In the context of peaking carbon dioxide emissions and carbon neutrality,development of feasible methods for converting CO_(2)into high value-added chemicals stands out as a hot subject.In this study,P[D+COO^(−)][Br^(...In the context of peaking carbon dioxide emissions and carbon neutrality,development of feasible methods for converting CO_(2)into high value-added chemicals stands out as a hot subject.In this study,P[D+COO^(−)][Br^(−)][DBUH^(+)],a series of novel heterogeneous dual-ionic poly(ionic liquid)s(PILs)were synthesized readily from 2-(dimethylamino)ethyl methacrylate(DMAEMA),bromo-substituted aliphatic acids,organic bases and divinylbenzene(DVB).The structures,compositions and morphologies were characterized or determined by nuclear magnetic resonance(NMR),thermal gravimetric analysis(TGA),infrared spectroscopy(IR),scanning electron microscopes(SEM),and Brunauer-Emmett-Teller analysis(BET),etc.Application of the P[D+COO^(−)][Br^(−)][DBUH^(+)]series as catalysts in converting CO_(2)into cyclic carbonates showed that P[D+COO^(−)][Br^(−)][DBUH^(+)]-2/1/0.6was able to catalyze epiclorohydrin-CO_(2)cycloaddition the most efficiently.This afforded chloropropylene carbonate(CPC)in 98.4%yield with≥99%selectivity in 24 hr under solvent-and additive-free conditions at atmospheric pressure.Reusability experiments showed that recycling of the catalyst 6 times only resulted in a slight decline in the catalytic performance.In addition,it could be used for the synthesis of a variety of differently substituted cyclic carbonates in good to excellent yields.Finally,key catalytic active sites were probed,and a reasonable mechanism was proposed accordingly.In summary,this work poses an efficient strategy for heterogenization of dual-ionic PILs and provides amild and environmentally benign approach to the fixation and utilization of carbon dioxide.展开更多
Novel dual-ionic imidazolium salts are shown to display excellent catalytic activity for cycloaddition of carbon dioxide and epoxides under room temperature and atmospheric pressure(0.1 MPa)without any solvent and co-...Novel dual-ionic imidazolium salts are shown to display excellent catalytic activity for cycloaddition of carbon dioxide and epoxides under room temperature and atmospheric pressure(0.1 MPa)without any solvent and co-catalyst leading to 96.1%product yield.It can be reused five times to keep the product yield over 90%.These intriguing results are attributed to a new reaction mechanism,which is supported by theoretical calculations along with the measurements of ^(13)C NMR spectrum and Fourier transform infrared spectroscopy(FT-IR).The excellent catalytic activity can be traced to a CO_(2)-philic group along with an electrophilic hydrogen atom.Our work shows that incorporation of CO_(2)-philic group is an feasible pathway to develop the new efficient ionic liquids.展开更多
A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the acti...A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure(XANES),X-ray photoelectron spectroscopy(XPS),and Rh extended X-ray absorption fine structure(EXAFS)analyses.As the highlight of this study,Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which[Rh(CO)_(2)I_(2)]^(-)is the traditional active center.A TOF of 350 h^(-1)was obtained for the reaction over[Rh(CO)I_(3)]^(2-),with>95%propionyl selectivity at 3.5 MPa and 468 K.No deactivation was detected during a near 1000 h running test.The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP,and the formation of two ionic bonds between[Rh(CO)I_(3)]^(2-)and the cationic P(V)framework([P]^(+))of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching.展开更多
Dual-ion batteries(DIBs)usually use carbon-based materials as electrodes,showing advantages in high operating volt-age,potential low cost,and environmental friendliness.Different from conventional“rocking chair”type...Dual-ion batteries(DIBs)usually use carbon-based materials as electrodes,showing advantages in high operating volt-age,potential low cost,and environmental friendliness.Different from conventional“rocking chair”type secondary batter-ies,DIBs perform a unique working mechanism,which employ both cation and anion taking part in capacity contribution at an anode and a cathode,respectively,during electrochemical reactions.Graphite has been identified as a suitable cathode material for anion intercalation at high voltages(>4.8 V)with fast reaction kinetics.However,the development of DIBs is being hindered by dynamic mismatch between a cathode and an anode due to sluggish Li+diffusion at a high rate.Herein,we prepared phyllostachys edulis derived carbon(PEC)through microstructure regulation strategy and investigated the carbonized temperature effect,which effectively tailored the rich short-range ordered graphite microdomains and disor-dered amorphous regions,as well as a unique nano-pore hierarchical structure.The pore size distribution of nano-pores was concentrated in 0.5-5 nm,providing suitable channels for rapid Li+transportation.It was found that PEC-500(carbon-ized at 500℃)achieved a high capacity of 436 mAh·g^(-1)at 300 mA·g^(-1)and excellent rate performance(maintaining a high capacity of 231 mAh·g^(-1)at 3 A·g^(-1)).The assembled dual-carbon PEC-500||graphite full battery delivered 114 mAh·g^(-1)at 10 C with 96%capacity retention after 3000 cycles and outstanding rate capability,providing 74 mAh·g^(-1)at 50 C.展开更多
