Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibili...Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibility with Li metal.However,the deployment of LLZTO is severely hampered by poor contact between LLZTO and Li metal anode.In this paper,an ultra-thin Al-Si interface buffer layer(10 nm)is constructed on LLZTO by a magnetron sputtering method,which allows superior wetting of Li onto the LLZTO surface due to the alloying reaction between the Al-Si layer and Li metal.The resulting Li/Al-Si coated LLZTO(ASL)/Li symmetrical cell delivers an interfacial resistance of 15.0Ωcm^(-2),which is much lower than that of 1140.3Ωcm^(-2)for the bare LLZTO symmetrical cell.Moreover,the Li/ASL/Li symmetrical cells exhibit stable plating/striping performance(800 h)with small voltage hysteresis at 1.0 mA cm^(-2).Besides,the full cell with LiFePO_(4)cathode reveals a high capacity of 124.1 mA h g^(-1)after 600 cycles at 0.5C with a lowcapacity decay of 0.032%per cycle.We believe this work will facilitate the development of solid-state rechargeable batteries.展开更多
Environmental stresses severely impair cotton production worldwide. To identify the genetic basis of, and molecular markers associated with, environmental stresses such as salt, cold and Verticillium wilt, association...Environmental stresses severely impair cotton production worldwide. To identify the genetic basis of, and molecular markers associated with, environmental stresses such as salt, cold and Verticillium wilt, association mapping of salt-, cold-, and disease-tolerance traits was performed in a population of 503 upland cotton accessions using 179 polymorphic SSR markers and 11,975 array-derived SNP markers. Salt and cold tolerance was evaluated via the relative germination rate(RGR) of the seeds under seven and four environments, respectively. The disease index of Verticillium wilt was investigated for two years in the field in Xinjiang. These three traits showed large variation across environments. A genome-wide association study revealed that 31, 19, and 15 SSR markers were associated with RGR-Salt(the relative germination rates of seeds under salt stress),RGR-Cold(the relative germination rates of seeds under cold stress), and DIV(the disease index of Verticillium wilt), respectively. Six SNPs in seven environments and two SNPs in BLUP(best linear unbiased prediction) results were associated with RGR-Salt, and the phenotypic variance explained ranged from 3.96 to 5.00%. Two SNPs(i02237 Gh, i02243 Gh)on D01 were concluded to be stable genetic loci associated with RGR-Salt. A total of 223 genes were found in a candidate gene interval(D01, 37771–1942912). Of these four genes,GhPIP3A, GhSAG29, GhTZF4, and GhTZF4a, showed expression changes in sensitive and tolerant genotype accessions under salt stress, and were assigned as candidate genes associated with RGR-Salt. This study revealed the genetic basis of stress resistance in upland cotton and will facilitate stress-resistance breeding in cotton.展开更多
Single-crystal cathodes(SCCs)are promising substitute materials for polycrystal cathodes(PCCs)in lithium-ion batteries(LIBs),because of their unique ordered structure,excellent cycling stability and high safety perfor...Single-crystal cathodes(SCCs)are promising substitute materials for polycrystal cathodes(PCCs)in lithium-ion batteries(LIBs),because of their unique ordered structure,excellent cycling stability and high safety performance.Cathode materials with layered(LiCoO_(2),LiNi_xCo_yMnzO_(2),LiNi_xCo_yAl_(2)O_(2))and spinel structure(LiMn_(2)O_(4),LiNi_(0.5)Mn_(1.5)O_(4))show a relatively stable electrochemical performance,but still lack of sufficient attention in research field.In this review,we begin with the definition,structural features and electrochemical advantages of SCCs.Common SCCs synthesis methods and the thermodynamic growth mechanism of SCCs with oriented facet exposure are summarized in the following part.Then we introduce the problems and challenges of SCCs faced and the corresponding modification strategies.Finally,the industrialization progress of SCCs is brifly outlined.We intend to tease out the difficulties and advances of SCCs to provide insights for future development of high-performance SCCs for practical LIBs.展开更多
