Green roofs play a vital role in promoting sustainable urban development and achieving carbon neutrality by enhancing carbon sequestration, oxygen release, and efficiency of land use. Despite these benefits, living ro...Green roofs play a vital role in promoting sustainable urban development and achieving carbon neutrality by enhancing carbon sequestration, oxygen release, and efficiency of land use. Despite these benefits, living roof coverage in China remains limited. To address the challenges in policy formulation, operational monitoring, and the absence of multi-scale retrofit strategies supported by robust assessment methods, this study develops a comprehensive evaluation framework. The framework integrates vector data, building age information, and point-of-interest(POI) data, and applies an optimized Prophet model to classify six major climate zones. This approach facilitates the selection of appropriate plant species and substrates while quantifying the potential for carbon sequestration and oxygen release. An assessment of 90 cities reveals approximately 1.3861 billion square meters of rooftop area suitable for green roof implementation, with an estimated annual carbon sequestration potential of 67.30 million tons and oxygen release of 30.36 million tons. Commercial buildings contribute significantly, comprising 65% of the total suitable area. Climate zones 2 and 3 exhibit the most favorable outcomes. The current study provides a reliable quantitative reference for evaluating the carbon sequestration and oxygen release capacities of green roofs and supports the formulation of effective retrofit policies.展开更多
Oxygen release from Ni-rich cathode is one of the major structural degradations resulting in rapid performance fading in lithium-ion batteries(LIBs).The energy gap between the transition metals(TM)-d band and the O-p ...Oxygen release from Ni-rich cathode is one of the major structural degradations resulting in rapid performance fading in lithium-ion batteries(LIBs).The energy gap between the transition metals(TM)-d band and the O-p band serves as an effective evaluation metric in characterizing the potential for oxygen release.Given that the primary oxidation factors of NCM811 materials vary at different states of charge(SOC),this study employs high-throughput density functional theory(DFT)calculations combined with machine learning(ML)to systematically investigate the regulation mechanism of heteroatoms on the energy gap between the TM-d band(TM=Ni,Co)and O-p band at various SOC levels.Highthroughput DFT calculations were used to study doping thermodynamic stability and complete the database.The results indicate that dopant atoms remain at their original sites even at 50%SOC.Correlation analysis reveals that at 0 SOC,the dopant reduces Ni-O bonding interactions by forming its own bonds with oxygen,thereby preventing lattice oxygen escape and weakening the oxygen binding of the system during Ni redox.At 50%SOC,the dopant and Co atoms synergistically strengthen their bonding interactions with oxygen,thereby maintaining structural stability and inhibiting lattice oxygen escape.Based on R^(2)and root-mean-square error(RMSE),the gradient boosting regression(GBR)algorithm is identified as optimal for predicting the energy gaps between the Ni-d band and O-p band,as well as between the Co-d band and O-p band.Feature importance analysis demonstrates that the magnetic moment(Dma)of the doped atom significantly contributes to the prediction of ΔNi-O and ΔCo-O.In this study,the energy gap regulation mechanisms of Ni-d/O-p and Co-d/O-p are systematically investigated using non-empirical first principle calculations combined with data-driven machine learning,aiming to provide insights into the electrochemical stability of NCM811 and related materials.展开更多
Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surf...Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.展开更多
Nickel-rich layered oxide cathode materials such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)undergo deleterious side reactions when coupled with sulfide solid-state electrolytes(SSEs).To address this issue,we propose a...Nickel-rich layered oxide cathode materials such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)undergo deleterious side reactions when coupled with sulfide solid-state electrolytes(SSEs).To address this issue,we propose a dual-functional Ti_(3)(PO_(4))_(4)coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs.The electrochemically stabilized Ti_(3)(PO_(4))_(4)coating prevents direct contact between the SSEs and NCM811,thereby inhibiting interfacial side reactions.In addition,the internal structure of NCM811 can be stabilized by Ti doping,which inhibits the oxygen release behavior of NCM811 at high charge state,preventing further electrochemical oxidation of the SSEs.The modified NCM811@TiP cathode exhibits excellent long cycle stability,with 74.4%capacity retention after 100 cycles at a cut-off voltage of 4.2 V.This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.展开更多
