Sodium-ion batteries have been deemed as a sustainable alternative to lithium-ion systems due to the abundance and affordability of sodium sources.Nevertheless,developing high-energy-density P2-type layered oxide cath...Sodium-ion batteries have been deemed as a sustainable alternative to lithium-ion systems due to the abundance and affordability of sodium sources.Nevertheless,developing high-energy-density P2-type layered oxide cathodes with long-term cycling stability poses challenges,stemming from irreversible phase transitions,structural degradation,and lattice oxygen instability during electrochemical cycling.Here,we propose a one-step NbB_(2)modification strategy that enhances both bulk and surface properties of Na_(0.8)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)cathodes.By exploiting different techniques,we disclose that bulk Nb and B doping combined with a Nb-Transition Metal-BO_(3)surface layer reconstruction enable a reversible P2-OP4 phase transition and,meanwhile,improve anionic redox reversibility.In addition,Li^(+)migrates into alkali-metal layers and underpins the layered structure through the“pillar effect”,thereby facilitating the Na^(+)diffusion in Na_(0.8)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)cathodes and retaining their structural integrity at high voltage.As a result,the modified cathodes achieve 93.6%capacity retention after 500 cycles at 1C and deliver specific capacities above 114 m A h g^(-1)at 10C within 2.0-4.3 V.Contrary to the previous studies reporting that OP4 phase are detrimental to the structural stability of layered cathodes,we experimentally validate that a well-regulated P2-OP4 phase transition is beneficial for structural and electrochemical stabilities.展开更多
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries;however,they face significant challenges,including structural degradation when charged at high cutoff voltages and structural changes u...Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries;however,they face significant challenges,including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere.In response to these issues,we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability.The redox reaction of Cu^(2+/3+)can provide certain charge compensation,and the introduction of Al can further suppress the Jahn-Teller effect of Mn,thereby achieving superior long-term cycling performance.The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage,thereby explaining the improvement in electrochemical performance.DFT calculations reveal a high chemical tolerance to moisture,with lower adsorption energy for H_(2)O compared to pure Na_(0.67)Cu_(0.25)Mn_(0.75)O_(2).A representative Na_(0.67)Cu_(0.20)Al_(0.05)Mn_(0.75)O_(2)cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C,along with a remarkable capacity retention of 79.1%(2 C,500 cycles).展开更多
Sodium-ion batteries(SIBs)are emerging as a promising alternative for large-scale energy storage,particularly in grid applications.Within the array of potential cathode materials,Fe/Mn-based layered oxides are notable...Sodium-ion batteries(SIBs)are emerging as a promising alternative for large-scale energy storage,particularly in grid applications.Within the array of potential cathode materials,Fe/Mn-based layered oxides are notable for their advantageous theoretical specific capacity,economic viability,and environmental sustainability.Nevertheless,the practical application of Fe/Mn-based layered oxides is constrained by their suboptimal cycle performance and rate capability during actual charging and discharging.Ion doping is an effective approach for addressing the aforementioned issues.In this context,we have successfully developed a novel K^(+) and Mg^(2+) codoped P2-Na_(0.7)Fe_(0.5)Mn_(0.5)O_(2) cathode to address these challenges.By doping with 0.05 K^(+) and 0.2 Mg^(2+),the cathode demonstrated excellent cycling stability,retaining 95% of its capacity after 50 cycles at 0.2C,whereas the undoped material retained only 59.7%.Even within a wider voltage range,the co-doped cathode retained 88% of its capacity after 100 cycles at 1C.This work integrated Mg^(2+) to activate oxygen redox reactions in Fe/Mn-based layered cathodes,thereby promoting a reversible hybrid redox process involving both anions and cations.Building on the Mg doping,larger K^(+) ions were introduced into the edge-sharing Na^(+) sites,enhancing the material's cyclic stability and expanding the interplanar distance.The significant improvement of Na^(+) diffusion coefficient by K^(+)/Mg^(2+) co-doping has been further confirmed via the galvanostatic intermittent titration technique(GITT).The study emphasizes the importance of co-doping with different coordination environments in future material design,aiming to achieve high operating voltage and energy density.展开更多