Metal phosphides have shown great potential for potassium-ion batteries because of their high theoretical specific capacity.Nevertheless,most of the metal phosphide anodes are plagued by rapid capacity decay(caused by...Metal phosphides have shown great potential for potassium-ion batteries because of their high theoretical specific capacity.Nevertheless,most of the metal phosphide anodes are plagued by rapid capacity decay(caused by the large volume changes during the discharge/charge process),which would restrict their further practical application.Herein,a chemically bonded CuP_(2)/C composite was prepared by a facile high-energy ball milling method.A potassium bis(trifluoromethanesulfonyl)imide(KFSI)-based electrolyte was adopted instead of a conventional KPF6-based electrolyte for the CuP_(2)/C composite anode.Benefiting from the synergistic effects of the formation of strong P-O-C chemical bonds and the KFSIbased electrolyte,the CuP_(2)/C composite anode exhibited high reversible capacity(451.4 mAh g^(-1) at50 mA g^(-1)),excellent rate performance(123.5 mAh g^(-1) at 1000 mA g^(-1)),and superior cycling stability(300 mAh g^(-1) after 100 cycles).This work paves the way for the development of high-performance CuP_(2) anode for potassium-ion batteries.展开更多
富锂层状氧化物是构筑高能量密度锂离子电池富有潜力的正极材料.然而,由于不可逆的结构变化和缓慢的界面动力学,传统的多晶富锂层状氧化物正极材料循环和倍率性能较差.本文提出了一种聚乙烯基吡咯烷酮(PVP-K30)辅助共沉淀制备单晶Li_(1....富锂层状氧化物是构筑高能量密度锂离子电池富有潜力的正极材料.然而,由于不可逆的结构变化和缓慢的界面动力学,传统的多晶富锂层状氧化物正极材料循环和倍率性能较差.本文提出了一种聚乙烯基吡咯烷酮(PVP-K30)辅助共沉淀制备单晶Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)纳米片的方法.这种方法操作简单、成本低且便于放大生产.所制备的单晶纳米片内部晶格连续且无晶界,缩短了Li+的嵌入/脱嵌路径,加快了电极反应动力学过程.单晶结构还能抑制层状相向尖晶石相的不可逆相变和颗粒内部裂纹的形成,起到稳定层状结构的作用.电化学测试结果表明,所制备的Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)单晶纳米片在0.1 C倍率下的可逆容量为254.5 mA h g^(-1),在5 C高倍率下循环1000次后容量保持率为71.9%.这种简单的制备纳米片单晶材料的方法为提高富锂层状氧化物正极材料的循环性能和倍率性能提供了新的思路.展开更多
Na-CO_(2) batteries have attracted extensive attention due to their high theoretical energy density(1125 Wh/kg),efficient utilization of CO_(2),and abundant sodium resources.However,they are trapped by the sluggish de...Na-CO_(2) batteries have attracted extensive attention due to their high theoretical energy density(1125 Wh/kg),efficient utilization of CO_(2),and abundant sodium resources.However,they are trapped by the sluggish decomposition kinetic of discharge products (mainly Na_(2)CO_(3)) on cathode side during the charging process.Here we prepared a series of nano-composites composed of RuO_(2) nanoparticles in situ loaded on activated multi-walled carbon nanotubes (RuO_(2)@a-MWCNTs) through hydrolyzing reaction followed by calcination method and used them as cathode catalysts to accelerate the decomposition of Na_(2)CO_(3).Among all catalysts,the RuO_(2)@a-MWCNTs with appropriate ratio of RuO_(2)(49.7 wt%) demonstrated best stability and rate performance in Na-CO_(2) batteries,benefiting from both high specific surface area (160.3 m^(2)/g) and highly dispersed RuO_(2) with ultrafine nanostructures (~2 nm).At a limited capacity of 500 mAh/g,Na-CO_(2) batteries could afford the operation of over 120 cycles at 100 mA/g,and even at the current density to 500 mA/g,the charge voltage was still lower than 4.0 V after 40 cycles.Further theoretical calculations proved that RuO_(2) was the catalytically active center and contributed to the decomposition of Na_(2)CO_(3) by weakening the C=O bond.The synergetic functions of high specific surface(CNTs) and high catalytic activity (RuO_(2)) will inspire more progress on metal-CO_(2) batteries.展开更多
Spinel oxides,with the formula AB_(2)O_(4)(A and B represent metal ions)perform superior electrocatalytic characteristic when A and B are transition metals like Co,Fe,Mn,etc.Abundant researches have been attached to t...Spinel oxides,with the formula AB_(2)O_(4)(A and B represent metal ions)perform superior electrocatalytic characteristic when A and B are transition metals like Co,Fe,Mn,etc.Abundant researches have been attached to the structure designments while methods are often energy-intensive and inefficient.Here,we devised a universal strategy to achieve rapid synthesis of nanocrystalline spinel materials with multiple components(Co_(3)O_(4),Mn_(3)O_(4),CoMn_(2)O_(4)and CoFe_(2)O_(4)are as examples),where phase formation is within 15 s.Under the Joule-heating shock,a crack-break process of microcosmic phase transformation is observed by in-situ transmission electron microscopy.The half-wave potential values of Co_(3)O_(4)-JH,Mn_(3)O_(4)-JH,CoMn_(2)O_(4)-JH and CoFe_(2)O_(4)-JH in the electrocatalytic oxygen reduction reaction were 0.77,0.78,0.79 and 0.76,respectively.This suggests that the Joule heating is a fast and efficient method for the preparation of spinel oxide electrocatalysts.展开更多
Silicon-based material is one of the most promising substitutes of widely used graphite anodes for the next generation Li-ion batteries due to its high theoretical capacity,low working potential,environmental friendli...Silicon-based material is one of the most promising substitutes of widely used graphite anodes for the next generation Li-ion batteries due to its high theoretical capacity,low working potential,environmental friendliness,and abundant natural resource.However,the huge volume expansion and serious interfacial side reactions during lithiation and delithiation progresses of the silicon anode are the key issues which impede their further practical applications.Rational designs of silicon nanostructures are effective ways to address these problems.In this progress report,we firstly highlight the fundamental scientific problems,and then focus on recent progresses in design,preparation,in-situ characterization methods and failure mechanism of nanostructured silicon anode for high capacity lithium battery.We also summarize the key lessons from the successes so far and offer perspectives and future challenges to promote the applications of silicon anode in practical lithium batteries.展开更多