High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based ...High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.展开更多
Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and sustainability.However,most AZIB cathode materials suffer from short cycling l...Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and sustainability.However,most AZIB cathode materials suffer from short cycling life and poor rate performance.Herein,a bipolar donor-acceptor(D-A)conjugated microporous polymer(PTZ-BDTB),consisting of electron-withdrawing benzo[1,2-b:4,5-b']dithiophene-4,8-dio ne(BDTB)units and electron-donating phenothiazine(PTZ)units,is developed as the cathode material of aqueous zinc dual-ion batteries(AZDIBs).The D-A type structure design could reduce the band gap,thus promoting electron transfer in the polymer framework.Therefore,the PTZ-BDTB cathode in a30 mol/kg(m)ZnCl_(2)water-in-salt electrolyte exhibits a high reversible capacity of 202 mA h g^(-1)at0.05 A g^(-1)with excellent rate performance(109 mA h g^(-1)at 15 A g^(-1)),which is far superior to its counterpart polymers PPTZ and PB-BDTB.Impressively,PTZ-BDTB shows ultra-stable cycle performance with capacity retention ratios of 76.2%after 460 cycles at 0.05 A g^(-1)and 96%after 27000 cycles at 5 A g^(-1).PTZBDTB also exhibits a low self-discharge ability with capacity retention about 76.4%after resting the battery for 28 days.These results demonstrate that D-A type structural design is a promising strategy for constructing high performance cathode materials for AZDIBs.展开更多
Compared with Zn^(2+),the current mainly reported charge carrier for zinc hybrid capacitors,small-hydrated-sized and light-weight NH_(4)^(+)is expected as a better one to mediate cathodic interfacial electrochemical b...Compared with Zn^(2+),the current mainly reported charge carrier for zinc hybrid capacitors,small-hydrated-sized and light-weight NH_(4)^(+)is expected as a better one to mediate cathodic interfacial electrochemical behaviors,yet has not been unraveled.Here we propose an NH_(4)^(+)-modulated cationic solvation strategy to optimize cathodic spatial charge distribution and achieve dynamic Zn^(2+)/NH_(4)^(+)co-storage for boosting Zinc hybrid capacitors.Owing to the hierarchical cationic solvated structure in hybrid Zn(CF_(3)SO_(3))_(2)–NH_4CF_(3)SO_(3)electrolyte,high-reactive Zn^(2+)and small-hydrate-sized NH_4(H_(2)O))(4)^(+)induce cathodic interfacial Helmholtz plane reconfiguration,thus effectively enhancing the spatial charge density to activate 20%capacity enhancement.Furthermore,cathodic interfacial adsorbed hydrated NH_(4)^(+)ions afford high-kinetics and ultrastable C···H(NH_(4)^(+))charge storage process due to a much lower desolvation energy barrier compared with heavy and rigid Zn(H_(2)O)_6^(2+)(5.81 vs.14.90 eV).Consequently,physical uptake and multielectron redox of Zn^(2+)/NH_(4)^(+)in carbon cathode enable the zinc capacitor to deliver high capacity(240 mAh g^(-1)at 0.5 A g^(-1)),large-current tolerance(130 mAh g^(-1)at 50 A g^(-1))and ultralong lifespan(400,000cycles).This study gives new insights into the design of cathode–electrolyte interfaces toward advanced zinc-based energy storage.展开更多
The worldwide proliferation of portable electronics has resulted in a dramatic increase in the number of spent lithium-ion batteries(LIBs).However,traditional recycling methods still have limitations because of such h...The worldwide proliferation of portable electronics has resulted in a dramatic increase in the number of spent lithium-ion batteries(LIBs).However,traditional recycling methods still have limitations because of such huge amounts of spent LIBs.Therefore,we proposed an ecofriendly and sustainable double recycling strategy to concurrently reuse the cathode(LiCoO_(2))and anode(graphite)materials of spent LIBs and recycled LiCoPO_(4)/graphite(RLCPG)in Li^(+)/PF^(-)_(6) co-de/intercalation dual-ion batteries.The recycle-derived dualion batteries of Li/RLCPG show impressive electrochemical performance,with an appropriate discharge capacity of 86.2 mAh·g^(-1) at25 mA·g^(-1) and 69%capacity retention after 400 cycles.Dual recycling of the cathode and anode from spent LIBs avoids wastage of resources and yields cathode materials with excellent performance,thereby offering an ecofriendly and sustainable way to design novel secondary batteries.展开更多
Dual-ion batteries(DIBs)have attracted great attention due to their affordable prices,environmentalfriendliness,and high operating voltage.However,the conventional graphite anode in DIBs has draw-backs such as unsatis...Dual-ion batteries(DIBs)have attracted great attention due to their affordable prices,environmentalfriendliness,and high operating voltage.However,the conventional graphite anode in DIBs has draw-backs such as unsatisfactory capacity and worrying safety.MoS_(2)is considered to be a competitive anodematerial that exhibits large capacity due to its unique layered structure for cation insertion/extraction.Nevertheless,the sluggish reaction kinetics of MoS_(2)does not match the cathode side,which makes theconstructed full DIBs show poor rate ability.Here,a flower-like MoS_(2)/polyaniline composite electrode(MoS_(2)-PANI)where PANI was grown in situ between layers of MoS_(2)nanosheets was designed.In thisdesign,the inserted PANI can broaden the layer distance of MoS_(2)to facilitate cation diffusion and pre-vent the restacking of nanosheets.Furthermore,PANI is also expected to increase the conductivity andrelieve the volume changes during repeated charge/discharge cycles.Benefiting from that,the MoS_(2)-PANIelectrode delivered a reversible capacity of 561.91 mA h g^(-1) at 5 A g^(-1) in half-cell test.Moreover,whencoupled with a mildly expanded graphite(MEG)cathode,the obtained MEG//MoS_(2)-PANI DIB shows ex-cellent rate ability with a reversible discharge capacity of 86.62 mA h g^(-1) and a desirable energy densityof 308.83 W h kg-1 at 20 C.These results provide some inspiration for the design of high-rate DIBs.展开更多