Phase engineering has proven to be an effective strategy for achieving superior thermoelectric performance,while pressure is an excellent means of expanding the phase space of a material.In this paper,the effect of pr...Phase engineering has proven to be an effective strategy for achieving superior thermoelectric performance,while pressure is an excellent means of expanding the phase space of a material.In this paper,the effect of pressure-induced phase transition on improving the crystal symmetry and enhancing the thermoelectric properties of AgCrSe2 under high pressure and high temperature are reported.A structural phase transition from the low-symmetry R3m phase to the high-symmetry P3m1 phase is discovered below 1 GPa,which increases band degeneracy and contributes to a high electrical conductivity.For the metallic P3m1 phase,the electrons surrounding the Se2−anion gradually transfer to the Ag+and Cr3+cations as the pressure increases,decreasing the density of states around the Fermi level and thus optimizing the carrier concentration,thereby increasing the Seebeck coefficient while maintaining a high electrical conductivity.Consequently,an ultrahigh power factor of 864μW⋅m−1⋅K−2 is achieved at 5 GPa and 297 K.This study provides new insights into improving thermoelectric transport properties by applying physical pressure to enhance crystal symmetry and optimize thermoelectric parameters,and also indicates that phase engineering is a compelling strategy to discover or design novel high-performance thermoelectric materials starting from low-symmetry compounds.展开更多
In this study, we report newly found strongly retrograded eclogite blocks in the Kekesu Valley, eastern segment of southwestern Tianshan, northwestern China. Based on detailed petrographi- cal studies and mineral chem...In this study, we report newly found strongly retrograded eclogite blocks in the Kekesu Valley, eastern segment of southwestern Tianshan, northwestern China. Based on detailed petrographi- cal studies and mineral chemistry analyses, we constrain P-T evolution of two representative samples via phase equilibrium modeling method using THERMOCALC software. The peak stage is evidenced by the primary inclusions of omphacite＋glaucophane＋lawsonite （inferred）＋chlorite＋white mica in garnet. Using grossular and pyrope isopleth thermobarometry in garnet, the P peak conditions for this stage were con- strained to be -23 kbar, 480-500℃ and the T peak conditions were constrained to be 19-20 kbar, 500-520℃. Subsequent exhumation led to the transformation of lawsonite to epidote. Using Si-in- phengite barometry, the P was constrained to be 16-20 kbar at T of 500-520 ℃ for this stage. Further retrograde stage was evidenced by the mineral assemblages of glaucophane＋garnet＋epidote＋paragonite＋ chlorite＋white mica＋quartz. Later stage retrogression is evidenced by glaucophane＋epidote＋chlorite＋ quartz＋white mica＋albite＋aetinolite with P of 5-9 kbar when T〈490 ~C, indicating the eclogite may have been exhumed to the middle crust level and overprinted by blueschist-greenschist facies metamorphism. The results show that eclogite at the eastern segment of SW Tianshan shares similar P-T path to the HP rocks from the western segment, implying a similar P-T evolution for these rocks.展开更多