The conventional ceramic synthesis of perovskite oxides involves extended high-temperature annealing in air and is unfavorable to the in situ hybridization of the conductive agent, thus resulting in large particle siz...The conventional ceramic synthesis of perovskite oxides involves extended high-temperature annealing in air and is unfavorable to the in situ hybridization of the conductive agent, thus resulting in large particle sizes, low surface area and limited electrochemical activities. Here we report a rapid gel auto-combustion approach for the synthesis of a perovskite/carbon hybrid at a low temperature of 180℃. The energy-saving synthetic strategy allows the formation of small and homogeneously dispersed LaxMnO3±6/C nanocomposites. Remarkably, the synthesized La0.99MnO3.03/C nanocomposite exhibits comparable oxygen reduction reaction （ORR） activity （with onset and peak potentials of 0.97 and 0.88 V, respectively） to the benchmark Pt/C due to the facilitated charge transfer, optimal eg electron filling of Mn, and coupled C-O-Mn bonding. Furthermore, the nanocomposite efficiently catalyzes a Zn-air battery that delivers a peak power density of 430 mW·cm^-2, an energy density of 837 W·h·kgzn^-1 and 340 h stability at a current rate of 10 mA·cm^-2.展开更多
Defects engineering is an efficient strategy to enhance the performance of electrode materials by modulating the local electronic structure but usually requires costly and complicated processing.Here,an electrochemica...Defects engineering is an efficient strategy to enhance the performance of electrode materials by modulating the local electronic structure but usually requires costly and complicated processing.Here,an electrochemical reduction etching method has been developed for controllable tailoring of the cationic defects in iron-based oxides under mild conditions.The optimized defective spinel-type iron nickel oxide exhibits an overpotential as low as 270 mV at 10 mA cm−2 and a Tafel slope of only 33.8 mV dec−1 for the oxygen evolution reaction(OER),outperforming the benchmark RuO2 and pristine oxide.Experiments and theoretical calculations reveal that Fe vacancies can enhance Ni–O covalency,increase the density of active sites,and optimize the surface electronic structure,which promote the water adsorption/activation and moderate oxygen intermediate species adsorption,thus significantly enhancing OER activity.This work provides a promising approach to create cation deficiency and mechanistic insight to understand the vacancy-induced enhancement of oxygen electrocatalysis.展开更多
The facile synthesis of highly active and stable bifunctional electrocatalysts to catalyze water splitting is attractive but challenging.Herein,we report the electrodeposition of Pt-decorated Ni(OH)_(2)/CeO_(2)(PNC)hy...The facile synthesis of highly active and stable bifunctional electrocatalysts to catalyze water splitting is attractive but challenging.Herein,we report the electrodeposition of Pt-decorated Ni(OH)_(2)/CeO_(2)(PNC)hybrid as an efficient and robust bifunctional electrocatalyst.The graphite-supported PNC catalyst delivers superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities over the benchmark Pt/C and RuO_(2),respectively.For overall water electrolysis,the PNC hybrid only requires a cell voltage of 1.45V at 10mAcm-2 and sustains over 85 h at 1000mAcm^(-2).The remarkable HER/OER performances are attributed to the superhydrophilicity and multiple effects of PNC,in which Ni(OH)_(2)and CeO_(2)accelerate HER on Pt due to promoted water dissociation and strong electronic interaction,while the electron-pulling Ce cations facilitate the generation of high-valence Ni OER-active species.These results suggest the promising application of PNC for H2 production from water electrolysis.展开更多
