Magnesium-lithium hybrid batteries(MLHBs)have gained increasing attention due to their combined advantages of rapid ion insertion/extraction cathode and magnesium metal anode.Herein,Sn S_(2)-SPAN hybrid cathode with s...Magnesium-lithium hybrid batteries(MLHBs)have gained increasing attention due to their combined advantages of rapid ion insertion/extraction cathode and magnesium metal anode.Herein,Sn S_(2)-SPAN hybrid cathode with strong C-Sn bond and rich defects is ingeniously constructed to realize Mg^(2+)/Li^(+)co-intercalation.The physical and chemical double-confinement synergistic engineering of sulfurized polyacrylonitrile can suppress the agglomeration of Sn S_(2)nanoparticles and the volume expansion,simultaneously promote charge transfer and enhance structural stability.The introduced abundant sulfur vacancies provide more active sites for Mg^(2+)/Li^(+)co-intercalation.Meanwhile,the beneficial effects of rich sulfur defects and C-Sn bond on enhanced electrochemical properties are further evidenced by density-functional theory(DFT)calculations.Therefore,compared with pristine SnS_(2),SnS_(2)-SPAN cathode displays high specific capacity(218 m Ah g^(-1)at 0.5A g^(-1)over 700 cycles)and ultra-long cycling life(101 m Ah g^(-1)at 5 A g^(-1)up to 28,000 cycles).And a high energy density of 307 Wh kg^(-1)can be realized by the Sn S_(2)-SPAN//Mg pouch cell.Such elaborate and simple design supplies a reference for the exploitation of advanced cathode materials with excellent electrochemical properties for MLHBs.展开更多
Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it ...Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.展开更多
Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the us...Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the use of a weakly solvating cyclic ether electrolyte with tetrahydropyran(THP)as the solvent.This approach induces the formation of a thin and dense inorganic-rich solid electrolyte interphase(SEI)film,which is accompanied by a decrease in the activation energy of electrode interfacial reactions due to the weak ligand binding of THP with K^(+).Density functional theory(DFT)simulations also corroborate the hypothesis that K^(+)has a lower binding energy with THP.During potassium storage process,the phenomenon of solvent co-intercalation of graphite does not occur,which greatly reduces the destruction of the graphite structure and enables a superior electrochemical performance and enhanced cycling stability at a lower concentration(2 M).At a current density of 0.2 C(55.8 mA·g^(-1)),the battery can be stably cycled for 800 cycles(approximately 8 months)with a specific capacity of 171.8 mAh·g^(-1).This study provides a new ether-based electrolyte for potassium ion batteries and effectively reduces the electrolyte cost,which is expected to inspire further development of energy storage batteries.展开更多
Carbonaceous materials have long been considered promising anode materials for Na-ion batteries. However, the electrochemical performance of conventional carbon anodes is generally poor because the sodium ion storage ...Carbonaceous materials have long been considered promising anode materials for Na-ion batteries. However, the electrochemical performance of conventional carbon anodes is generally poor because the sodium ion storage solely relies on the disordered region of the carbon materials in a carbonate-based electrolyte. The solvent co-intercalation mechanism for Na ions has been recently reported in natural graphite anodes for Na-ion batteries with ether-based electrolytes, but their capacities are still unsatisfactory. We show here for the first time that by combining regular Na ion storage in the disordered carbon layer and solvent co-intercalation mechanism in the graphitized layer of a commercial N330 carbon black as an anode material for Na-ion batteries in ether-based electrolyte, the reversible capacity could be fully realized and doubled in magnitude. This unique sodium intercalation process resulted in a significantly improved electrochemical performance for the N330 electrode with an initial reversible capacity of 234 mAh.g-1 at 50 mA.g-1 and a superior rate capability of 105 mAh.g-1 at 3,200 mA-g-1. When cycled at 3,200 mA.g-1 over 2,000 cycles, the electrode still exhibited a highly reversible capacity of 72 mAh.g-1 with a negligible capacity loss per cycle （0.0167%）. Additionally, surface-sensitive C K-edge X-ray absorption spectroscopy, with the assistance of electrochemical and physicochemical characterizations, helped in identifying the controlled formation and evolution of a thin and robust solid electrolyte interphase film. This film not only reduced the resistance for sodium ion diffusion, but also maintained the structural stability of the electrode for extended cycle reversibility. The superior electrochemical performance of N330 carbon black strongly demonstrated the potential of applying ether-based electrolytes for a wide range of carbon anodes apart from natural graphite.展开更多
