbon nanotube (CNT)/electrode interface on luminescence stability in printed CNT film, a new co-sintering process for cathode fabrication was presented to improve the lumi...Aiming at the influences of poor contact at carbon nanotube (CNT)/electrode interface on luminescence stability in printed CNT film, a new co-sintering process for cathode fabrication was presented to improve the luminescent stability of fully printed CNT-FED. By co-sintering the printed silver and CNT layers, CNTs geometrically matched with Ag surface and/or embedded into Ag layer at the bottom of the co-sintered film, large CNTs block and bulk silver nested each other at the top of the co-sintered film. All these structures increased the contact area at CNT/Ag interface, which could increase the probability of forming ohmic contact at CNT/Ag interface. The luminescent stability of printed CNT-FED with co-sintered cathode could be improved as 5.6 times high as that of common devices.展开更多
Yttria-stabilized zirconia(YSZ) is the most common electrolyte material for solid oxide fuel cells. Herein, we conducted a comparative study on the densification behavior of three different kinds of commercial 8 mol% ...Yttria-stabilized zirconia(YSZ) is the most common electrolyte material for solid oxide fuel cells. Herein, we conducted a comparative study on the densification behavior of three different kinds of commercial 8 mol% YSZ powders:(i) TZ-8Y(Tosoh, Japan),(ii) MELox 8Y(MEL Chemicals, UK), and(iii) YSZ-HT(Huatsing Power, China). The comparison was made on both the selfsupporting pellets and thin-film electrolytes coated onto a NiO–YSZ anode support. For the pellets, MELox 8Y showed the highest densification at lower sintering temperatures with 93% and 96% of the theoretical density at 1250 and 1300 ℃, respectively. Although YSZ-HT showed a higher sintering rate than TZ-8Y, a sintering temperature of 1350 ℃ was required for both the powders to reach 95% of the theoretical density. For the thin-film electrolytes, on the other hand, YSZ-HT showed the highest sintering rate with a dense microstructure at a co-sintering temperature of 1250 ℃. Our results indicate that besides the average particle size, other factors such as particle size distribution and post-processing play a significant role in determining the sintering rate and densification behavior of the YSZ powders. Additionally, a close match in the sintering shrinkage of the electrolyte and anode support is important for facilitating the densification of the thin-film electrolytes.展开更多
基金financially supported by the National Natural Science Foundation of China(52102206)the Natural Science Foundation of Beijing Municipality-Shunyi Innovation Collaborative Joint Fund(L247018)+2 种基金the Natural Science Foundation of Beijing Municipality(2254076 and 2252024)the Central Guidance on Local Science and Technology Development Fund of Hebei Province(246Z4412G)the Fundamental Research Funds for the Central Universities(2025MS022,North China Electric Power University)。
文摘Composite cathodes integrating Ni-rich layered oxides and oxide solid electrolytes are essential for highenergy all-solid-state lithium-ion batteries(ASSLBs),yet interfacial degradation during high-temperature co-sintering(>600℃)remains a critical challenge.While surface passivation strategies mitigate reactions below 400℃,their effectiveness diminishes at elevated temperatures due to inability to counteract Li^(+)concentration gradients.Here,we introduce in situ lithium compensators,i.e.,LiOH/Li_(2)CO_(3),into NCM-LATP composite cathodes to dynamically replenish Li^(+)during co-sintering.These additives melt to form transient Li^(+)-rich phases that back-diffuse Li^(+)into NCM lattices,suppressing layered-to-rock salt transitions and stabilizing the interface.Quasi in situ XRD confirms retention of the layered structure at temperature up to 700℃,while electrochemical tests demonstrate a reversible capacity of 222.2 mA h g^(-1)—comparable to NCM before co-sintering—and an impressive 65.3% capacity retention improvement over100 cycles.In contrast,uncompensated cathodes exhibit severe degradation to 96.5 mA h g^(-1)due to Li depletion and resistive Li-Ti-O interphases.This strategy integrates sacrificial chemistry with scalable powder-mixing workflows,achieving a 93.4% reduction in interfacial impedance.By addressing Li^(+)flux homogenization and structural stability,this work provides a practical pathway toward industrialscale fabrication of high-performance ASSLBs.