A novel carbon foam with microporous structure(CFMS),with the advantages of a simple fabrication process,low energy consumption,large specific surface area and high conductivity,has been prepared by a facile one-step ...A novel carbon foam with microporous structure(CFMS),with the advantages of a simple fabrication process,low energy consumption,large specific surface area and high conductivity,has been prepared by a facile one-step carbonization.In addition,the carbon foam possesses suitable interlayer spacing in short range which is flexible to accommodate the deformation of carbon layer caused by the ion insertion and deinsertion at the charge and discharge state.Furthermore,a low cost carbon-based symmetric potassium dual-ion capacitor(PDIC),which integrates the virtues of potassium ion capacitors and dual-ion batteries,is successfully established with CFMS as both the battery-type cathode and the capacitor-type anode.PDIC displays a superior rate performance,an ultra-long cycle life(90%retention after 10000 cycles),and a high power density of 7800 W kg^-1 at an energy density of 39Whkg^-1.The PDIC also exhibits excellent ultrafast charge and slow discharge properties,with a full charge in just 60 s and a discharge time of more than 3000 s.展开更多
With the increasing popularity of new en ergy electric vehicles,the dema nd for lithium-ion batteries(LIBs)has been growing rapidly,which will produce a large number of spent LIBs.Therefore,recycling of spe nt LIBs ha...With the increasing popularity of new en ergy electric vehicles,the dema nd for lithium-ion batteries(LIBs)has been growing rapidly,which will produce a large number of spent LIBs.Therefore,recycling of spe nt LIBs has become an urge nt task to be solved,otherwise it will inevitably lead to serious environmental pollution.Herein,a unique recycling strategy is proposed to achieve the concurrent reuse of cathode and anode in the spent graphite/LiFePO_(4) batteries.Along with such recycling process,a unique cathode composed of recycled LFP/graphite(RLFPG)with cation/anion-co-storage ability is designed for new-type dual-ion battery(DIB).As a result,the recycle-derived DIB of Li/RLFPG is established with good electrochemical performance,such as an initial discharge capacity of 117.4 mA h g^(-1) at 25 mA g^(-1) and 78% capacity retention after 1000 cycles at 100 mA g^(-1).The working mechanism of Li/RLFPG DIB is also revealed via in situ X-ray diffraction and electrode kinetics studies.This work not only presents a farreaching significance for large-scale recycling of spent LIBs in the future,but also proposed a sustainable and econo mical method to design n ew-type sec on dary batteries as recycling of spe nt LIBs.展开更多
Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at h...Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at high potential(usually ≥ 4.5 V versus Li+/Li) is confronted with severe challenges including electrolyte decomposition on cathode interface, and structural deterioration of graphite accompanying with anions de-/intercalation, hinder its cyclic life. To address those drawbacks and preserve the DIB virtues, a feasible and scalable surface modification is achieved for the commercial graphite cathode of mesocarbon microbead. In/ex-situ studies reveal that, such an interfacial engineering facilitates and reconstructs the formation of chemically stable cathode electrolyte interphase with better flexibility alleviating the decomposition of electrolyte, regulating the anions de-/intercalation behavior in graphite with the retainment of structural integrity and without exerting considerable influence on kinetics of anions diffusion. As a result, the modified mesocarbon microbead exhibits a much-extended cycle life with high capacity retention of 82.3% even after 1000 cycles. This study demonstrates that the interface modification of electrode and coating skeleton play important roles on DIB performance improvement, providing the feasible basis for practical application of DIB owing to the green and scalable coating procedures.展开更多
High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and sol...High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.展开更多
Li4Ti5O(12)(LTO)has drawn great attention due to its safety and stability in lithium-ion batteries(LIBs).However,high potential plateau at 1.5 V vs.Li reduces the cell voltage,leading to a limited use of LTO.Dual-ion ...Li4Ti5O(12)(LTO)has drawn great attention due to its safety and stability in lithium-ion batteries(LIBs).However,high potential plateau at 1.5 V vs.Li reduces the cell voltage,leading to a limited use of LTO.Dual-ion batteries(DIBs)can achieve high working voltage due to high intercalation potential of cathode.Herein,we propose a DIB configuration in which LTO is used as anode and the working voltage was 3.5 V.This DIB achieves a maximum specific energy of 140 Wh/kg at a specific power of 35 W/kg,and the specific power of 2933 W/kg can be obtained with a remaining specific energy of 11 Wh/kg.Traditional LIB material shows greatly improved properties in the DIB configuration.Thus,reversing its disadvantage leads to upgraded performance of batteries.Our configuration has also widened the horizon of materials for DIBs.展开更多
Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIB...Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.展开更多
In dual-ion batteries (DIBs), energy storage is achieved by intercalation/de-intercalation of both cations and anions. Due to the mismatch between ion diameter and layer space of active materials, however, volume expa...In dual-ion batteries (DIBs), energy storage is achieved by intercalation/de-intercalation of both cations and anions. Due to the mismatch between ion diameter and layer space of active materials, however, volume expansion and exfoliation always occur for electrode materials. Herein, an integrated electrode Co3O4/carbon fiber paper (CFP) is prepared as the anode of DIB. As the Co3O4 nanosheets grow on CFP substrate vertically, it promotes the immersion of electrolyte and shortens the pathway for ionic transport. Besides, the strong interaction between Co3O4 and CFP substrate reduces the possibility of sheet exfoliation. An integrated-electrode-based DIB is therefore packaged using Co3O4/CFP as anode and graphite as cathode. As a result, a high energy density of 72 Wh/kg is achieved at a power density of 150 W/kg. The design of integrated electrode provides a new route for the development of high-performance DIBs.展开更多
The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based ...The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based on nanostructured Ni_3S_2/Ni foam@RGO(NSNR) composite anode is developed, utilizing graphite as cathode material and LiPF6-VC-based solvent as electrolyte. The battery operates at high working voltage of 4.2–4.5 V, with superior discharge capacity of ～90 m A h g^(-1) at 100 mA g^(-1), outstanding rate performance, and long-term cycling stability over 500 cycles with discharge capacity retention of ～85.6%. Moreover, the composite simultaneously acts as the anode material and the current collector, and the corrosion phenomenon can be greatly reduced compared to metallic Al anode. Thus, this work represents a significant step forward for practical safe, low-cost and high working voltage dual-ion batteries,showing attractive potential for future energy storage application.展开更多
基金supported by the Applied Basic Research Foundation of Guangdong Province(No.2019A1515110551)the Science Foundation for Distinguished Scholars of Dongguan University of Technology(No.196100041051).
文摘In the context of peaking carbon dioxide emissions and carbon neutrality,development of feasible methods for converting CO_(2)into high value-added chemicals stands out as a hot subject.In this study,P[D+COO^(−)][Br^(−)][DBUH^(+)],a series of novel heterogeneous dual-ionic poly(ionic liquid)s(PILs)were synthesized readily from 2-(dimethylamino)ethyl methacrylate(DMAEMA),bromo-substituted aliphatic acids,organic bases and divinylbenzene(DVB).The structures,compositions and morphologies were characterized or determined by nuclear magnetic resonance(NMR),thermal gravimetric analysis(TGA),infrared spectroscopy(IR),scanning electron microscopes(SEM),and Brunauer-Emmett-Teller analysis(BET),etc.Application of the P[D+COO^(−)][Br^(−)][DBUH^(+)]series as catalysts in converting CO_(2)into cyclic carbonates showed that P[D+COO^(−)][Br^(−)][DBUH^(+)]-2/1/0.6was able to catalyze epiclorohydrin-CO_(2)cycloaddition the most efficiently.This afforded chloropropylene carbonate(CPC)in 98.4%yield with≥99%selectivity in 24 hr under solvent-and additive-free conditions at atmospheric pressure.Reusability experiments showed that recycling of the catalyst 6 times only resulted in a slight decline in the catalytic performance.In addition,it could be used for the synthesis of a variety of differently substituted cyclic carbonates in good to excellent yields.Finally,key catalytic active sites were probed,and a reasonable mechanism was proposed accordingly.In summary,this work poses an efficient strategy for heterogenization of dual-ionic PILs and provides amild and environmentally benign approach to the fixation and utilization of carbon dioxide.
基金supported by the National Natural Science Foundation of China(21975064)Program of Henan Center for Outstanding Overseas Scientists(GZS2020011)+1 种基金Henan University's first-class discipline science and technology research project(2018YLTD07,2018YLZDYJ11,2019YLZDYJ09)the Excellent Foreign Experts Project of Henan University。
文摘Novel dual-ionic imidazolium salts are shown to display excellent catalytic activity for cycloaddition of carbon dioxide and epoxides under room temperature and atmospheric pressure(0.1 MPa)without any solvent and co-catalyst leading to 96.1%product yield.It can be reused five times to keep the product yield over 90%.These intriguing results are attributed to a new reaction mechanism,which is supported by theoretical calculations along with the measurements of ^(13)C NMR spectrum and Fourier transform infrared spectroscopy(FT-IR).The excellent catalytic activity can be traced to a CO_(2)-philic group along with an electrophilic hydrogen atom.Our work shows that incorporation of CO_(2)-philic group is an feasible pathway to develop the new efficient ionic liquids.