With low cost and high safety,aqueous zinc-based batteries have received considerable interest.Nevertheless,the excess utilization of zinc metal in the anodes of these batteries reduces energy density and increases co...With low cost and high safety,aqueous zinc-based batteries have received considerable interest.Nevertheless,the excess utilization of zinc metal in the anodes of these batteries reduces energy density and increases costs.Herein,an ultrathin electrode of approximately 6.2μm thick is constructed by coating Ti_(3)C_(2)T_(x)/nanocellulose hybrid onto a stainless steel foil.This electrode is used as the Zn-free anode for aqueous hybrid Zn-Na battery,in which,a concentrated electrolyte is used to improve electrochemical reversibility.The Ti_(3)C_(2)T_(x)/nanocellulose coating is found to improve the electrolyte wettability,facilitate desolvation process of hydrated Zn^(2+) ions,lower nucleation overpotential,improve zinc plating kinetics,guide horizontal zinc plating along the Zn(002)facet,and inhibit parasitic side reactions.It is also found that the Na_(3)V_(2)(PO_(4))_(3) cathode material adopts a highly reversible Zn^(2+)/Na^(+)co-intercalation charge storage mechanism in this system.Thanks to these benefits,the assembled hybrid Zn-Na battery exhibits excellent rate capability,superior cyclability,and good anti-freezing ability.This work provides a new concept of electrode design for electrochemical energy storage.展开更多
Magnetic expanded graphite(EG)hybrids were synthesized by co-intercalation polymerization of aniline together with transition metal ions.Experimental results show that metal ions(Fe,Co,Ni,Cu)and even their mixtures ca...Magnetic expanded graphite(EG)hybrids were synthesized by co-intercalation polymerization of aniline together with transition metal ions.Experimental results show that metal ions(Fe,Co,Ni,Cu)and even their mixtures can co-intercalate into graphite interlayers with flexibly controllable ratios and contents.Among these co-intercalation compounds,Fe/Ni-intercalated graphite with a predesigned mole ratio of 1:3 transforms into NiFe_(2)O_(4)/FeNi_(3)@EG during the annealing process.The synthesized magnetic EG hybrids present multiband microwave absorption in C and X bands due to improved impedance match as well as significantly enhanced interfacial polarization relaxation induced by multi-componential metals.The reflection values of−39.1 dB at 6.95 GHz and−25.7 dB at 9.4 GHz are achieved with an ultra-low loading of 5 wt.%.This work provides a flexible approach for tuning the components and structures of magnetic EG hybrids,which may contribute to the development of microwave absorption materials with superior performances.展开更多
Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with ...Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.展开更多
The stability and safety of aqueous aluminum metal batteries(AAMBs)have garnered an enormous amount of attention.However,severe corrosion during cycling and inefficient deposition behavior at the Al anode hinder their...The stability and safety of aqueous aluminum metal batteries(AAMBs)have garnered an enormous amount of attention.However,severe corrosion during cycling and inefficient deposition behavior at the Al anode hinder their application.In this paper,CeCl_(3)was selected as a water inhibition additive to achieve active water confinement,which dramatically improved the corrosion behavior and prolonged the cycle life of the Al electrode.A combination of spectroscopic characterization and computational analysis showed that Cl^(-)breaks hydrogen bonds in the electrolyte and has higher adsorption energy on Al,thus inhibiting water-induced corrosion.Meanwhile,Ce^(3+)has a stronger affinity for Al than H_(2)O,thus promoting the formation of the surface protective layer.Cl^(-)in the modified electrolyte results in less hydration around Al^(3+).Due to the excellent water inhibition effect of CeCl_(3),the corrosion phenomenon of Al electrodes was significantly improved,and the dominant growth of the Al(111)crystal plane was achieved.Al//Prussian blue analogue(PBA)full cells with CeCl_(3)exhibit significantly improved voltage polarization(0.342 V),cycle life(550 cycles),discharge specific capacity(112 mAh g^(-1)),and selfdischarge behavior(87.97%).The Ce^(3+)in the additive is also able to be co-intercalated into the PBA with Al^(3+),improving the stability of the PBA.However,the conductivity reduction of this strategy at higher concentrations needs to be further addressed.Compared with organic electrolyte and molten salt systems,the cycle life of the aqueous electrolyte in this work still falls short.This modification method paves the way for further development of efficient AAMBs.展开更多
Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are...Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.展开更多
Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature(low-T).However,sluggish kinetics and aggravated dendrites present two major challenges for ano...Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature(low-T).However,sluggish kinetics and aggravated dendrites present two major challenges for anodes to achieve the goal at low-T.Herein,we propose an interlayer confined strategy for tailoring nitrogen terminals on Ti_(3)C_(2) MXene(Ti_(3)C_(2)-N_(funct)) to address these issues.The introduction of nitrogen terminals endows Ti_(3)C_(2)-N_(funct) with large interlayer space and charge redistribution,improved conductivity and sufficient adsorption sites for Na^(+),which improves the possibility of Ti_(3)C_(2) for accommodating more Na atoms,further enhancing the Na^(+) storage capability of Ti_(3)C_(2).As revealed,Ti_(3)C_(2)-N_(funct) not only possesses a lower Na-ion diffusion energy barrier and charge trans-fer activation energy,but also exhibits Na^(+)-solvent co-intercalation behavior to circumvent a high de-solvation energy barrier at low-T.Besides,the solid electrolyte interface dominated by inorganic com-pounds is more beneficial for the Na^(+)transfer at the electrode/electrolyte interface.Compared with of the unmodified sample,Ti_(3)C_(2)-Nfunct exhibits a twofold capacity(201 mAh g^(-1)),fast-charging ability(18 min at 80% capacity retention),and great superiority in cycle life(80.9%@5000 cycles)at -25℃.When coupling with Na_(3)V_(2)(PO_(4))_(2)F_(3) cathode,the Ti_(3)C_(2)-N_(funct)//NVPF exhibits high energy density and cycle stability at -25℃.展开更多
Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applica...Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries(DISBs) possess higher energy density,especially owning high power density for its higher operating voltage(> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier(artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG(covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage.Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.展开更多
The practical application of Na metal anode is plagued by the dendrite growth,unstable solid electrolyte interphase(SEI)formation and volume change during the cycling process.Herein,poly(tetrafluoroethylene)(noted as ...The practical application of Na metal anode is plagued by the dendrite growth,unstable solid electrolyte interphase(SEI)formation and volume change during the cycling process.Herein,poly(tetrafluoroethylene)(noted as PTFE)coating microcrystalline graphite is designed as the sodium metal anode host by a facile and cost-effective strategy.The isotropous microcrystalline graphite(MG)is conducive to guiding Na+to form a co-intercalation structure into MG.And the PTFE coating layer can form NaF as artificial SEI film for uniform ion transport and deposition.As a result,the gained PTFE coating MG electrode can deliver a long-life span over 1,200 cycles with an average Coulombic efficiency(CE)of 99.88%.To note,almost the CE in each cycle is around 99.8%–100%.When assembled with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode as full cells,the full cell paired with PTFE coating MG electrode can operate much stable than that of MG electrode for the existence of PTFE coating layer.Even utilized as sodium-free Na metal anode paired with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode,it can also deliver a high initial CE of 76.27%at 0.5 C.After 100 cycles,it still has a high discharge capacity of 83.5 mAh·g^(−1).展开更多