Metallic zinc is attractive anode material of rechargeable aqueous Zn-based batteries due to its ambient stability,high volumetric capacity,and abundant reserves.Nonetheless,Zn anodes suffer from issues such as low co...Metallic zinc is attractive anode material of rechargeable aqueous Zn-based batteries due to its ambient stability,high volumetric capacity,and abundant reserves.Nonetheless,Zn anodes suffer from issues such as low coulombic efficiency(CE),large polarization and dendrite formation.Herein,uniform Zn electrodeposition is reported on carbon substrates by selective nitrogen doping.Combined experimental and theoretical investigations demonstrate that pyrrolic and pyridinic nitrogen doped in carbon play beneficial effect as zinc-philic sites to direct nucleation and growth of metallic Zn,while negligible effect is observed for graphite nitrogen in Zn plating.The carbon cloth with modified amount of doped pyrrolic and pyridinic nitrogen stabilizes Zn plating/stripping with 99.3%CE after 300 cycles and significantly increases the deliverable capacity at high depth of charge and discharge compared to undoped carbon substrate and Zn foil.This work provides a better understanding of heteroatom doping effect in design and preparation of stable 3 D carbon-supported zinc anode.展开更多
Numerous studies have evaluated the toxicity and endocrine disrupting properties of organic UV filters for aquatic organisms,but little is known about their biodegradation in river sediments and their impact on microo...Numerous studies have evaluated the toxicity and endocrine disrupting properties of organic UV filters for aquatic organisms,but little is known about their biodegradation in river sediments and their impact on microorganisms.We have set up the sterile and microbiological systems in the laboratory,adding 2-ethylhexyl-4-methoxycinnamate(EHMC),one of organic UV filters included in the list of high yield chemicals,at concentrations of 2,20 and 200μg/L,and characterized the microbial community composition and diversity in sediments.Monitoring of EHMC degradation within 30 days revealed that the half-life in the microbial system(3.49 days)was much shorter than that in the sterile system(7.55 days).Two potential degradation products,4-mercaptobenzoic acid and 3-methoxyphenol were identified in the microbial system.Furthermore,high-throughput 16s and 18s rRNA gene sequencing showed that Proteobacteria dominated the sediment bacterial assemblages followed by Chloroflexi,Acidobacteria,Bacteroidetes and Nitrospirae;Eukaryota_uncultured fungus dominated the sediment fungal assemblages.Correlation analysis demonstrated that two bacterium genera(Anaerolineaceae_uncultured and Burkholderiaceae_uncultured)were significantly correlated with the biodegradation of EHMC.These results illustrate the biodegradability of EHMC in river sediments and its potential impact on microbial communities,which can provide useful information for eliminating the pollution of organic UV filters in natural river systems and assessing their potential ecological risks.展开更多
It is desirable to exploit cost-effective and earth-abundant catalysts for the oxygen evolution reaction (OER) in developing electrochemical energy conversion and storage technologies. Here we report a facile hydrothe...It is desirable to exploit cost-effective and earth-abundant catalysts for the oxygen evolution reaction (OER) in developing electrochemical energy conversion and storage technologies. Here we report a facile hydrothermal synthesis of NiMo04 nanorods as active and stable OER catalyst in alkaline condition. The prepared NiMoO_4 nanorods exhibit a considerably low overpotential of 340 mV at the current density of10 mA/cm^2 and a low Tafel slope of 45.6 mV/dec, which is comparable to the benchmark Ru02.Furthermore, the performance of NiMoO_4 significantly surpasses binary NiO and MoO_3 oxides due to enhanced charge transfer and promoted formation of catalytically active Ni^(3+) species. The results highlight the importance of designing ternary oxides in oxygen electrocatalysis.展开更多
基金supported by the National Natural Science Foundation of China(22209140,52072328,and 52175192)the Incubation Program of Youth Innovation in Shandong Province and Natural Science Foundation of Shandong Province(ZR2022QE059)。
文摘Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibility with Li metal.However,the deployment of LLZTO is severely hampered by poor contact between LLZTO and Li metal anode.In this paper,an ultra-thin Al-Si interface buffer layer(10 nm)is constructed on LLZTO by a magnetron sputtering method,which allows superior wetting of Li onto the LLZTO surface due to the alloying reaction between the Al-Si layer and Li metal.The resulting Li/Al-Si coated LLZTO(ASL)/Li symmetrical cell delivers an interfacial resistance of 15.0Ωcm^(-2),which is much lower than that of 1140.3Ωcm^(-2)for the bare LLZTO symmetrical cell.Moreover,the Li/ASL/Li symmetrical cells exhibit stable plating/striping performance(800 h)with small voltage hysteresis at 1.0 mA cm^(-2).Besides,the full cell with LiFePO_(4)cathode reveals a high capacity of 124.1 mA h g^(-1)after 600 cycles at 0.5C with a lowcapacity decay of 0.032%per cycle.We believe this work will facilitate the development of solid-state rechargeable batteries.