文摘A single-Rh-site catalyst(Rh-TPISP)that was ionically-embedded on a P(V)quaternary phosphonium porous polymer was evaluated for heterogeneous ethanol carbonylation.The[Rh(CO)I_(3)]^(2-)unit was proposed to be the active center of Rh-TPISP for the carbonylation reaction based on detailed Rh L3-edge X-ray absorption near edge structure(XANES),X-ray photoelectron spectroscopy(XPS),and Rh extended X-ray absorption fine structure(EXAFS)analyses.As the highlight of this study,Rh-TPISP displayed distinctly higher activity for heterogeneous ethanol carbonylation than the reported catalytic systems in which[Rh(CO)_(2)I_(2)]^(-)is the traditional active center.A TOF of 350 h^(-1)was obtained for the reaction over[Rh(CO)I_(3)]^(2-),with>95%propionyl selectivity at 3.5 MPa and 468 K.No deactivation was detected during a near 1000 h running test.The more electron-rich Rh center was thought to be crucial for explaining the superior activity and selectivity of Rh-TPISP,and the formation of two ionic bonds between[Rh(CO)I_(3)]^(2-)and the cationic P(V)framework([P]^(+))of the polymer was suggested to play a key role in firmly immobilizing the active species to prevent Rh leaching.
基金supported by the National Natural Science Foundation of China(Grant Nos.52272208,22309057)the Natural Science Foundation of Hubei Province(Grant No.2023AFB355)the Fundamental Research Funds for the Central Universities of China(Grant No.2662022LXQD001).
文摘Dual-ion batteries(DIBs)usually use carbon-based materials as electrodes,showing advantages in high operating volt-age,potential low cost,and environmental friendliness.Different from conventional“rocking chair”type secondary batter-ies,DIBs perform a unique working mechanism,which employ both cation and anion taking part in capacity contribution at an anode and a cathode,respectively,during electrochemical reactions.Graphite has been identified as a suitable cathode material for anion intercalation at high voltages(>4.8 V)with fast reaction kinetics.However,the development of DIBs is being hindered by dynamic mismatch between a cathode and an anode due to sluggish Li+diffusion at a high rate.Herein,we prepared phyllostachys edulis derived carbon(PEC)through microstructure regulation strategy and investigated the carbonized temperature effect,which effectively tailored the rich short-range ordered graphite microdomains and disor-dered amorphous regions,as well as a unique nano-pore hierarchical structure.The pore size distribution of nano-pores was concentrated in 0.5-5 nm,providing suitable channels for rapid Li+transportation.It was found that PEC-500(carbon-ized at 500℃)achieved a high capacity of 436 mAh·g^(-1)at 300 mA·g^(-1)and excellent rate performance(maintaining a high capacity of 231 mAh·g^(-1)at 3 A·g^(-1)).The assembled dual-carbon PEC-500||graphite full battery delivered 114 mAh·g^(-1)at 10 C with 96%capacity retention after 3000 cycles and outstanding rate capability,providing 74 mAh·g^(-1)at 50 C.
基金the financial support received from the National Natural Science Foundation of China(22378426,22138013)the Natural Science Foundation of Shandong Province(ZR2022MB088)the Taishan Scholar Project(ts201712020)。
文摘High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.
基金financial supported by the National Natural Science Foundation of China(22175110&22375076,52103264)the Hubei Provincial Natural Science Foundation of China(2024AFA031)the Key Research and Development Program of Wuhan(2024010802030157)。
文摘Aqueous zinc-ion batteries(AZIBs)have hugely latent advantages in large-scale energy storage due to its innate safety,reasonable price,and sustainability.However,most AZIB cathode materials suffer from short cycling life and poor rate performance.Herein,a bipolar donor-acceptor(D-A)conjugated microporous polymer(PTZ-BDTB),consisting of electron-withdrawing benzo[1,2-b:4,5-b']dithiophene-4,8-dio ne(BDTB)units and electron-donating phenothiazine(PTZ)units,is developed as the cathode material of aqueous zinc dual-ion batteries(AZDIBs).The D-A type structure design could reduce the band gap,thus promoting electron transfer in the polymer framework.Therefore,the PTZ-BDTB cathode in a30 mol/kg(m)ZnCl_(2)water-in-salt electrolyte exhibits a high reversible capacity of 202 mA h g^(-1)at0.05 A g^(-1)with excellent rate performance(109 mA h g^(-1)at 15 A g^(-1)),which is far superior to its counterpart polymers PPTZ and PB-BDTB.Impressively,PTZ-BDTB shows ultra-stable cycle performance with capacity retention ratios of 76.2%after 460 cycles at 0.05 A g^(-1)and 96%after 27000 cycles at 5 A g^(-1).PTZBDTB also exhibits a low self-discharge ability with capacity retention about 76.4%after resting the battery for 28 days.These results demonstrate that D-A type structural design is a promising strategy for constructing high performance cathode materials for AZDIBs.