Aqueous ammonium-ion(NH_(4)^(+))hybrid supercapacitor(AA-HSC),as a new type of energy storage device with great potential,is in the initial stage of rapid development.Based on its special energy storage mechanism,expl...Aqueous ammonium-ion(NH_(4)^(+))hybrid supercapacitor(AA-HSC),as a new type of energy storage device with great potential,is in the initial stage of rapid development.Based on its special energy storage mechanism,exploiting novel NH_(4)^(+)-hostingmaterials is still a great challenge.Herein,vanadium oxide hydration(VOH)tuned by interlayer engineering of K+/PANI co-intercalation,named KVO/PANI,is designed for AA-HSC.Intercalated PANI can shield interaction between NH_(4)^(+)and V–O layers to some extent and enlarge interlayer space,which improves the efficiency of reversible NH_(4)^(+)(de)insertion.However,K+enhances redox activity and electronic conductivity.The synergistic effect of co-intercalation optimizes intercalation pseudocapacitive behavior during the(de)ammonization process,which is reported in NH_(4)^(+)storage for the first time.Theoretical calculations reveal that the lowered electron transport barrier and enhanced electronic conductivity improveNH_(4)^(+)kinetics and exhibit high capacitance for charge storage.The KVO/PANI can deliver the specific capacitance of 340 F g^(−1) at 0.5 A g^(−1) and retain 177 F g^(−1) at 10 A g^(−1).Pairing with activated carbon,the AA-HSC can achieve a decent energy density of 31.8 Wh kg^(−1).This work gives inorganic/organic co-intercalation that can enhance the NH_(4)^(+)storage of VOH by interlayer engineering.The strategy can be used to design other materials for aqueous energy storage systems.展开更多
基金financially supported by the National Key R&D Program of China(No.2023YFB3809500)National Natural Science Foundation of China(Grant No.51931006,52272240 and U22A20118)+2 种基金the Fundamental Research Funds for the Central Universities of China(Xiamen University:No.20720220074)Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(HRTP-[2022]-22)the“Double-First Class”Foundation of Materials Intelligent Manufacturing Discipline of Xiamen University。
文摘Magnesium-lithium hybrid batteries(MLHBs)have gained increasing attention due to their combined advantages of rapid ion insertion/extraction cathode and magnesium metal anode.Herein,Sn S_(2)-SPAN hybrid cathode with strong C-Sn bond and rich defects is ingeniously constructed to realize Mg^(2+)/Li^(+)co-intercalation.The physical and chemical double-confinement synergistic engineering of sulfurized polyacrylonitrile can suppress the agglomeration of Sn S_(2)nanoparticles and the volume expansion,simultaneously promote charge transfer and enhance structural stability.The introduced abundant sulfur vacancies provide more active sites for Mg^(2+)/Li^(+)co-intercalation.Meanwhile,the beneficial effects of rich sulfur defects and C-Sn bond on enhanced electrochemical properties are further evidenced by density-functional theory(DFT)calculations.Therefore,compared with pristine SnS_(2),SnS_(2)-SPAN cathode displays high specific capacity(218 m Ah g^(-1)at 0.5A g^(-1)over 700 cycles)and ultra-long cycling life(101 m Ah g^(-1)at 5 A g^(-1)up to 28,000 cycles).And a high energy density of 307 Wh kg^(-1)can be realized by the Sn S_(2)-SPAN//Mg pouch cell.Such elaborate and simple design supplies a reference for the exploitation of advanced cathode materials with excellent electrochemical properties for MLHBs.
基金supported by the National Natural Science Foundation of China(Nos.52072061,22322903,12174162)the Natural Science Foundation of Sichuan,China(No.2023NSFSC1914)21C Innovation Laboratory,Contemporary Amperex Technology Ltd.by project No.21C-OP-202103。
文摘Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.
基金financial support from the National Key Research and Development Program of China(No.2022YFB2404300)the National Natural Science Foundation of China(Nos.22409153 and 52101269).
文摘Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the use of a weakly solvating cyclic ether electrolyte with tetrahydropyran(THP)as the solvent.This approach induces the formation of a thin and dense inorganic-rich solid electrolyte interphase(SEI)film,which is accompanied by a decrease in the activation energy of electrode interfacial reactions due to the weak ligand binding of THP with K^(+).Density functional theory(DFT)simulations also corroborate the hypothesis that K^(+)has a lower binding energy with THP.During potassium storage process,the phenomenon of solvent co-intercalation of graphite does not occur,which greatly reduces the destruction of the graphite structure and enables a superior electrochemical performance and enhanced cycling stability at a lower concentration(2 M).At a current density of 0.2 C(55.8 mA·g^(-1)),the battery can be stably cycled for 800 cycles(approximately 8 months)with a specific capacity of 171.8 mAh·g^(-1).This study provides a new ether-based electrolyte for potassium ion batteries and effectively reduces the electrolyte cost,which is expected to inspire further development of energy storage batteries.