Recognized as one of the important active species involved in varicus ractions,singlet oxygen(^(1)O_(2))shows potential applications in chemical.blological,and environmental related fields.However,the con-trolled capt...Recognized as one of the important active species involved in varicus ractions,singlet oxygen(^(1)O_(2))shows potential applications in chemical.blological,and environmental related fields.However,the con-trolled capture and release of^(1)O_(2)are still facing huge challenges due to its short lifetime and high re-activity.Herein,a framework-interpenetration tuning strategy was applied on a metal-organic framework(MOF)that aiming to improve the capture and release rate of O.The porosity of the MOF was remark-ably enhanced with the structural evolution from seven-fold(termed NKM-181)to six-fold interpene-tration(termed NKM-182),and the active anthracene sites became much mare accessible.Such drastic process can be achieved as simple as exchanging the primitive MOF in selected solvent and occurred surprisingly as single-crystal to single-crystal transformation.Also,additionally owing to the unblocked regular channels,NKM-182 shown significantly improved^(1)O_(2)trapping and releasing rates compared to strates an unprecedented regulation of^(1)O_(2)capture and release that of in NKM-181.This work demon process,along with achieving the highest^(1)O_(2)capture and release rate among reported porous materi-als.furthermore.the obtalned endoperoxides with^(1)O_(2)loaded(termed EPO-NKM-181 and EPO-NKM-182)can be used as a high efficiency smart material for anti-fake application.展开更多
To create evaluation methods in reclamation area according to specific conditions in coal mines, introduced the re- search trends both at home and abroad on plants＇ carbon fixation and oxygen release, offered, at the...To create evaluation methods in reclamation area according to specific conditions in coal mines, introduced the re- search trends both at home and abroad on plants＇ carbon fixation and oxygen release, offered, at the same time, several method models on carbon fixation and oxygen release by plants, and gave some suggestions in this field on the basis of reading the ex- periences of former experts. Finally, used biomass method and instrument measurement method to analyze carbon emission benefits in the study area.展开更多
Lithium-rich manganese-based oxides(LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes of...Lithium-rich manganese-based oxides(LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes often declines because of capacity fading during cycling. This decline is primarily attributed to anisotropic lattice strain and oxygen release from cathode surfaces. Given notable structural transformations, complex redox reactions, and detrimental interface side reactions in LRMOs, the development of a single modification approach that addresses bulk and surface issues is challenging. Therefore,this study introduces a surface double-coupling engineering strategy that mitigates bulk strain and reduces surface side reactions. The internal spinel-like phase coating layer, featuring threedimensional(3D) lithium-ion diffusion channels, effectively blocks oxygen release from the cathode surface and mitigates lattice strain. In addition, the external Li_(3)PO_(4) coating layer, noted for its superior corrosion resistance, enhances the interfacial lithium transport and inhibits the dissolution of surface transition metals. Notably, the spinel phase, as excellent interlayer, securely anchors Li_(3)PO_(4) to the bulk lattice and suppresses oxygen release from lattices. Consequently, these modifications considerably boost structural stability and durability, achieving an impressive capacity retention of 83.4% and a minimal voltage decay of 1.49 m V per cycle after 150 cycles at 1 C. These findings provide crucial mechanistic insights into the role of surface modifications and guide the development of high-capacity cathodes with enhanced cyclability.展开更多
FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen tempe...FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen temperature-programmed reduction （H2-TPR） techniques. The dynamic oxygen storage capacity （DOSC） was investigated by mass spectrometry with CO/O2 transient pulses. The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/（Ce＋Fe）. The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2. TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties, which influenced the oxygen handling properties. DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC. The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect. The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface, which seriously influenced the catalytic properties, especially after hydrothermal aging treatment.展开更多
Gas generation induced by parasitic reactions in lithium-metal batteries(LMB)has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry,which occurs via the complex interplays ...Gas generation induced by parasitic reactions in lithium-metal batteries(LMB)has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry,which occurs via the complex interplays among electrolytes,cathode,anode,and the decomposition species that travel across the cell.In this work,a novel in situ differential electrochemical mass spectrometry is constructed to differentiate the speciation and source of each gas product generated either during cycling or during storage in the presence of cathode chemistries of varying structure and nickel contents.It unambiguously excludes the trace moisture in electrolyte as the major source of hydrogen and convincingly identifies the layer-structured NCM cathode material as the source of instability that releases active oxygen from the lattice at high voltages when NCM experiences H2→H3 phase transition,which in turn reacts with carbonate solvents,producing both CO_(2)and proton at the cathode side.Such proton in solvated state travels across the cell and becomes the main source for hydrogen generated at the anode side.Mechanisms are proposed to account for these irreversible reactions,and two electrolyte additives based on phosphate structure are adopted to mitigate the gas generation based on the understanding of the above decomposition chemistries.展开更多