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111 and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300 and 19DZ2271500)+3 种基金China Postdoctoral Science Foundation(2022M712402)Shanghai Rising-Star Program(23YF1449200)Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(22120210529 and 2023-3-YB-07)。
文摘Compared with Zn^(2+),the current mainly reported charge carrier for zinc hybrid capacitors,small-hydrated-sized and light-weight NH_(4)^(+)is expected as a better one to mediate cathodic interfacial electrochemical behaviors,yet has not been unraveled.Here we propose an NH_(4)^(+)-modulated cationic solvation strategy to optimize cathodic spatial charge distribution and achieve dynamic Zn^(2+)/NH_(4)^(+)co-storage for boosting Zinc hybrid capacitors.Owing to the hierarchical cationic solvated structure in hybrid Zn(CF_(3)SO_(3))_(2)–NH_4CF_(3)SO_(3)electrolyte,high-reactive Zn^(2+)and small-hydrate-sized NH_4(H_(2)O))(4)^(+)induce cathodic interfacial Helmholtz plane reconfiguration,thus effectively enhancing the spatial charge density to activate 20%capacity enhancement.Furthermore,cathodic interfacial adsorbed hydrated NH_(4)^(+)ions afford high-kinetics and ultrastable C···H(NH_(4)^(+))charge storage process due to a much lower desolvation energy barrier compared with heavy and rigid Zn(H_(2)O)_6^(2+)(5.81 vs.14.90 eV).Consequently,physical uptake and multielectron redox of Zn^(2+)/NH_(4)^(+)in carbon cathode enable the zinc capacitor to deliver high capacity(240 mAh g^(-1)at 0.5 A g^(-1)),large-current tolerance(130 mAh g^(-1)at 50 A g^(-1))and ultralong lifespan(400,000cycles).This study gives new insights into the design of cathode–electrolyte interfaces toward advanced zinc-based energy storage.
基金the National Natural Science Foundation of China(No.52173246)the Science and Technology Planning Project of Guangzhou City,China(No.2023B03J1278)。
文摘The worldwide proliferation of portable electronics has resulted in a dramatic increase in the number of spent lithium-ion batteries(LIBs).However,traditional recycling methods still have limitations because of such huge amounts of spent LIBs.Therefore,we proposed an ecofriendly and sustainable double recycling strategy to concurrently reuse the cathode(LiCoO_(2))and anode(graphite)materials of spent LIBs and recycled LiCoPO_(4)/graphite(RLCPG)in Li^(+)/PF^(-)_(6) co-de/intercalation dual-ion batteries.The recycle-derived dualion batteries of Li/RLCPG show impressive electrochemical performance,with an appropriate discharge capacity of 86.2 mAh·g^(-1) at25 mA·g^(-1) and 69%capacity retention after 400 cycles.Dual recycling of the cathode and anode from spent LIBs avoids wastage of resources and yields cathode materials with excellent performance,thereby offering an ecofriendly and sustainable way to design novel secondary batteries.
基金supported by the Natural Science Foundation of Shandong Province with Grant No.ZR2020QE048the National Natural Science Foundation of China with Grant No.21905304+1 种基金the State Key Laboratory of Heavy Oil Processing with Grant No.SKLHOP202101006the National Defense Science and Technology Innovation Special Zone Project No.22-05-CXZX-04-04-29.The authors also want to thank Shiyanjia Lab(www.shiyanjia.com)for the TEM test.
文摘Dual-ion batteries(DIBs)have attracted great attention due to their affordable prices,environmentalfriendliness,and high operating voltage.However,the conventional graphite anode in DIBs has draw-backs such as unsatisfactory capacity and worrying safety.MoS_(2)is considered to be a competitive anodematerial that exhibits large capacity due to its unique layered structure for cation insertion/extraction.Nevertheless,the sluggish reaction kinetics of MoS_(2)does not match the cathode side,which makes theconstructed full DIBs show poor rate ability.Here,a flower-like MoS_(2)/polyaniline composite electrode(MoS_(2)-PANI)where PANI was grown in situ between layers of MoS_(2)nanosheets was designed.In thisdesign,the inserted PANI can broaden the layer distance of MoS_(2)to facilitate cation diffusion and pre-vent the restacking of nanosheets.Furthermore,PANI is also expected to increase the conductivity andrelieve the volume changes during repeated charge/discharge cycles.Benefiting from that,the MoS_(2)-PANIelectrode delivered a reversible capacity of 561.91 mA h g^(-1) at 5 A g^(-1) in half-cell test.Moreover,whencoupled with a mildly expanded graphite(MEG)cathode,the obtained MEG//MoS_(2)-PANI DIB shows ex-cellent rate ability with a reversible discharge capacity of 86.62 mA h g^(-1) and a desirable energy densityof 308.83 W h kg-1 at 20 C.These results provide some inspiration for the design of high-rate DIBs.
