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Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry
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作者 Jieyou Huang Weiliang Li +3 位作者 Debin Ye Lin Xu Wenwei Wu Xuehang Wu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第7期466-476,共11页
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas... P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs. 展开更多
关键词 Sodium-ion batteries P2/O3-type layered oxides Na distribution Oxygen redox chemistry Hydrostability
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Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping 被引量:1
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作者 Yongchao Yao Shengjun Sun +14 位作者 Hui Zhang Zixiao Li Chaoxin Yang Zhengwei Cai Xun He Kai Dong Yonglan Luo Yan Wang Yuchun Ren Qian Liu Dongdong Zheng Weihua Zhuang Bo Tang Xuping Sun Wenchuang(Walter)Hu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第4期306-312,共7页
Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability cau... Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution. 展开更多
关键词 Ce doping NiFe layered double hydroxide Seawater oxidation Electrocatalysis Cl^(-) repulsion
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Phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries
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作者 Feifei Hong Xin Zhou +9 位作者 Xiaohong Liu Guilin Feng Heng Zhang Weifeng Fan Bin Zhang Meihua Zuo Wangyan Xing Ping Zhang Hua Yan Wei Xiang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第4期501-511,共11页
Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Dive... Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries. 展开更多
关键词 Phase engineering Ni-Mn layered oxide CATHODE Sodium-ion batteries
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Surface encapsulation of layered oxide cathode material with NiTiO_(3) for enhanced cycling stability of Na-ion batteries
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作者 胡紫霖 唐彬 +8 位作者 林挺 张楚 牛耀申 刘渊 高立克 谢飞 容晓晖 陆雅翔 胡勇胜 《Chinese Physics B》 SCIE EI CAS CSCD 2024年第8期551-558,共8页
In Na-ion batteries,O3-type layered oxide cathode materials encounter challenges such as particle cracking,oxygen loss,electrolyte side reactions,and multi-phase transitions during the charge/discharge process.This st... In Na-ion batteries,O3-type layered oxide cathode materials encounter challenges such as particle cracking,oxygen loss,electrolyte side reactions,and multi-phase transitions during the charge/discharge process.This study focuses on surface coating with NiTiO_(3) achieved via secondary heat treatment using a coating precursor and the surface material.Through in-situ x-ray diffraction(XRD)and differential electrochemical mass spectrometry(DEMS),along with crystal structure characterizations of post-cycling materials,it was determined that the NiTiO_(3) coating layer facilitates the formation of a stable lattice structure,effectively inhibiting lattice oxygen loss and reducing side reaction with the electrolyte.This enhancement in cycling stability was evidenced by a capacity retention of approximately 74%over 300 cycles at 1 C,marking a significant 30%improvement over the initial sample.Furthermore,notable advancements in rate performance were observed.Experimental results indicate that a stable and robust surface structure substantially enhances the overall stability of the bulk phase,presenting a novel approach for designing layered oxide cathodes with higher energy density. 展开更多
关键词 Na-ion battery layered oxides high voltage surface coating
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Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries
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作者 Yunting Wang Gaohui Du +7 位作者 Di Han Wenhao Shi Jiahao Deng Huayu Li Wenqi Zhao Shukai Ding Qingmei Su Bingshe Xu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第4期670-679,共10页
Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from ... Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes. 展开更多
关键词 Cobalt-free layered oxide Cathode Dual dopants Density functional theory calculation
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Cationic ordering transition in oxygen-redox layered oxide cathodes
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作者 Xinyan Li Ang Gao +10 位作者 Qinghua Zhang Hao Yu Pengxiang Ji Dongdong Xiao Xuefeng Wang Dong Su Xiaohui Rong Xiqian Yu Hong Li Yong-Sheng Hu Lin Gu 《Carbon Energy》 SCIE EI CAS CSCD 2024年第1期197-206,共10页
Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na... Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes. 展开更多
关键词 cationic ordering layered oxide cathodes oxygen redox sodium-ion batteries
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High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries
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作者 Tianxun Cai Mingzhi Cai +5 位作者 Jinxiao Mu Siwei Zhao Hui Bi Wei Zhao Wujie Dong Fuqiang Huang 《Nano-Micro Letters》 SCIE EI CAS CSCD 2024年第1期160-171,共12页
Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instabilit... Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries. 展开更多
关键词 High-entropy High-rate performance Li-TM interaction Air stability O3 layered oxide cathode
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Achieving structurally stable O3-type layered oxide cathodes through site-specific cation-anion co-substitution for sodium-ion batteries