A series of Pt-Pd bimetallic catalysts supported on CeO_(2)-ZrO_(2)-La_(2)O_(3) mixed oxides were synthesized through the conventional impregnation method.Three-way catalytic performance evaluations along with detaile...A series of Pt-Pd bimetallic catalysts supported on CeO_(2)-ZrO_(2)-La_(2)O_(3) mixed oxides were synthesized through the conventional impregnation method.Three-way catalytic performance evaluations along with detailed physio-chemical characterizations were carried out to establish possible structure-activity correlations.Results show that on the one hand,different Pt/Pd ratios can strongly affect the TWC behaviors of Pt-Pd/CZL catalysts by modulating the synergistic effect between Pt and Pd.On the other hand,higher Pt/Pd ratio also favors better dispersion of precious metals.Such improved precious metals(PM)dispersion can promote the metal-support interaction and increase the surface oxygen vacancies concentration,thereby raising the dynamic oxygen storage/release capacity,improving the redox ability as well as enha ncing the thermal stability of the Pt-Pd/CZL catalyst.Moreover,the stro ng metal-support interaction can augment surface oxygen vacancy concentration,thereby benefiting low temperature CO and NO reaction via augmented NOxadsorption and nitrate conversion.展开更多
High-voltage LiCoO_(2)(LCO)offers a prelude to breaking the bottleneck of the energy density of lithium-ion batteries,however,LiCoO_(2)is subject to serious structural and interfacial degradation above voltages>4.5...High-voltage LiCoO_(2)(LCO)offers a prelude to breaking the bottleneck of the energy density of lithium-ion batteries,however,LiCoO_(2)is subject to serious structural and interfacial degradation above voltages>4.55 V(vs.Li/Li^(+)).Herein,an in-situ Li_(6.25)La_(3)Zr_(2)A_(l0.25)O_(12)(LLZAO)layer is constructed on the LCO surface to achieve operating voltage at 4.6 V.The detailed characterizations(ex-situ XRD,ex-situ Raman,DFT,etc.)reveal that the LLZAO layer greatly enhances Li+conductivity attributed to the ionconducting layer on the surface/interface,and closely combines with LiCoO_(2)particle to ensure stable cathode/electrolyte interface,thus suppressing the highly reactive Co^(4+)and O^(-)triggered surface side reactions at high-voltage.Moreover,the introduction of La^(3+)/Zr^(4+)/Al^(3+)with a larger ionic radius(La^(3+)/Zr^(4+)are larger than Co^(3+))and weaker electronegativity(La/Zr/Al are weaker than Co)into Co^(3+)sites readjusts the electron cloud density between Co–O–Li,which reinforces the Co–O bond and widens the band-center gap of Co 3d and O 2p,thus restraining the detrimental phase transition(from H3 to H1-3 phase)and the formation of Co_(3)O_(4)spinel phase(attributed to lattice oxygen release),subsequently alleviating the particle cracking and structural collapse during repeated Li^(+)de/intercalation.Therefore,after 100 cycles at 3.0–4.6 V,LCO@1.0LLZAO exhibits a superior discharge capacity of 188.5 m A h g^(-1),with a capacity retention of 85.1%.The above research has brought about meaningful guidance for the evolution of cathode materials with high voltage.展开更多
Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO ...Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.展开更多
Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition ...Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.展开更多
The invention covers the process for preparing an oxide complex that can absorb and release oxygen. The covered procedures include:preparation of CeO2, ZrO2 and HfO2 as raw material; preparation of the complex oxide ...The invention covers the process for preparing an oxide complex that can absorb and release oxygen. The covered procedures include:preparation of CeO2, ZrO2 and HfO2 as raw material; preparation of the complex oxide with the raw material by employing heating and deoxidation method;and the process for re-heating and oxidizing the deoxidized complex oxide.展开更多
The dual role of reactive oxygen and nitrogen species(RONS)in physiological and pathological processes in biological systems has been widely reported.It has been recently suggested that the regulation of RONS levels u...The dual role of reactive oxygen and nitrogen species(RONS)in physiological and pathological processes in biological systems has been widely reported.It has been recently suggested that the regulation of RONS levels under physiological and pathological conditions is a potential therapy to promote health and treat diseases,respectively.Injectable hydrogels have been emerging as promising biomaterials for RONS-related biomedical applications owing to their excellent biocompatibility,three-dimensional and extracellular matrix-mimicking structures,tunable properties and easy functionalization.These hydrogels have been developed as advanced injectable platforms for locally generating or scavenging RONS,depending on the specific conditions of the target disease.In this review article,the design principles and mechanism by which RONS are generated/scavenged from hydrogels are outlined alongside a discussion of their in vitro and in vivo evaluations.Additionally,we highlight the advantages and recent developments of these injectable RONS-controlling hydrogels for regenerativemedicines and tissue engineering applications.展开更多