基金financially supported by the National Natural Science Foundation of China(Nos.51672078 and 21473052)Hunan University State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project(No.71675004)+2 种基金the Fundamental Research Funds for the Central UniversitiesHunan Natural Science Foundation(2019JJ40031)Foundation of State Key Laboratory of Coal Conversion(Grant J1718-903)。
文摘A novel carbon foam with microporous structure(CFMS),with the advantages of a simple fabrication process,low energy consumption,large specific surface area and high conductivity,has been prepared by a facile one-step carbonization.In addition,the carbon foam possesses suitable interlayer spacing in short range which is flexible to accommodate the deformation of carbon layer caused by the ion insertion and deinsertion at the charge and discharge state.Furthermore,a low cost carbon-based symmetric potassium dual-ion capacitor(PDIC),which integrates the virtues of potassium ion capacitors and dual-ion batteries,is successfully established with CFMS as both the battery-type cathode and the capacitor-type anode.PDIC displays a superior rate performance,an ultra-long cycle life(90%retention after 10000 cycles),and a high power density of 7800 W kg^-1 at an energy density of 39Whkg^-1.The PDIC also exhibits excellent ultrafast charge and slow discharge properties,with a full charge in just 60 s and a discharge time of more than 3000 s.
基金support from the National Natural Science Foundation of China(No.91963118)the Science Technology Program of Jilin Province(No.20200201066JC)the 111 Project(No.B13013).
文摘With the increasing popularity of new en ergy electric vehicles,the dema nd for lithium-ion batteries(LIBs)has been growing rapidly,which will produce a large number of spent LIBs.Therefore,recycling of spe nt LIBs has become an urge nt task to be solved,otherwise it will inevitably lead to serious environmental pollution.Herein,a unique recycling strategy is proposed to achieve the concurrent reuse of cathode and anode in the spent graphite/LiFePO_(4) batteries.Along with such recycling process,a unique cathode composed of recycled LFP/graphite(RLFPG)with cation/anion-co-storage ability is designed for new-type dual-ion battery(DIB).As a result,the recycle-derived DIB of Li/RLFPG is established with good electrochemical performance,such as an initial discharge capacity of 117.4 mA h g^(-1) at 25 mA g^(-1) and 78% capacity retention after 1000 cycles at 100 mA g^(-1).The working mechanism of Li/RLFPG DIB is also revealed via in situ X-ray diffraction and electrode kinetics studies.This work not only presents a farreaching significance for large-scale recycling of spent LIBs in the future,but also proposed a sustainable and econo mical method to design n ew-type sec on dary batteries as recycling of spe nt LIBs.
基金the financial support from the National Natural Science Foundation of China(91963118)the Fundamental Research Funds for the Central Universities(2412019ZD010)。
文摘Dual-ion battery(DIB) composed of graphite cathode and lithium anode is regarded as an advanced secondary battery because of the low cost, high working voltage and environmental friendliness. However,DIB operated at high potential(usually ≥ 4.5 V versus Li+/Li) is confronted with severe challenges including electrolyte decomposition on cathode interface, and structural deterioration of graphite accompanying with anions de-/intercalation, hinder its cyclic life. To address those drawbacks and preserve the DIB virtues, a feasible and scalable surface modification is achieved for the commercial graphite cathode of mesocarbon microbead. In/ex-situ studies reveal that, such an interfacial engineering facilitates and reconstructs the formation of chemically stable cathode electrolyte interphase with better flexibility alleviating the decomposition of electrolyte, regulating the anions de-/intercalation behavior in graphite with the retainment of structural integrity and without exerting considerable influence on kinetics of anions diffusion. As a result, the modified mesocarbon microbead exhibits a much-extended cycle life with high capacity retention of 82.3% even after 1000 cycles. This study demonstrates that the interface modification of electrode and coating skeleton play important roles on DIB performance improvement, providing the feasible basis for practical application of DIB owing to the green and scalable coating procedures.
基金supported by the Australian Research Council Discovery Projects(DP150104365 and DP160104835)the financial support by the China Scholarship Council(201808340038) for his visiting at Curtin University,Australiathe ARC Discovery Early Career Researcher Award(DE180100773)。
文摘High-temperature solid-state electrolyte is a key component of several important electrochemical devices,such as oxygen sensors for automobile exhaust control,solid oxide fuel cells(SOFCs) for power generation,and solid oxide electrolysis cells for H_(2) production from water electrolysis or CO_(2) electrochemical reduction to value-added chemicals.In particular,internal diffusion of protons or oxygen ions is a fundamental and crucial issue in the research of SOFCs,hypothetically based on either oxygen-ionconducting electrolytes or proton-conducting electrolytes.Up to now,some electrolyte materials based on fluorite or perovskite structure were found to show certain degree of dual-ion transportation capability,while in available electrolyte database,particularly in the field of SOFCs,such dual-ion conductivity was seriously overlooked.Actually,few concerns arising to the simultaneous proton and oxygen-ion conductivities in electrolyte of SOFCs inevitably induce various inadequate and confusing results in literature.Understanding dual-ion transportation behavior in electrolyte is indisputably of great importance to explain some unusual fuel cell performance as reported in literature and enrich the knowledge of solid state ionics.On the other hand,exploration of novel dual-ion conducting electrolytes will benefit the development of SOFCs.In this review,we provide a comprehensive summary of the understanding of dual-ion transportation in solid electrolyte and recent advances of dual-ion conducting SOFCs.The oxygen ion and proton conduction mechanisms at elevated temperature inside oxide-based electrolyte materials are first introduced,and then(mixed) oxygen ion and proton conduction behaviors of fluorite and perovskite-type oxides are discussed.Following on,recent advances in the development of dual-ion conducting SOFCs based on fluorite and perovskite-type single-phase or composite electrolytes,are reviewed.Finally,the challenges in the development of dual-ion conducting SOFCs are discussed and future prospects are proposed.