基金supported by Grants from the National Natural Science Foundation of China(Nos.52205363,52235008 and U2037203)Fundamental Research Funds for the Central Universities(Nos.2019kfyRCPY044 and 2021GCRC002)+1 种基金Program for HUST Academic Frontier Youth Team(No.2018QYTD04)the Program for Innovative Research Team of the Ministry of Education(No.IRT1244)。
文摘Additive manufacturing(AM)offers the unique capability of directly creating three-dimensional complicated ceramic components with high process flexibility and outstanding geometry controllability.However,current ceramic AM technology is mainly limited to the creation of a single material,which falls short of meeting the multiple functional requirements under increasingly harsh service circumstances.Ceramic multi-material additive manufacturing(MMAM)technology has great potential for integrally producing multi-dimensional multi-functional components,allowing for point-by-point precision manufacturing of programmable performance/functions.However,there is a huge gap between the capabilities of the existing ceramic MMAM technology and the requirements for industrial application.In this review,we discuss and summarize the research status of ceramic MMAM technology from the perspectives of feedstock selection,printing process,post-processing,component performance,and application.Throughout the discussion,the challenges associated with ceramic MMAM such as heterogeneous material coupled printing,heterogeneous interfacial bonding,and co-sintering densification have been put forward.This review aims to bridge the gap between AM technologies and the requirements for multifunctional ceramic components by analyzing the existing limitations in ceramic MMAM and pointing out future needs.
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 No.60036010)the National High Technology Research and Development Program of China(Grant No.2001AA313090)the Doctoral Foundation of the National Education Administration of P.R.China(Grant No.20020698014).
文摘Aiming at the influences of poor contact at carbon nanotube (CNT)/electrode interface on luminescence stability in printed CNT film, a new co-sintering process for cathode fabrication was presented to improve the luminescent stability of fully printed CNT-FED. By co-sintering the printed silver and CNT layers, CNTs geometrically matched with Ag surface and/or embedded into Ag layer at the bottom of the co-sintered film, large CNTs block and bulk silver nested each other at the top of the co-sintered film. All these structures increased the contact area at CNT/Ag interface, which could increase the probability of forming ohmic contact at CNT/Ag interface. The luminescent stability of printed CNT-FED with co-sintered cathode could be improved as 5.6 times high as that of common devices.
基金supported by National Aeronautics and Space Administration (NASA) through Contract No.NNX15CC12C
文摘Yttria-stabilized zirconia(YSZ) is the most common electrolyte material for solid oxide fuel cells. Herein, we conducted a comparative study on the densification behavior of three different kinds of commercial 8 mol% YSZ powders:(i) TZ-8Y(Tosoh, Japan),(ii) MELox 8Y(MEL Chemicals, UK), and(iii) YSZ-HT(Huatsing Power, China). The comparison was made on both the selfsupporting pellets and thin-film electrolytes coated onto a NiO–YSZ anode support. For the pellets, MELox 8Y showed the highest densification at lower sintering temperatures with 93% and 96% of the theoretical density at 1250 and 1300 ℃, respectively. Although YSZ-HT showed a higher sintering rate than TZ-8Y, a sintering temperature of 1350 ℃ was required for both the powders to reach 95% of the theoretical density. For the thin-film electrolytes, on the other hand, YSZ-HT showed the highest sintering rate with a dense microstructure at a co-sintering temperature of 1250 ℃. Our results indicate that besides the average particle size, other factors such as particle size distribution and post-processing play a significant role in determining the sintering rate and densification behavior of the YSZ powders. Additionally, a close match in the sintering shrinkage of the electrolyte and anode support is important for facilitating the densification of the thin-film electrolytes.