The storage and controlled release of singlet oxygen(^(1)O_(2))have attracted increasing attention due to the wide application and microsecond lifetime of^(1)O_(2)in water.Herein we provide an integrated nanoplatform ...The storage and controlled release of singlet oxygen(^(1)O_(2))have attracted increasing attention due to the wide application and microsecond lifetime of^(1)O_(2)in water.Herein we provide an integrated nanoplatform consisting of a diphenylanthracene derivative,a water-soluble pillar[5]arene and a photosensitizer tetrakis(4-hydroxyphenyl)porphyrin(TPP),that may provide the controlled generation,storage and release of singlet oxygen.We design a new diphenylanthracene derivative with two trimethylammonium bromide groups on both ends that can be well recognized by the pillar[5]arene.The formed nanocarriers can be used to load TPP through their supramolecular self-assembly.The resulting nanoparticles show good water-solubility and uniform spherical morphology.After laser irradiation(660 nm),the nanoparticles exhibit excellent ability for the generation and storage of^(1)O_(2).When the irradiated nanoparticles are heated above 80°C,^(1)O_(2)can be released from the system.Therefore,in this paper we pioneer the use of noncovalent interaction to integrate the diphenylanthracene derivatives and photosensitizers into one functional system,which provides a new strategy for the controlled generation,storage and release of singlet oxygen.We believe this groundbreaking strategy will have a great potential in providing necessary amounts of^(1)O_(2)for the photodynamic therapy of tumors in dark.展开更多
The paper reviewed the references of carbon sequence and oxygen release of forest resources. The dynastic physical accounting model is established, and benefit transfer model is adopted to calculate willing to pay for...The paper reviewed the references of carbon sequence and oxygen release of forest resources. The dynastic physical accounting model is established, and benefit transfer model is adopted to calculate willing to pay for carbon sequence and oxygen. Benghe Forestry Farm of Linyi Prefecture of Shandong Province is selected as the case study area, the accounting result is presented in the paper.展开更多
Coupled with anionic and cationic redox chemistry,Li-rich/excess cathode materials are prospective high-energy-density candidates for the next-generation Li-ion batteries.However,irreversible lattice oxygen loss would...Coupled with anionic and cationic redox chemistry,Li-rich/excess cathode materials are prospective high-energy-density candidates for the next-generation Li-ion batteries.However,irreversible lattice oxygen loss would exacerbate irreversible transition metal migration,resulting in a drastic voltage decay and capacity degeneration.Herein,a metastable layered Li-excess cathode material,T2-type Li_(0.72)[Li_(0.12)Ni_(0.36)Mn_(0.52)]O_(2),was developed,in which both oxygen stacking arrangement and Li coordination environment fundamentally differ from that in conventional O3-type layered structures.By means of the reversible Li migration processes and structural evolutions,not only can voltage decay be effectively restrained,but also excellent capacity retention can be achieved upon long-term cycling.Moreover,irreversible/reversible anionic/cationic redox activities have been well assigned and quantified by various in/ex-situ spectroscopic techniques,further clarifying the charge compensation mechanism associated with(de)lithiation.These findings of the novel T2 structure with the enhanced anionic redox stability will provide a new scope for the development of high-energy-density Li-rich cathode materials.展开更多
文摘Green roofs play a vital role in promoting sustainable urban development and achieving carbon neutrality by enhancing carbon sequestration, oxygen release, and efficiency of land use. Despite these benefits, living roof coverage in China remains limited. To address the challenges in policy formulation, operational monitoring, and the absence of multi-scale retrofit strategies supported by robust assessment methods, this study develops a comprehensive evaluation framework. The framework integrates vector data, building age information, and point-of-interest(POI) data, and applies an optimized Prophet model to classify six major climate zones. This approach facilitates the selection of appropriate plant species and substrates while quantifying the potential for carbon sequestration and oxygen release. An assessment of 90 cities reveals approximately 1.3861 billion square meters of rooftop area suitable for green roof implementation, with an estimated annual carbon sequestration potential of 67.30 million tons and oxygen release of 30.36 million tons. Commercial buildings contribute significantly, comprising 65% of the total suitable area. Climate zones 2 and 3 exhibit the most favorable outcomes. The current study provides a reliable quantitative reference for evaluating the carbon sequestration and oxygen release capacities of green roofs and supports the formulation of effective retrofit policies.