基金supported by the National Key Research and Development Program of China (2016YFD0101006)the Fundamental Research Funds for the Central Universities (2662016PY001)
文摘Environmental stresses severely impair cotton production worldwide. To identify the genetic basis of, and molecular markers associated with, environmental stresses such as salt, cold and Verticillium wilt, association mapping of salt-, cold-, and disease-tolerance traits was performed in a population of 503 upland cotton accessions using 179 polymorphic SSR markers and 11,975 array-derived SNP markers. Salt and cold tolerance was evaluated via the relative germination rate(RGR) of the seeds under seven and four environments, respectively. The disease index of Verticillium wilt was investigated for two years in the field in Xinjiang. These three traits showed large variation across environments. A genome-wide association study revealed that 31, 19, and 15 SSR markers were associated with RGR-Salt(the relative germination rates of seeds under salt stress),RGR-Cold(the relative germination rates of seeds under cold stress), and DIV(the disease index of Verticillium wilt), respectively. Six SNPs in seven environments and two SNPs in BLUP(best linear unbiased prediction) results were associated with RGR-Salt, and the phenotypic variance explained ranged from 3.96 to 5.00%. Two SNPs(i02237 Gh, i02243 Gh)on D01 were concluded to be stable genetic loci associated with RGR-Salt. A total of 223 genes were found in a candidate gene interval(D01, 37771–1942912). Of these four genes,GhPIP3A, GhSAG29, GhTZF4, and GhTZF4a, showed expression changes in sensitive and tolerant genotype accessions under salt stress, and were assigned as candidate genes associated with RGR-Salt. This study revealed the genetic basis of stress resistance in upland cotton and will facilitate stress-resistance breeding in cotton.
基金supported by the National Natural Science Foundation of China(52001171,21835004,51901104,22020102002,51801105 and 52101226)the National Key R&D Program of China(2017YFA0206700 and 2018YFB1502101)+1 种基金the NCC Fund(NCC2020FH03)the 111 Project from the Ministry of Education of China(B12015)。
文摘Single-crystal cathodes(SCCs)are promising substitute materials for polycrystal cathodes(PCCs)in lithium-ion batteries(LIBs),because of their unique ordered structure,excellent cycling stability and high safety performance.Cathode materials with layered(LiCoO_(2),LiNi_xCo_yMnzO_(2),LiNi_xCo_yAl_(2)O_(2))and spinel structure(LiMn_(2)O_(4),LiNi_(0.5)Mn_(1.5)O_(4))show a relatively stable electrochemical performance,but still lack of sufficient attention in research field.In this review,we begin with the definition,structural features and electrochemical advantages of SCCs.Common SCCs synthesis methods and the thermodynamic growth mechanism of SCCs with oriented facet exposure are summarized in the following part.Then we introduce the problems and challenges of SCCs faced and the corresponding modification strategies.Finally,the industrialization progress of SCCs is brifly outlined.We intend to tease out the difficulties and advances of SCCs to provide insights for future development of high-performance SCCs for practical LIBs.