基金the financial supports from the National Natural Science Foundation of China (51932003, 51902050, 51872115 & 51802110)Program for the Development of Science and Technology of Jilin Province (20190201309JC)+4 种基金the Open Project Program of Wuhan National Laboratory for Optoelectronics (2018WNLOKF022)the Jilin Province/Jilin University co-Construction Project-Funds for New Materials (SXGJSF2017-3, Branch-2/440050316A36)Program for JLU Science and Technology Innovative Research Team (JLUSTIRT, 2017TD-09)the Fundamental Research Funds for the Central Universities JLU“Double-First Class” Discipline for Materials Science & Engineering.
文摘Li4Ti5O(12)(LTO)has drawn great attention due to its safety and stability in lithium-ion batteries(LIBs).However,high potential plateau at 1.5 V vs.Li reduces the cell voltage,leading to a limited use of LTO.Dual-ion batteries(DIBs)can achieve high working voltage due to high intercalation potential of cathode.Herein,we propose a DIB configuration in which LTO is used as anode and the working voltage was 3.5 V.This DIB achieves a maximum specific energy of 140 Wh/kg at a specific power of 35 W/kg,and the specific power of 2933 W/kg can be obtained with a remaining specific energy of 11 Wh/kg.Traditional LIB material shows greatly improved properties in the DIB configuration.Thus,reversing its disadvantage leads to upgraded performance of batteries.Our configuration has also widened the horizon of materials for DIBs.
基金financially supported by the National key Research & Development Program of China (2022YFE0115900, 2021YFA1501500)the National Natural Science Foundation of China (Nos. 22225902, U22A20436, 22209185)+3 种基金the CAS-Commonwealth Scientific and Industrial Research Organization (CSIRO) Joint Research Projects (121835KYSB20200039)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (Grant. YLUDNL Fund 2021011)Fujian Province Central Government Guides to Science and Technology Development Special Project (No. 2022L3024)Natural Science Foundation of Fujian Province, China (No. 2021J02020)。
文摘Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.
基金Supports from the National Natural Science Foundation of China (51872115 and 51802110)the National Key R&D Program of China (2016YFA0200400)+2 种基金the Jilin Province/Jilin University Co-construction Project-Funds for New Materials (SXGJSF20173, Branch-2/440050316A36)the Program for JLU Science and Technology Innovative Research Team (JLUSTIRT, 2017TD-09)“Double-First Class” Discipline for Materials Science & Engineering, are greatly acknowledged
文摘In dual-ion batteries (DIBs), energy storage is achieved by intercalation/de-intercalation of both cations and anions. Due to the mismatch between ion diameter and layer space of active materials, however, volume expansion and exfoliation always occur for electrode materials. Herein, an integrated electrode Co3O4/carbon fiber paper (CFP) is prepared as the anode of DIB. As the Co3O4 nanosheets grow on CFP substrate vertically, it promotes the immersion of electrolyte and shortens the pathway for ionic transport. Besides, the strong interaction between Co3O4 and CFP substrate reduces the possibility of sheet exfoliation. An integrated-electrode-based DIB is therefore packaged using Co3O4/CFP as anode and graphite as cathode. As a result, a high energy density of 72 Wh/kg is achieved at a power density of 150 W/kg. The design of integrated electrode provides a new route for the development of high-performance DIBs.
基金supported by the National Natural Science Foundation of China (No. 51725401)the Fundamental Research Funds for the Central Universities (FRF-TP-15-002C1 and FRF-TP17-002C2)
文摘The growing global demands of safe, low-cost and high working voltage energy storage devices trigger strong interests in novel battery concepts beyond state-of-art lithium-ion battery. Herein, a dualion battery based on nanostructured Ni_3S_2/Ni foam@RGO(NSNR) composite anode is developed, utilizing graphite as cathode material and LiPF6-VC-based solvent as electrolyte. The battery operates at high working voltage of 4.2–4.5 V, with superior discharge capacity of ～90 m A h g^(-1) at 100 mA g^(-1), outstanding rate performance, and long-term cycling stability over 500 cycles with discharge capacity retention of ～85.6%. Moreover, the composite simultaneously acts as the anode material and the current collector, and the corrosion phenomenon can be greatly reduced compared to metallic Al anode. Thus, this work represents a significant step forward for practical safe, low-cost and high working voltage dual-ion batteries,showing attractive potential for future energy storage application.