基金supported by the National Natural Science Foundation of China(Grant no.52463025,and 52062035)the Major Discipline Academic and Technical Leaders Training Program of Jiangxi Province(Grant no.20213BCJ22056)+2 种基金the Key R&D Program of Jiangxi Province(Grant no.20223BBE51028)the Jiangxi Province Key Laboratory of Lithium-ion Battery Materials and Application(2024SSY05202)the Jiangxi Province Graduate Innovation Special Fund Project(YC2023-B004)。
文摘Oxygen release from Ni-rich cathode is one of the major structural degradations resulting in rapid performance fading in lithium-ion batteries(LIBs).The energy gap between the transition metals(TM)-d band and the O-p band serves as an effective evaluation metric in characterizing the potential for oxygen release.Given that the primary oxidation factors of NCM811 materials vary at different states of charge(SOC),this study employs high-throughput density functional theory(DFT)calculations combined with machine learning(ML)to systematically investigate the regulation mechanism of heteroatoms on the energy gap between the TM-d band(TM=Ni,Co)and O-p band at various SOC levels.Highthroughput DFT calculations were used to study doping thermodynamic stability and complete the database.The results indicate that dopant atoms remain at their original sites even at 50%SOC.Correlation analysis reveals that at 0 SOC,the dopant reduces Ni-O bonding interactions by forming its own bonds with oxygen,thereby preventing lattice oxygen escape and weakening the oxygen binding of the system during Ni redox.At 50%SOC,the dopant and Co atoms synergistically strengthen their bonding interactions with oxygen,thereby maintaining structural stability and inhibiting lattice oxygen escape.Based on R^(2)and root-mean-square error(RMSE),the gradient boosting regression(GBR)algorithm is identified as optimal for predicting the energy gaps between the Ni-d band and O-p band,as well as between the Co-d band and O-p band.Feature importance analysis demonstrates that the magnetic moment(Dma)of the doped atom significantly contributes to the prediction of ΔNi-O and ΔCo-O.In this study,the energy gap regulation mechanisms of Ni-d/O-p and Co-d/O-p are systematically investigated using non-empirical first principle calculations combined with data-driven machine learning,aiming to provide insights into the electrochemical stability of NCM811 and related materials.
基金supported by the National Key Research and Development Program (2019YFA0405601)National Science Foundation of China(No. 22309097, 22179066, 21902179)+1 种基金Shandong Provincial Natural Science Foundation (2023KJ228, ZR2021QE061, ZR202103010205)the Startup Foundation for Advanced Talents in Qingdao University (DC2000005106)
文摘Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.
基金supported by the National Natural Science Foundation of China(No.52272258),the Beijing Nova Program(No.20220484214)Key R&D and transformation projects in Qinghai Province(No.2023-HZ-801)the Fundamental Research Funds for the Central Universities(No.2023ZKPYJD07)。
文摘Nickel-rich layered oxide cathode materials such as LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)undergo deleterious side reactions when coupled with sulfide solid-state electrolytes(SSEs).To address this issue,we propose a dual-functional Ti_(3)(PO_(4))_(4)coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs.The electrochemically stabilized Ti_(3)(PO_(4))_(4)coating prevents direct contact between the SSEs and NCM811,thereby inhibiting interfacial side reactions.In addition,the internal structure of NCM811 can be stabilized by Ti doping,which inhibits the oxygen release behavior of NCM811 at high charge state,preventing further electrochemical oxidation of the SSEs.The modified NCM811@TiP cathode exhibits excellent long cycle stability,with 74.4%capacity retention after 100 cycles at a cut-off voltage of 4.2 V.This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.
基金the financial support of the National Natural Science Foundation of China(Nos.22035003 and 22201137)Nature Science Fund of Tianjin,China(No.19JCZDJC37200)+1 种基金Fundamental Research Funds for the Central Universities(No.63223020)the Haihe Laboratory of Sustainable Chemical Transformations(No.YYJC202101).
文摘Recognized as one of the important active species involved in varicus ractions,singlet oxygen(^(1)O_(2))shows potential applications in chemical.blological,and environmental related fields.However,the con-trolled capture and release of^(1)O_(2)are still facing huge challenges due to its short lifetime and high re-activity.Herein,a framework-interpenetration tuning strategy was applied on a metal-organic framework(MOF)that aiming to improve the capture and release rate of O.The porosity of the MOF was remark-ably enhanced with the structural evolution from seven-fold(termed NKM-181)to six-fold interpene-tration(termed NKM-182),and the active anthracene sites became much mare accessible.Such drastic process can be achieved as simple as exchanging the primitive MOF in selected solvent and occurred surprisingly as single-crystal to single-crystal transformation.Also,additionally owing to the unblocked regular channels,NKM-182 shown significantly improved^(1)O_(2)trapping and releasing rates compared to strates an unprecedented regulation of^(1)O_(2)capture and release that of in NKM-181.This work demon process,along with achieving the highest^(1)O_(2)capture and release rate among reported porous materi-als.furthermore.the obtalned endoperoxides with^(1)O_(2)loaded(termed EPO-NKM-181 and EPO-NKM-182)can be used as a high efficiency smart material for anti-fake application.