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作者 Yihao Shen Chen Cheng +5 位作者 Xiao Xia Lei Wang Xi Zhou Pan Zeng Jianrong Zeng Liang Zhang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第6期411-418,I0011,共9页
O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrolla... O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries. 展开更多
关键词 Sodium-ion batteries O3-type layered oxides Site-specific co-doping Phase transition
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Cycling performance of layered oxide cathode materials for sodium-ion batteries
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作者 Jinpin Wu Junhang Tian +1 位作者 Xueyi Sun Weidong Zhuang 《International Journal of Minerals,Metallurgy and Materials》 SCIE EI CAS CSCD 2024年第7期1720-1744,共25页
Layered oxide is a promising cathode material for sodium-ion batteries because of its high-capacity,high operating voltage,and simple synthesis.Cycling performance is an important criterion for evaluating the applicat... Layered oxide is a promising cathode material for sodium-ion batteries because of its high-capacity,high operating voltage,and simple synthesis.Cycling performance is an important criterion for evaluating the application prospects of batteries.However,facing challenges,including phase transitions,ambient stability,side reactions,and irreversible anionic oxygen activity,the cycling performance of layered oxide cathode materials still cannot meet the application requirements.Therefore,this review proposes several strategies to address these challenges.First,bulk doping is introduced from three aspects:cationic single doping,anionic single doping,and multi-ion doping.Second,homogeneous surface coating and concentration gradient modification are reviewed.In addition,methods such as mixed structure design,particle engineering,high-entropy material construction,and integrated modification are proposed.Finally,a summary and outlook provide a new horizon for developing and modifying layered oxide cathode materials. 展开更多
关键词 sodium-ion battery layered oxide materials cycling performance bulking doping surface coating concentration gradient mixed structure high-entropy
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Inhibiting Voltage Decay in Li-Rich Layered Oxide Cathode:From O3-Type to O2-Type Structural Design
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作者 Guohua Zhang Xiaohui Wen +2 位作者 Yuheng Gao Renyuan Zhang Yunhui Huang 《Nano-Micro Letters》 SCIE EI CAS CSCD 2024年第12期81-102,共22页
Li-rich layered oxide(LRLO)cathodes have been regarded as promising candidates for next-generation Li-ion batteries due to their exceptionally high energy density,which combines cationic and anionic redox activities.H... Li-rich layered oxide(LRLO)cathodes have been regarded as promising candidates for next-generation Li-ion batteries due to their exceptionally high energy density,which combines cationic and anionic redox activities.However,continuous voltage decay during cycling remains the primary obstacle for practical applications,which has yet to be fundamentally addressed.It is widely acknowledged that voltage decay originates from the irreversible migration of transition metal ions,which usually further exacerbates structural evolution and aggravates the irreversible oxygen redox reactions.Recently,constructing O2-type structure has been considered one of the most promising approaches for inhibiting voltage decay.In this review,the relationship between voltage decay and structural evolution is systematically elucidated.Strategies to suppress voltage decay are systematically summarized.Additionally,the design of O2-type structure and the corresponding mechanism of suppressing voltage decay are comprehensively discussed.Unfortunately,the reported O2-type LRLO cathodes still exhibit partially disordered structure with extended cycles.Herein,the factors that may cause the irreversible transition metal migrations in O2-type LRLO materials are also explored,while the perspectives and challenges for designing high-performance O2-type LRLO cathodes without voltage decay are proposed. 展开更多
关键词 Lithium-ion batteries Li-rich layered oxide Voltage decay Migration of transition metal ions O2-type structural design
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Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene
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作者 Weixiao Ding Kun Zhao +2 位作者 Shican Jiang Zhen Huang Fang He 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第4期53-64,共12页
Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the... Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions. 展开更多
关键词 Chemical-looping oxidative DEHYDROGENATION ETHANE ETHYLENE NaNO_(3)-doped Ca_(2)MnO_(4)redox catalyst layered perovskites
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Tuning exsolution of nanoparticles in defect engineered layered perovskite oxides for efficient CO_(2) electrolysis 被引量:1
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作者 Zhengrong Liu Jun Zhou +7 位作者 Yueyue Sun Xiangling Yue Jiaming Yang Lei Fu Qinyuan Deng Hongfei Zhao Chaofan Yin Kai Wu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第9期219-227,共9页
Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite ox... Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite oxides,(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2) with n=5,8,and 12(LSTNn) for application as catalysts of CO_(2) electrolysis with the exsolution of Ni nanoparticles through a simple in-situ growth method.It is found that the density,size,and distribution of exsolved Ni nanoparticles are determined by the number of n in LSTNn due to the different stack structures of TiO_6 octahedra along the c axis.The Ni doping in LSTNn significantly improved the electrochemical activity by increasing oxygen vacancies,and the Ni metallic nanoparticles afford much more active sites.The results show that LSTNn cathodes can successfully be manipulated the activity by controlling both the n number and Ni exsolution.Among these LSTNn(n=5,8,and 12),LSTN8 renders a higher activity for electrolysis of CO_(2) with a current density of 1.50A cm^(-2)@2.0 V at 800℃ It is clear from these results that the number of n in(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2)with Ni-doping is a key factor in controlling the electrochemical performance and catalytic activity in SOEC. 展开更多
关键词 layered perovskite oxides In-situ growth SOEC TITANATE
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Oxygen-defects evolution to stimulate continuous capacity increase in Co-free Li-rich layered oxides 被引量:2
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作者 Yibin Zhang Xiaohui Wen +3 位作者 Zhepu Shi Bao Qiu Guoxin Chen Zhaoping Liu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第7期259-267,I0006,共10页
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i... Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides. 展开更多
关键词 Li-rich layered oxide Irreversible oxygen loss Nano-scale oxygen defect Li_(2)MnO_(3)-domain activation
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Self-supported ultrathin NiCo layered double hydroxides nanosheets electrode for efficient electrosynthesis of formate 被引量:1
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作者 Haoyuan Chi Jianlong Lin +6 位作者 Siyu Kuang Minglu Li Hai Liu Qun Fan Tianxiang Yan Sheng Zhang Xinbin Ma 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第10期267-275,I0008,共10页
Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,... Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions. 展开更多
关键词 CO_(2)reduction Methanol oxidation reaction FORMATE layered double hydroxides Oxygen vacancies
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Facet-dependent Thermal and Electrochemical Degradation of Lithium-rich Layered Oxides
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作者 Guohua Li Zhimin Ren +12 位作者 Haoxiang Zhuo Changhong Wang Biwei Xiao Jianwen Liang Ruizhi Yu Ting Lin Alin Li Tianwei Yu Wei Huang Anbang Zhang Qinghua Zhang Jiantao Wang Xueliang Sun 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2023年第6期345-355,共11页
Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox ... Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox activity,which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns.Herein,a flake-like LLO is prepared and aberration-corrected scanning transmission electron microscopy(STEM),in situ high-temperature X-ray diffraction(HT-XRD),and soft X-ray absorption spectrum(sXAS)are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes.Void-induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage.Particle degradation originates from side facets,such as the(010)facet,while the close(003)facet is stable.These results are further understood through ab initio molecular dynamics calculations,which show that oxygen atoms are lost from the{010}facets.Therefore,the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating,which result in crevice-voids in the ab plane facets.The study reveals important aspects of the mechanism responsible for oxygen-anionic activity-based degradation of LLO cathode materials used in lithium-ion batteries.In particular,this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO. 展开更多
关键词 electrochemical degradation facet degradation lithium-rich layered oxides thermal degradation
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The superhydrophobic sponge decorated with Ni-Co double layered oxides with thiol modification for continuous oil/water separation
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作者 Xiaodong Yang Na Yang +4 位作者 Ziqiang Gong Feifei Peng Bin Jiang Yongli Sun Luhong Zhang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2023年第2期296-305,共10页
In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modific... In this paper, the superhydrophobic polyurethane sponge(SS-PU) was facilely fabricated by etching with Jones reagent to bind the nanoparticles of Ni-Co double layered oxides(LDOs) on the surface, and following modification with n-dodecyl mercaptan(DDT). This method provides a new strategy to fabricate superhydrophobic PU sponge with a water contact angle of 157° for absorbing oil with low cost and in large scale. It exhibits the strong absorption capacity and highly selective characteristic for various kinds of oils which can be recycled by simple squeezing. Besides, the as-prepared sponge can deal with the floating and underwater oils, indicating its application value in handling oil spills and domestic oily wastewater. The good self-cleaning ability shows the potential to clear the pollutants due to the ultralow adhesion to water. Especially, the most important point is that the superhydrophobic sponge can continuously and effectively separate the oil/water mixture against the condition of turbulent disturbance by using our designed device system, which exhibit its good superhydrophobicity, strong stability.Furthermore, the SS-PU still maintained stable absorption performance after 150 cycle tests without losing capacity obviously, showing excellent durability in long-term operation and significant potential as an efficient absorbent in large-scale dispose of oily water. 展开更多