基金supported by the National Natural Science Foundation of China (21835004 and 51971124)the National Key R&D Program of China (2017YFA0206700)the 111 Project from the Ministry of Education of China (B12015)。
文摘Metal phosphides have shown great potential for potassium-ion batteries because of their high theoretical specific capacity.Nevertheless,most of the metal phosphide anodes are plagued by rapid capacity decay(caused by the large volume changes during the discharge/charge process),which would restrict their further practical application.Herein,a chemically bonded CuP_(2)/C composite was prepared by a facile high-energy ball milling method.A potassium bis(trifluoromethanesulfonyl)imide(KFSI)-based electrolyte was adopted instead of a conventional KPF6-based electrolyte for the CuP_(2)/C composite anode.Benefiting from the synergistic effects of the formation of strong P-O-C chemical bonds and the KFSIbased electrolyte,the CuP_(2)/C composite anode exhibited high reversible capacity(451.4 mAh g^(-1) at50 mA g^(-1)),excellent rate performance(123.5 mAh g^(-1) at 1000 mA g^(-1)),and superior cycling stability(300 mAh g^(-1) after 100 cycles).This work paves the way for the development of high-performance CuP_(2) anode for potassium-ion batteries.
基金supported by the National Natural Science Foundation of China (22121005, 22020102002 and 21835004)the Frontiers Science Center for New Organic Matter of Nankai University (63181206)Tianjin Lishen New Energy Technology Co., Ltd. for financial support。
文摘富锂层状氧化物是构筑高能量密度锂离子电池富有潜力的正极材料.然而,由于不可逆的结构变化和缓慢的界面动力学,传统的多晶富锂层状氧化物正极材料循环和倍率性能较差.本文提出了一种聚乙烯基吡咯烷酮(PVP-K30)辅助共沉淀制备单晶Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)纳米片的方法.这种方法操作简单、成本低且便于放大生产.所制备的单晶纳米片内部晶格连续且无晶界,缩短了Li+的嵌入/脱嵌路径,加快了电极反应动力学过程.单晶结构还能抑制层状相向尖晶石相的不可逆相变和颗粒内部裂纹的形成,起到稳定层状结构的作用.电化学测试结果表明,所制备的Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)单晶纳米片在0.1 C倍率下的可逆容量为254.5 mA h g^(-1),在5 C高倍率下循环1000次后容量保持率为71.9%.这种简单的制备纳米片单晶材料的方法为提高富锂层状氧化物正极材料的循环性能和倍率性能提供了新的思路.
基金supported by the National Key R&D Program of China(2016YFA0202500)the National Natural Science Foundation of China(22020102002,21835004,21673243,52001171 and 51771094)+1 种基金Jayuan TechnologyJEVE for financial support。
基金supported by the National Natural Science Foundation of China(Nos.52001170,21835004)the National Key R&D Program of China(Nos.2017YFA0206700,2021YFB2500300)the Natural Science Foundation of Tianjin(No.20JCQNJC02060)。
文摘Na-CO_(2) batteries have attracted extensive attention due to their high theoretical energy density(1125 Wh/kg),efficient utilization of CO_(2),and abundant sodium resources.However,they are trapped by the sluggish decomposition kinetic of discharge products (mainly Na_(2)CO_(3)) on cathode side during the charging process.Here we prepared a series of nano-composites composed of RuO_(2) nanoparticles in situ loaded on activated multi-walled carbon nanotubes (RuO_(2)@a-MWCNTs) through hydrolyzing reaction followed by calcination method and used them as cathode catalysts to accelerate the decomposition of Na_(2)CO_(3).Among all catalysts,the RuO_(2)@a-MWCNTs with appropriate ratio of RuO_(2)(49.7 wt%) demonstrated best stability and rate performance in Na-CO_(2) batteries,benefiting from both high specific surface area (160.3 m^(2)/g) and highly dispersed RuO_(2) with ultrafine nanostructures (~2 nm).At a limited capacity of 500 mAh/g,Na-CO_(2) batteries could afford the operation of over 120 cycles at 100 mA/g,and even at the current density to 500 mA/g,the charge voltage was still lower than 4.0 V after 40 cycles.Further theoretical calculations proved that RuO_(2) was the catalytically active center and contributed to the decomposition of Na_(2)CO_(3) by weakening the C=O bond.The synergetic functions of high specific surface(CNTs) and high catalytic activity (RuO_(2)) will inspire more progress on metal-CO_(2) batteries.