文摘To create evaluation methods in reclamation area according to specific conditions in coal mines, introduced the re- search trends both at home and abroad on plants＇ carbon fixation and oxygen release, offered, at the same time, several method models on carbon fixation and oxygen release by plants, and gave some suggestions in this field on the basis of reading the ex- periences of former experts. Finally, used biomass method and instrument measurement method to analyze carbon emission benefits in the study area.
基金National Natural Science Foundation of China (22179008, 21875022)Yibin ‘Jie Bang Gua Shuai’ (2022JB004)+3 种基金support from the Beijing Nova Program (20230484241)support from the Postdoctoral Fellowship Program of CPSF (GZB20230931)Special Support of the Chongqing Postdoctoral Research Project (2023CQBSHTB2041)Initial Energy Science & Technology Co., Ltd (IEST)。
文摘Lithium-rich manganese-based oxides(LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes often declines because of capacity fading during cycling. This decline is primarily attributed to anisotropic lattice strain and oxygen release from cathode surfaces. Given notable structural transformations, complex redox reactions, and detrimental interface side reactions in LRMOs, the development of a single modification approach that addresses bulk and surface issues is challenging. Therefore,this study introduces a surface double-coupling engineering strategy that mitigates bulk strain and reduces surface side reactions. The internal spinel-like phase coating layer, featuring threedimensional(3D) lithium-ion diffusion channels, effectively blocks oxygen release from the cathode surface and mitigates lattice strain. In addition, the external Li_(3)PO_(4) coating layer, noted for its superior corrosion resistance, enhances the interfacial lithium transport and inhibits the dissolution of surface transition metals. Notably, the spinel phase, as excellent interlayer, securely anchors Li_(3)PO_(4) to the bulk lattice and suppresses oxygen release from lattices. Consequently, these modifications considerably boost structural stability and durability, achieving an impressive capacity retention of 83.4% and a minimal voltage decay of 1.49 m V per cycle after 150 cycles at 1 C. These findings provide crucial mechanistic insights into the role of surface modifications and guide the development of high-capacity cathodes with enhanced cyclability.
基金support the National HighTech Research and Development Program of China (No.2011AA03A405)
文摘FeOx-CeO2 mixed oxides with increasing Fe/（Ce＋Fe） atomic ratio （1-20 mol%） were prepared by sol-gel method and characterized by X-ray powder diffraction （XRD）, Brunauer-Emrnett-Teller （BET） and Hydrogen temperature-programmed reduction （H2-TPR） techniques. The dynamic oxygen storage capacity （DOSC） was investigated by mass spectrometry with CO/O2 transient pulses. The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/（Ce＋Fe）. The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2. TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties, which influenced the oxygen handling properties. DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC. The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect. The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface, which seriously influenced the catalytic properties, especially after hydrothermal aging treatment.
基金the financial supports from the Key-Area Research and Development Program of Guangdong Province(2020B090919001)Shenzhen Key Laboratory of Solid-State Batteries(ZDSYS20180208184346531)+1 种基金Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(2018B030322001)Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices(2019B121205001)。
文摘Gas generation induced by parasitic reactions in lithium-metal batteries(LMB)has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry,which occurs via the complex interplays among electrolytes,cathode,anode,and the decomposition species that travel across the cell.In this work,a novel in situ differential electrochemical mass spectrometry is constructed to differentiate the speciation and source of each gas product generated either during cycling or during storage in the presence of cathode chemistries of varying structure and nickel contents.It unambiguously excludes the trace moisture in electrolyte as the major source of hydrogen and convincingly identifies the layer-structured NCM cathode material as the source of instability that releases active oxygen from the lattice at high voltages when NCM experiences H2→H3 phase transition,which in turn reacts with carbonate solvents,producing both CO_(2)and proton at the cathode side.Such proton in solvated state travels across the cell and becomes the main source for hydrogen generated at the anode side.Mechanisms are proposed to account for these irreversible reactions,and two electrolyte additives based on phosphate structure are adopted to mitigate the gas generation based on the understanding of the above decomposition chemistries.