关键词 Superhydrophobic sponge Ni-Co double layered oxides Thiol modification Oil absorption Oil/water separation
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Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides 被引量:6
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作者 张丽 戴超华 +2 位作者 张秀秀 刘又年 阎建辉 《Transactions of Nonferrous Metals Society of China》 SCIE EI CAS CSCD 2016年第9期2380-2389,共10页
ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered d... ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides(LDHs) as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange(MO) under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2:1:1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed. 展开更多
关键词 ZnNiAl layered double hydroxide mixed oxide photocatalytic degradation phototatalytic activity
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Impact of Transition Metal Layer Vacancy on the Structure and Performance of P2 Type Layered Sodium Cathode Material
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作者 Orynbay Zhanadilov Sourav Baiju +7 位作者 Natalia Voronina Jun Ho Yu A.-Yeon Kim Hun‑Gi Jung Kyuwook Ihm Olivier Guillon Payam Kaghazchi Seung‑Taek Myung 《Nano-Micro Letters》 SCIE EI CAS CSCD 2024年第11期340-358,共19页
This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances t... This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances the structural stability during extensive cycling,increases the operation voltage,and induces a capacity increase while also activating oxygen redox,respectively,in Na_(0.7)[Ni_(0.2)V_(Ni0.1)Ru_(0.3)Mn_(0.4)]O_(2)(V-NRM)compound.Various analytical techniques including transmission electron microscopy,X-ray absorption near edge spectroscopy,operando X-ray diffraction,and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions.The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81%after 100 cycles.Furthermore,the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation,leading to a widened dominance of the OP4 phase without releasing O_(2) gas.These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries. 展开更多
关键词 layered oxide Oxygen evolution Sodium battery VACANCY CATHODE
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Enhancing layered perovskite ferrites with ultra-high-density nanoparticles via cobalt doping for ceramic fuel cell anode
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作者 Shuo Zhai Rubao Zhao +9 位作者 Hailong Liao Ling Fu Senran Hao Junyu Cai Yifan Wu Jian Wang Yunhong Jiang Jie Xiao Tao Liu Heping Xie 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第9期39-48,共10页
Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural co... Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural configuration.Herein,we employ controlled Co doping to effectively enhance the nanoparticle exsolution process in layered perovskite ferrites materials.CoFe alloy nanoparticles with ultra-high-density are exsolved on the(PrBa)_(0.95)(Fe_(0.8)Co_(0.1)Nb_(0.1))2O_(5+δ)(PBFCN_(0.1))surface under reducing atmosphere,providing significant amounts of reaction sites and good durability for hydrocarbon catalysis.Under a reducing atmosphere,cobalt facilitates the reduction of iron cations within PBFCN_(0.1),leading to the formation of CoFe alloy nanoparticles.This formation is accompanied by a cation exchange process,wherein,with the increase in temperature,partial cobalt ions are substituted by iron.Meanwhile,Co doping significantly enhance the electrical conductivity due to the stronger covalency of the Cosingle bondO bond compared with Fesingle bondO bond.A single cell with the configuration of PBFCN_(0.1)-Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)|SDC|Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF)-SDC achieves an extremely low polarization resistance of 0.0163Ωcm^(2)and a high peak power density of 740 mW cm^(−2)at 800℃.The cell also shows stable operation for 120 h in H_(2)with a constant current density of 285 mA cm^(−2).Furthermore,employing wet C_(2)H_(6)as fuel,the cell demonstrates remarkable performance,achieving peak power densities of 455 mW cm^(−2)at 800℃and 320 mW cm^(−2)at 750℃,marking improvements of 36%and 70%over the cell with(PrBa)_(0.95)(Fe_(0.9)Nb_(0.1))_(2)O_(5+δ)(PBFN)-SDC at these respective temperatures.This discovery emphasizes how temperature influences alloy nanoparticles exsolution within doped layered perovskite ferrites materials,paving the way for the development of high-performance ceramic fuel cell anodes. 展开更多
关键词 Solid oxide fuel cell ANODE Ethane fuel NANOPARTICLE EXSOLUTION layered perovskite Ferrites
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Graphene effectively activating "dead" water molecules between manganese dioxide layers in potassium-ion battery
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作者 Xinhai Wang Wensheng Yang +5 位作者 Shengshang Lu Shangshu Peng Tong Guo Quan Xie Qingquan Xiao Yunjun Ruan 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第6期306-315,I0008,共11页
Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower... Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies. 展开更多
关键词 GRAPHENE K-ion batteries Mn-based layered oxide Water molecules Density functional theory
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