基金supported by the National Programs for NanoKey Project(No.2022YFA1504002)the National Natural Science Foundation of China(Nos.22121005,22020102002,and 21835004)the Fundamental Research Funds for the Central Universities,and Collaborative Innovation Center of Chemical Science and Engineering(Tianjin)。
文摘Spinel oxides,with the formula AB_(2)O_(4)(A and B represent metal ions)perform superior electrocatalytic characteristic when A and B are transition metals like Co,Fe,Mn,etc.Abundant researches have been attached to the structure designments while methods are often energy-intensive and inefficient.Here,we devised a universal strategy to achieve rapid synthesis of nanocrystalline spinel materials with multiple components(Co_(3)O_(4),Mn_(3)O_(4),CoMn_(2)O_(4)and CoFe_(2)O_(4)are as examples),where phase formation is within 15 s.Under the Joule-heating shock,a crack-break process of microcosmic phase transformation is observed by in-situ transmission electron microscopy.The half-wave potential values of Co_(3)O_(4)-JH,Mn_(3)O_(4)-JH,CoMn_(2)O_(4)-JH and CoFe_(2)O_(4)-JH in the electrocatalytic oxygen reduction reaction were 0.77,0.78,0.79 and 0.76,respectively.This suggests that the Joule heating is a fast and efficient method for the preparation of spinel oxide electrocatalysts.
基金supported by the National Programs for Nano-Key Project (2017YFA0206700)the National Key R&D Program of China (2018YFB1502100)+2 种基金the National Natural Science Foundation of China (21835004)111 Project from the Ministry of Education of China (B12015)the Fundamental Research Funds for the Central Universities, Nankai University (63191711 and 63191416)
文摘Silicon-based material is one of the most promising substitutes of widely used graphite anodes for the next generation Li-ion batteries due to its high theoretical capacity,low working potential,environmental friendliness,and abundant natural resource.However,the huge volume expansion and serious interfacial side reactions during lithiation and delithiation progresses of the silicon anode are the key issues which impede their further practical applications.Rational designs of silicon nanostructures are effective ways to address these problems.In this progress report,we firstly highlight the fundamental scientific problems,and then focus on recent progresses in design,preparation,in-situ characterization methods and failure mechanism of nanostructured silicon anode for high capacity lithium battery.We also summarize the key lessons from the successes so far and offer perspectives and future challenges to promote the applications of silicon anode in practical lithium batteries.
文摘The conventional ceramic synthesis of perovskite oxides involves extended high-temperature annealing in air and is unfavorable to the in situ hybridization of the conductive agent, thus resulting in large particle sizes, low surface area and limited electrochemical activities. Here we report a rapid gel auto-combustion approach for the synthesis of a perovskite/carbon hybrid at a low temperature of 180℃. The energy-saving synthetic strategy allows the formation of small and homogeneously dispersed LaxMnO3±6/C nanocomposites. Remarkably, the synthesized La0.99MnO3.03/C nanocomposite exhibits comparable oxygen reduction reaction （ORR） activity （with onset and peak potentials of 0.97 and 0.88 V, respectively） to the benchmark Pt/C due to the facilitated charge transfer, optimal eg electron filling of Mn, and coupled C-O-Mn bonding. Furthermore, the nanocomposite efficiently catalyzes a Zn-air battery that delivers a peak power density of 430 mW·cm^-2, an energy density of 837 W·h·kgzn^-1 and 340 h stability at a current rate of 10 mA·cm^-2.
基金supported by MOST(2017YFA0206700 and 2018YFB1502100)NSFC(21871149,21925503,and 51571125)+2 种基金MOE(B12015)Tianjin Project(18JCZDJC31100)the Fundamental Research Funds for the Central Universities.
文摘Defects engineering is an efficient strategy to enhance the performance of electrode materials by modulating the local electronic structure but usually requires costly and complicated processing.Here,an electrochemical reduction etching method has been developed for controllable tailoring of the cationic defects in iron-based oxides under mild conditions.The optimized defective spinel-type iron nickel oxide exhibits an overpotential as low as 270 mV at 10 mA cm−2 and a Tafel slope of only 33.8 mV dec−1 for the oxygen evolution reaction(OER),outperforming the benchmark RuO2 and pristine oxide.Experiments and theoretical calculations reveal that Fe vacancies can enhance Ni–O covalency,increase the density of active sites,and optimize the surface electronic structure,which promote the water adsorption/activation and moderate oxygen intermediate species adsorption,thus significantly enhancing OER activity.This work provides a promising approach to create cation deficiency and mechanistic insight to understand the vacancy-induced enhancement of oxygen electrocatalysis.
基金This work was supported by the National Natural Science Foundation of China(21871149,52001171,and 51571125)the Ministry of Science and Technology(2018YFB1502100)+3 种基金the Tianjin Project(18JCZDJC31100)the Ministry of Education(B12015)the NCC Fund(NCC2020FH03)the Fundamental Research Funds for the Central Universities.