基金Project supported by the Key Program of Science Technology Department of Zhejiang Province(2018C03037)the Natural Science Foundation of Jiangsu Province(BK20201037)+2 种基金Jiangsu Industry-University-Research Cooperation Project(BY2022101)the Scientific Research Fund of Nanjing Institute of Technology(YKJ2019111)Students'Science and Technology Innovation Fund of Nanjing Institute of Technology(TB202312034).
文摘A series of Pt-Pd bimetallic catalysts supported on CeO_(2)-ZrO_(2)-La_(2)O_(3) mixed oxides were synthesized through the conventional impregnation method.Three-way catalytic performance evaluations along with detailed physio-chemical characterizations were carried out to establish possible structure-activity correlations.Results show that on the one hand,different Pt/Pd ratios can strongly affect the TWC behaviors of Pt-Pd/CZL catalysts by modulating the synergistic effect between Pt and Pd.On the other hand,higher Pt/Pd ratio also favors better dispersion of precious metals.Such improved precious metals(PM)dispersion can promote the metal-support interaction and increase the surface oxygen vacancies concentration,thereby raising the dynamic oxygen storage/release capacity,improving the redox ability as well as enha ncing the thermal stability of the Pt-Pd/CZL catalyst.Moreover,the stro ng metal-support interaction can augment surface oxygen vacancy concentration,thereby benefiting low temperature CO and NO reaction via augmented NOxadsorption and nitrate conversion.
基金supported by the Chongzuo Science and Technology Program Project Fund(No.FA20210713)。
文摘High-voltage LiCoO_(2)(LCO)offers a prelude to breaking the bottleneck of the energy density of lithium-ion batteries,however,LiCoO_(2)is subject to serious structural and interfacial degradation above voltages>4.55 V(vs.Li/Li^(+)).Herein,an in-situ Li_(6.25)La_(3)Zr_(2)A_(l0.25)O_(12)(LLZAO)layer is constructed on the LCO surface to achieve operating voltage at 4.6 V.The detailed characterizations(ex-situ XRD,ex-situ Raman,DFT,etc.)reveal that the LLZAO layer greatly enhances Li+conductivity attributed to the ionconducting layer on the surface/interface,and closely combines with LiCoO_(2)particle to ensure stable cathode/electrolyte interface,thus suppressing the highly reactive Co^(4+)and O^(-)triggered surface side reactions at high-voltage.Moreover,the introduction of La^(3+)/Zr^(4+)/Al^(3+)with a larger ionic radius(La^(3+)/Zr^(4+)are larger than Co^(3+))and weaker electronegativity(La/Zr/Al are weaker than Co)into Co^(3+)sites readjusts the electron cloud density between Co–O–Li,which reinforces the Co–O bond and widens the band-center gap of Co 3d and O 2p,thus restraining the detrimental phase transition(from H3 to H1-3 phase)and the formation of Co_(3)O_(4)spinel phase(attributed to lattice oxygen release),subsequently alleviating the particle cracking and structural collapse during repeated Li^(+)de/intercalation.Therefore,after 100 cycles at 3.0–4.6 V,LCO@1.0LLZAO exhibits a superior discharge capacity of 188.5 m A h g^(-1),with a capacity retention of 85.1%.The above research has brought about meaningful guidance for the evolution of cathode materials with high voltage.
基金This work was financially supported by the High‐level Talents'Discipline Construction Fund of Shandong University(31370089963078)the Shandong Provincial Science and Technology Major Project(2018JM RH0211 and 2017CXGC1010)+3 种基金the Research Funds of Shandong University(10000089395121)the Natural Science Foundation of Shandong Province(ZR2019MEM052 and ZR2017MEM002)The National Natural Science Foundation of China(grant no.52002287)the Start‐up Funding of Wenzhou University are acknowledged.
文摘Layered lithium-rich manganese-based oxide(LRMO)has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation.Herein,a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue.The multilayer interface is visually observed using an atomic-resolution scanning transmission electron microscope and a high-resolution transmission electron microscope.Combined with the electrochemical characterization,the redox of lattice oxygen is suppressed during the initial charging.In situ X-ray diffraction and the high-resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial(de)lithiation,which further prevents lattice distortion during long cycling.As a result,the initial Coulombic efficiency of the modified LRMO is up to 87.31%,and the rate capacity and long-term cycle stability also improved considerably.In this work,a facile surface reconstruction strategy is used to suppress vigorous anionic redox,which is expected to stimulate material design in high-performance lithium ion batteries.
基金supported by the National Natural Science Foundation of China(22175070,22293041,51902081,and 21871106)Key Fund in Hebei Province Department of Education China(ZD2022042)。
文摘Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.