The high-pressure （HP） eclogite in the western Dabie Mountain encloses numerous hornblendes, mostly barroisite. Opinions on the peak metamorphic P-T condition, PT path and mineral paragenesis of it are still in disp...The high-pressure （HP） eclogite in the western Dabie Mountain encloses numerous hornblendes, mostly barroisite. Opinions on the peak metamorphic P-T condition, PT path and mineral paragenesis of it are still in dispute. Generally, HP eclogite involves garnet, omphacite, hornblendes and quartz, with or without glaucophane, zoisite and phengite. The garnet has compositional zoning with XMg increase, XCa and XMn decrease from core to rim, which indicates a progressive metamorphism. The phase equilibria of the HP eclogite modeled by the P-T pseudosection method developed recently showed the following： （1） the growth zonation of garnet records a progressive metamorphic PT path from pre-peak condition of 1.9-2.1 GPa at 508~C-514~C to a peak one of 2.3-2.5 GPa at 528~C-531~C for the HP eclogite; （2） the peak mineral assemblage is garnet＋omphacite＋glaucophane＋quartz_＋phengite, likely paragenetic with lawsonite; （3） the extensive hornblendes derive mainly from glaucophane, partial omphacite and even a little garnet due to the decompression with some heating during the post-peak stage, mostly representing the conditions of about 1.4-1.6 GPa and 580~C-640~C, and their growth is favored by the dehydration of lawsonite into zoisite or epidote, but most of the garnet, omphacite or phengite in the HP eclogite still preserve their compositions at peak condition, and they are not obviously equilibrious with the hornblendes.展开更多
Oil spills result in tremendous damage to the environment and ecosystem.In this study,several p-alkoxybenzoyl-based gelators(1,2a,2b,2c,3)synthesized from commercially available materials were designed for recovering ...Oil spills result in tremendous damage to the environment and ecosystem.In this study,several p-alkoxybenzoyl-based gelators(1,2a,2b,2c,3)synthesized from commercially available materials were designed for recovering oil from an oil–water mixture.Gels with remarkable gelation ability in various oils were characterized by nuclear magnetic resonance,Fourier transform infrared spectroscopy and X-ray diffraction to study the driving forces of self-assembly.Notably,these gelators could achieve the goal of recycling oil from the oil–water mixture at room temperature.In addition,gelator 2b could be used to remove toxic dyes from aqueous solutions with high efficiency.Therefore,these compounds were considered promising materials for oil spill recovery and dye removal due to their practicality and high efficiency.展开更多
The Precambrian lower crust rocks at the southeastern margin of the North China Craton （NCC） are mainly exposed as granulite xenoliths hosted by Mesozoic dioritic porphyry and metamorphic terrains in the Xuzhou-Suzh...The Precambrian lower crust rocks at the southeastern margin of the North China Craton （NCC） are mainly exposed as granulite xenoliths hosted by Mesozoic dioritic porphyry and metamorphic terrains in the Xuzhou-Suzhou area. Garnet amphiholites and garnet granulites are two kinds of typical lower-crustal xenoliths and were selected to reconstruct different stages of the metamorphic process. In this study, in view of multistage metamorphic evolution and reworking, phase equilibria modeling was used for the first time to better constrain peak P-T conditions of the xenoliths. Some porphyroblastic garnets have a weak zonal structure in composition with homogeneous cores and were surrounded by thin rims with an increase in XMg and a decrease in X Ca （or X Mg）- Clinopyroxene contain varying amounts of Na2O and Al2O3 as well as amphibole of TiO2, while plagioclases are different in calcium contents. Peak metamorphic P-T conditions are calculated by the smallest garnet x（g） （Fe2＋/（Fe2＋＋Mg）） contours and the smallest plagioclase ca（pl） （Ca/（Ca＋Na）） contours in NCFMASHTO （Na2O-CaO-FeO-MgO-Al2O3-SiO2- H20-TiO2-Fe2O3） system, which are consistent with those estimated by conventional geothermobarometry. The new results show that the peak and decompressional P-T conditions for the rocks are 850-900 ℃/ 1.4-1.6 GPa and 820-850 ℃/0.9-1.3 GPa, respectively, suggestive of high and middle-low pressure granulite-facies metamorphism. Combined with previous zircon U-Pb dating and conventional geothermobarometry data, it is indicated that the xenoliths experienced a clockwise P-T-t evolution with nearisothermal deeompressional process, suggestive of the Paleoproterozoic subduction-collision setting. In this regard, the studied region together with Jiao-Liao-Ji belt is further documented to make up a Paleopro- terozoic collisional orogen in the eastern block of the NCC.展开更多