文摘The facile synthesis of highly active and stable bifunctional electrocatalysts to catalyze water splitting is attractive but challenging.Herein,we report the electrodeposition of Pt-decorated Ni(OH)_(2)/CeO_(2)(PNC)hybrid as an efficient and robust bifunctional electrocatalyst.The graphite-supported PNC catalyst delivers superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities over the benchmark Pt/C and RuO_(2),respectively.For overall water electrolysis,the PNC hybrid only requires a cell voltage of 1.45V at 10mAcm-2 and sustains over 85 h at 1000mAcm^(-2).The remarkable HER/OER performances are attributed to the superhydrophilicity and multiple effects of PNC,in which Ni(OH)_(2)and CeO_(2)accelerate HER on Pt due to promoted water dissociation and strong electronic interaction,while the electron-pulling Ce cations facilitate the generation of high-valence Ni OER-active species.These results suggest the promising application of PNC for H2 production from water electrolysis.
基金supported by Tianjin Project(No.18JCZDJC31100)Ministry of Science and Technology(No.2017YFA0206702)+2 种基金National Natural Science Foundation of China,(Nos.21871149 and 21925503)Ministry of Education(No.B12015)the Fundamental Research Funds for the Central Universities(No.63201035)。
文摘Metallic zinc is attractive anode material of rechargeable aqueous Zn-based batteries due to its ambient stability,high volumetric capacity,and abundant reserves.Nonetheless,Zn anodes suffer from issues such as low coulombic efficiency(CE),large polarization and dendrite formation.Herein,uniform Zn electrodeposition is reported on carbon substrates by selective nitrogen doping.Combined experimental and theoretical investigations demonstrate that pyrrolic and pyridinic nitrogen doped in carbon play beneficial effect as zinc-philic sites to direct nucleation and growth of metallic Zn,while negligible effect is observed for graphite nitrogen in Zn plating.The carbon cloth with modified amount of doped pyrrolic and pyridinic nitrogen stabilizes Zn plating/stripping with 99.3%CE after 300 cycles and significantly increases the deliverable capacity at high depth of charge and discharge compared to undoped carbon substrate and Zn foil.This work provides a better understanding of heteroatom doping effect in design and preparation of stable 3 D carbon-supported zinc anode.
基金supported by the National Natural Science Foundation of China(Nos.51879228,51769034)the National Science Funds for Creative Research Groups of China(No.51421006)the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Numerous studies have evaluated the toxicity and endocrine disrupting properties of organic UV filters for aquatic organisms,but little is known about their biodegradation in river sediments and their impact on microorganisms.We have set up the sterile and microbiological systems in the laboratory,adding 2-ethylhexyl-4-methoxycinnamate(EHMC),one of organic UV filters included in the list of high yield chemicals,at concentrations of 2,20 and 200μg/L,and characterized the microbial community composition and diversity in sediments.Monitoring of EHMC degradation within 30 days revealed that the half-life in the microbial system(3.49 days)was much shorter than that in the sterile system(7.55 days).Two potential degradation products,4-mercaptobenzoic acid and 3-methoxyphenol were identified in the microbial system.Furthermore,high-throughput 16s and 18s rRNA gene sequencing showed that Proteobacteria dominated the sediment bacterial assemblages followed by Chloroflexi,Acidobacteria,Bacteroidetes and Nitrospirae;Eukaryota_uncultured fungus dominated the sediment fungal assemblages.Correlation analysis demonstrated that two bacterium genera(Anaerolineaceae_uncultured and Burkholderiaceae_uncultured)were significantly correlated with the biodegradation of EHMC.These results illustrate the biodegradability of EHMC in river sediments and its potential impact on microbial communities,which can provide useful information for eliminating the pollution of organic UV filters in natural river systems and assessing their potential ecological risks.
基金financially supported by the Ministry of Science and Technology(No. 2017YFA0206700)the National Natural Science Foundation of China(No. 51571125) and Ministry of Education(No. B12015)
文摘It is desirable to exploit cost-effective and earth-abundant catalysts for the oxygen evolution reaction (OER) in developing electrochemical energy conversion and storage technologies. Here we report a facile hydrothermal synthesis of NiMo04 nanorods as active and stable OER catalyst in alkaline condition. The prepared NiMoO_4 nanorods exhibit a considerably low overpotential of 340 mV at the current density of10 mA/cm^2 and a low Tafel slope of 45.6 mV/dec, which is comparable to the benchmark Ru02.Furthermore, the performance of NiMoO_4 significantly surpasses binary NiO and MoO_3 oxides due to enhanced charge transfer and promoted formation of catalytically active Ni^(3+) species. The results highlight the importance of designing ternary oxides in oxygen electrocatalysis.