文摘The invention covers the process for preparing an oxide complex that can absorb and release oxygen. The covered procedures include:preparation of CeO2, ZrO2 and HfO2 as raw material; preparation of the complex oxide with the raw material by employing heating and deoxidation method;and the process for re-heating and oxidizing the deoxidized complex oxide.
基金supported by a grant from Priority Research Centers Program(2019R1A6A1A11051471)funded by the National Research Foundation of Korea(NRF)and Korea Medical Device Development Fund grant funded by the Korea government(the Ministry of Science and ICT,the Ministry of Trade,Industry and Energy,the Ministry of Health&Welfare and the Ministry of Food and Drug Safety)(Project Number:RS-2020-KD000033)Korea Evaluation Institute of Industrial Technology(KEIT 20018560,NTIS 1415180625)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘The dual role of reactive oxygen and nitrogen species(RONS)in physiological and pathological processes in biological systems has been widely reported.It has been recently suggested that the regulation of RONS levels under physiological and pathological conditions is a potential therapy to promote health and treat diseases,respectively.Injectable hydrogels have been emerging as promising biomaterials for RONS-related biomedical applications owing to their excellent biocompatibility,three-dimensional and extracellular matrix-mimicking structures,tunable properties and easy functionalization.These hydrogels have been developed as advanced injectable platforms for locally generating or scavenging RONS,depending on the specific conditions of the target disease.In this review article,the design principles and mechanism by which RONS are generated/scavenged from hydrogels are outlined alongside a discussion of their in vitro and in vivo evaluations.Additionally,we highlight the advantages and recent developments of these injectable RONS-controlling hydrogels for regenerativemedicines and tissue engineering applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.21801139,21871227)the Innovation and Entrepreneurship Program of Jiangsu Province(Grant No.JSSCBS20211106)the National Undergraduates Innovating Experimentation Project(Grant No.202110304134H).
文摘The storage and controlled release of singlet oxygen(^(1)O_(2))have attracted increasing attention due to the wide application and microsecond lifetime of^(1)O_(2)in water.Herein we provide an integrated nanoplatform consisting of a diphenylanthracene derivative,a water-soluble pillar[5]arene and a photosensitizer tetrakis(4-hydroxyphenyl)porphyrin(TPP),that may provide the controlled generation,storage and release of singlet oxygen.We design a new diphenylanthracene derivative with two trimethylammonium bromide groups on both ends that can be well recognized by the pillar[5]arene.The formed nanocarriers can be used to load TPP through their supramolecular self-assembly.The resulting nanoparticles show good water-solubility and uniform spherical morphology.After laser irradiation(660 nm),the nanoparticles exhibit excellent ability for the generation and storage of^(1)O_(2).When the irradiated nanoparticles are heated above 80°C,^(1)O_(2)can be released from the system.Therefore,in this paper we pioneer the use of noncovalent interaction to integrate the diphenylanthracene derivatives and photosensitizers into one functional system,which provides a new strategy for the controlled generation,storage and release of singlet oxygen.We believe this groundbreaking strategy will have a great potential in providing necessary amounts of^(1)O_(2)for the photodynamic therapy of tumors in dark.
文摘The paper reviewed the references of carbon sequence and oxygen release of forest resources. The dynastic physical accounting model is established, and benefit transfer model is adopted to calculate willing to pay for carbon sequence and oxygen. Benghe Forestry Farm of Linyi Prefecture of Shandong Province is selected as the case study area, the accounting result is presented in the paper.
基金supported by the National Science Foundation under Grant No.DMR1809372。
文摘Coupled with anionic and cationic redox chemistry,Li-rich/excess cathode materials are prospective high-energy-density candidates for the next-generation Li-ion batteries.However,irreversible lattice oxygen loss would exacerbate irreversible transition metal migration,resulting in a drastic voltage decay and capacity degeneration.Herein,a metastable layered Li-excess cathode material,T2-type Li_(0.72)[Li_(0.12)Ni_(0.36)Mn_(0.52)]O_(2),was developed,in which both oxygen stacking arrangement and Li coordination environment fundamentally differ from that in conventional O3-type layered structures.By means of the reversible Li migration processes and structural evolutions,not only can voltage decay be effectively restrained,but also excellent capacity retention can be achieved upon long-term cycling.Moreover,irreversible/reversible anionic/cationic redox activities have been well assigned and quantified by various in/ex-situ spectroscopic techniques,further clarifying the charge compensation mechanism associated with(de)lithiation.These findings of the novel T2 structure with the enhanced anionic redox stability will provide a new scope for the development of high-energy-density Li-rich cathode materials.