基金financially supported by the National Key R&D Program of China(2020YFA0406203)National Natural Science Foundation of China(92472115,52371225 and 52072008)+5 种基金Guangdong Basic and Applied Basic Research Foundation(2022B1515120070,2022A1515110816 and 2022A1515110596)the Large Scientific Facility Open Subject of Songshan Lake,Dongguan,Guangdong(KFKT2022A04)Jialin Xie Fund(E4546IU2)the open research fund of Songshan Lake Materials Laboratory(2023SLABFN02)The Major Science and Technology Infrastructure Project of Material Genome Big-science Facilities Platform supported by the Municipal Development and Reform Commission of Shenzhen also contributed to this researchthe allocation of beamtime at BL15U and BL02B02 beamlines at SSRF。
文摘Sodium-ion batteries have been deemed as a sustainable alternative to lithium-ion systems due to the abundance and affordability of sodium sources.Nevertheless,developing high-energy-density P2-type layered oxide cathodes with long-term cycling stability poses challenges,stemming from irreversible phase transitions,structural degradation,and lattice oxygen instability during electrochemical cycling.Here,we propose a one-step NbB_(2)modification strategy that enhances both bulk and surface properties of Na_(0.8)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)cathodes.By exploiting different techniques,we disclose that bulk Nb and B doping combined with a Nb-Transition Metal-BO_(3)surface layer reconstruction enable a reversible P2-OP4 phase transition and,meanwhile,improve anionic redox reversibility.In addition,Li^(+)migrates into alkali-metal layers and underpins the layered structure through the“pillar effect”,thereby facilitating the Na^(+)diffusion in Na_(0.8)Li_(0.12)Ni_(0.22)Mn_(0.66)O_(2)cathodes and retaining their structural integrity at high voltage.As a result,the modified cathodes achieve 93.6%capacity retention after 500 cycles at 1C and deliver specific capacities above 114 m A h g^(-1)at 10C within 2.0-4.3 V.Contrary to the previous studies reporting that OP4 phase are detrimental to the structural stability of layered cathodes,we experimentally validate that a well-regulated P2-OP4 phase transition is beneficial for structural and electrochemical stabilities.
基金supported by National Natural Science Youth Foundation of China(No.22308294)National Natural Science Foundation of China(No.22179077)+1 种基金Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX23_1868)Qing Lan Project of Jiangsu University and the Funding for school-level research projects of Yancheng Institute of Technology.
文摘Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries;however,they face significant challenges,including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere.In response to these issues,we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability.The redox reaction of Cu^(2+/3+)can provide certain charge compensation,and the introduction of Al can further suppress the Jahn-Teller effect of Mn,thereby achieving superior long-term cycling performance.The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage,thereby explaining the improvement in electrochemical performance.DFT calculations reveal a high chemical tolerance to moisture,with lower adsorption energy for H_(2)O compared to pure Na_(0.67)Cu_(0.25)Mn_(0.75)O_(2).A representative Na_(0.67)Cu_(0.20)Al_(0.05)Mn_(0.75)O_(2)cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C,along with a remarkable capacity retention of 79.1%(2 C,500 cycles).
基金financially supported by the National Natural Science Foundation of China(12175089,12205127,52220105010)the Key Research and Development Program of Yunnan Province(202103AF140006)+3 种基金the Applied Basic Research Programs of Yunnan Provincial Science and Technology Department(202001AW070004,202301AS070051,202301AU070064)Yunnan Industrial Innovative Talents Program for“Xingdian Talent Support Plan”(KKXY202252001)Yunnan Program for Introducing Foreign Talents(202305AO350042)Yunnan Major Scientific and Technological Projects(202202AG050003).
文摘Sodium-ion batteries(SIBs)are emerging as a promising alternative for large-scale energy storage,particularly in grid applications.Within the array of potential cathode materials,Fe/Mn-based layered oxides are notable for their advantageous theoretical specific capacity,economic viability,and environmental sustainability.Nevertheless,the practical application of Fe/Mn-based layered oxides is constrained by their suboptimal cycle performance and rate capability during actual charging and discharging.Ion doping is an effective approach for addressing the aforementioned issues.In this context,we have successfully developed a novel K^(+) and Mg^(2+) codoped P2-Na_(0.7)Fe_(0.5)Mn_(0.5)O_(2) cathode to address these challenges.By doping with 0.05 K^(+) and 0.2 Mg^(2+),the cathode demonstrated excellent cycling stability,retaining 95% of its capacity after 50 cycles at 0.2C,whereas the undoped material retained only 59.7%.Even within a wider voltage range,the co-doped cathode retained 88% of its capacity after 100 cycles at 1C.This work integrated Mg^(2+) to activate oxygen redox reactions in Fe/Mn-based layered cathodes,thereby promoting a reversible hybrid redox process involving both anions and cations.Building on the Mg doping,larger K^(+) ions were introduced into the edge-sharing Na^(+) sites,enhancing the material's cyclic stability and expanding the interplanar distance.The significant improvement of Na^(+) diffusion coefficient by K^(+)/Mg^(2+) co-doping has been further confirmed via the galvanostatic intermittent titration technique(GITT).The study emphasizes the importance of co-doping with different coordination environments in future material design,aiming to achieve high operating voltage and energy density.
基金supported by the Jilin Province Science and Technology Development Program,China(Grant No.20250102013JC).
文摘Phase engineering has proven to be an effective strategy for achieving superior thermoelectric performance,while pressure is an excellent means of expanding the phase space of a material.In this paper,the effect of pressure-induced phase transition on improving the crystal symmetry and enhancing the thermoelectric properties of AgCrSe2 under high pressure and high temperature are reported.A structural phase transition from the low-symmetry R3m phase to the high-symmetry P3m1 phase is discovered below 1 GPa,which increases band degeneracy and contributes to a high electrical conductivity.For the metallic P3m1 phase,the electrons surrounding the Se2−anion gradually transfer to the Ag+and Cr3+cations as the pressure increases,decreasing the density of states around the Fermi level and thus optimizing the carrier concentration,thereby increasing the Seebeck coefficient while maintaining a high electrical conductivity.Consequently,an ultrahigh power factor of 864μW⋅m−1⋅K−2 is achieved at 5 GPa and 297 K.This study provides new insights into improving thermoelectric transport properties by applying physical pressure to enhance crystal symmetry and optimize thermoelectric parameters,and also indicates that phase engineering is a compelling strategy to discover or design novel high-performance thermoelectric materials starting from low-symmetry compounds.
基金supported by the National Natural Science Foundation of China (No. 41502043)China Postdoctoral Science Foundation (No. 2016T90742)
文摘In this study, we report newly found strongly retrograded eclogite blocks in the Kekesu Valley, eastern segment of southwestern Tianshan, northwestern China. Based on detailed petrographi- cal studies and mineral chemistry analyses, we constrain P-T evolution of two representative samples via phase equilibrium modeling method using THERMOCALC software. The peak stage is evidenced by the primary inclusions of omphacite＋glaucophane＋lawsonite （inferred）＋chlorite＋white mica in garnet. Using grossular and pyrope isopleth thermobarometry in garnet, the P peak conditions for this stage were con- strained to be -23 kbar, 480-500℃ and the T peak conditions were constrained to be 19-20 kbar, 500-520℃. Subsequent exhumation led to the transformation of lawsonite to epidote. Using Si-in- phengite barometry, the P was constrained to be 16-20 kbar at T of 500-520 ℃ for this stage. Further retrograde stage was evidenced by the mineral assemblages of glaucophane＋garnet＋epidote＋paragonite＋ chlorite＋white mica＋quartz. Later stage retrogression is evidenced by glaucophane＋epidote＋chlorite＋ quartz＋white mica＋albite＋aetinolite with P of 5-9 kbar when T〈490 ~C, indicating the eclogite may have been exhumed to the middle crust level and overprinted by blueschist-greenschist facies metamorphism. The results show that eclogite at the eastern segment of SW Tianshan shares similar P-T path to the HP rocks from the western segment, implying a similar P-T evolution for these rocks.
基金funded by the National Natural Science Foundation of China (No.40525006 and 40372032).
文摘The high-pressure （HP） eclogite in the western Dabie Mountain encloses numerous hornblendes, mostly barroisite. Opinions on the peak metamorphic P-T condition, PT path and mineral paragenesis of it are still in dispute. Generally, HP eclogite involves garnet, omphacite, hornblendes and quartz, with or without glaucophane, zoisite and phengite. The garnet has compositional zoning with XMg increase, XCa and XMn decrease from core to rim, which indicates a progressive metamorphism. The phase equilibria of the HP eclogite modeled by the P-T pseudosection method developed recently showed the following： （1） the growth zonation of garnet records a progressive metamorphic PT path from pre-peak condition of 1.9-2.1 GPa at 508~C-514~C to a peak one of 2.3-2.5 GPa at 528~C-531~C for the HP eclogite; （2） the peak mineral assemblage is garnet＋omphacite＋glaucophane＋quartz_＋phengite, likely paragenetic with lawsonite; （3） the extensive hornblendes derive mainly from glaucophane, partial omphacite and even a little garnet due to the decompression with some heating during the post-peak stage, mostly representing the conditions of about 1.4-1.6 GPa and 580~C-640~C, and their growth is favored by the dehydration of lawsonite into zoisite or epidote, but most of the garnet, omphacite or phengite in the HP eclogite still preserve their compositions at peak condition, and they are not obviously equilibrious with the hornblendes.
文摘Oil spills result in tremendous damage to the environment and ecosystem.In this study,several p-alkoxybenzoyl-based gelators(1,2a,2b,2c,3)synthesized from commercially available materials were designed for recovering oil from an oil–water mixture.Gels with remarkable gelation ability in various oils were characterized by nuclear magnetic resonance,Fourier transform infrared spectroscopy and X-ray diffraction to study the driving forces of self-assembly.Notably,these gelators could achieve the goal of recycling oil from the oil–water mixture at room temperature.In addition,gelator 2b could be used to remove toxic dyes from aqueous solutions with high efficiency.Therefore,these compounds were considered promising materials for oil spill recovery and dye removal due to their practicality and high efficiency.
基金financially supported by the National Natural Science Foundation of China (No. 41773020)the National Basic Research Program of China (No. 2015CB856104)the PhD Foundation of the Ministry of Education of China (No. 20133402130008)
文摘The Precambrian lower crust rocks at the southeastern margin of the North China Craton （NCC） are mainly exposed as granulite xenoliths hosted by Mesozoic dioritic porphyry and metamorphic terrains in the Xuzhou-Suzhou area. Garnet amphiholites and garnet granulites are two kinds of typical lower-crustal xenoliths and were selected to reconstruct different stages of the metamorphic process. In this study, in view of multistage metamorphic evolution and reworking, phase equilibria modeling was used for the first time to better constrain peak P-T conditions of the xenoliths. Some porphyroblastic garnets have a weak zonal structure in composition with homogeneous cores and were surrounded by thin rims with an increase in XMg and a decrease in X Ca （or X Mg）- Clinopyroxene contain varying amounts of Na2O and Al2O3 as well as amphibole of TiO2, while plagioclases are different in calcium contents. Peak metamorphic P-T conditions are calculated by the smallest garnet x（g） （Fe2＋/（Fe2＋＋Mg）） contours and the smallest plagioclase ca（pl） （Ca/（Ca＋Na）） contours in NCFMASHTO （Na2O-CaO-FeO-MgO-Al2O3-SiO2- H20-TiO2-Fe2O3） system, which are consistent with those estimated by conventional geothermobarometry. The new results show that the peak and decompressional P-T conditions for the rocks are 850-900 ℃/ 1.4-1.6 GPa and 820-850 ℃/0.9-1.3 GPa, respectively, suggestive of high and middle-low pressure granulite-facies metamorphism. Combined with previous zircon U-Pb dating and conventional geothermobarometry data, it is indicated that the xenoliths experienced a clockwise P-T-t evolution with nearisothermal deeompressional process, suggestive of the Paleoproterozoic subduction-collision setting. In this regard, the studied region together with Jiao-Liao-Ji belt is further documented to make up a Paleopro- terozoic collisional orogen in the eastern block of the NCC.