文摘Carbonaceous materials have long been considered promising anode materials for Na-ion batteries. However, the electrochemical performance of conventional carbon anodes is generally poor because the sodium ion storage solely relies on the disordered region of the carbon materials in a carbonate-based electrolyte. The solvent co-intercalation mechanism for Na ions has been recently reported in natural graphite anodes for Na-ion batteries with ether-based electrolytes, but their capacities are still unsatisfactory. We show here for the first time that by combining regular Na ion storage in the disordered carbon layer and solvent co-intercalation mechanism in the graphitized layer of a commercial N330 carbon black as an anode material for Na-ion batteries in ether-based electrolyte, the reversible capacity could be fully realized and doubled in magnitude. This unique sodium intercalation process resulted in a significantly improved electrochemical performance for the N330 electrode with an initial reversible capacity of 234 mAh.g-1 at 50 mA.g-1 and a superior rate capability of 105 mAh.g-1 at 3,200 mA-g-1. When cycled at 3,200 mA.g-1 over 2,000 cycles, the electrode still exhibited a highly reversible capacity of 72 mAh.g-1 with a negligible capacity loss per cycle （0.0167%）. Additionally, surface-sensitive C K-edge X-ray absorption spectroscopy, with the assistance of electrochemical and physicochemical characterizations, helped in identifying the controlled formation and evolution of a thin and robust solid electrolyte interphase film. This film not only reduced the resistance for sodium ion diffusion, but also maintained the structural stability of the electrode for extended cycle reversibility. The superior electrochemical performance of N330 carbon black strongly demonstrated the potential of applying ether-based electrolytes for a wide range of carbon anodes apart from natural graphite.
基金We acknowledge the financial support from the National Natural Science Foundation of China(No.51902165)the Program of High-Level Talents in Six Industries of Jiangsu Province(No.XCL-040)the Jiangsu Specially-Appointed Professor Program.
文摘With low cost and high safety,aqueous zinc-based batteries have received considerable interest.Nevertheless,the excess utilization of zinc metal in the anodes of these batteries reduces energy density and increases costs.Herein,an ultrathin electrode of approximately 6.2μm thick is constructed by coating Ti_(3)C_(2)T_(x)/nanocellulose hybrid onto a stainless steel foil.This electrode is used as the Zn-free anode for aqueous hybrid Zn-Na battery,in which,a concentrated electrolyte is used to improve electrochemical reversibility.The Ti_(3)C_(2)T_(x)/nanocellulose coating is found to improve the electrolyte wettability,facilitate desolvation process of hydrated Zn^(2+) ions,lower nucleation overpotential,improve zinc plating kinetics,guide horizontal zinc plating along the Zn(002)facet,and inhibit parasitic side reactions.It is also found that the Na_(3)V_(2)(PO_(4))_(3) cathode material adopts a highly reversible Zn^(2+)/Na^(+)co-intercalation charge storage mechanism in this system.Thanks to these benefits,the assembled hybrid Zn-Na battery exhibits excellent rate capability,superior cyclability,and good anti-freezing ability.This work provides a new concept of electrode design for electrochemical energy storage.
基金the financial support of the National Natural Science Foundation of China(No.51573149)the Key R&D Projects in Sichuan Province(Nos.2020ZDZX0005 and 2020ZDZX0008).
文摘Magnetic expanded graphite(EG)hybrids were synthesized by co-intercalation polymerization of aniline together with transition metal ions.Experimental results show that metal ions(Fe,Co,Ni,Cu)and even their mixtures can co-intercalate into graphite interlayers with flexibly controllable ratios and contents.Among these co-intercalation compounds,Fe/Ni-intercalated graphite with a predesigned mole ratio of 1:3 transforms into NiFe_(2)O_(4)/FeNi_(3)@EG during the annealing process.The synthesized magnetic EG hybrids present multiband microwave absorption in C and X bands due to improved impedance match as well as significantly enhanced interfacial polarization relaxation induced by multi-componential metals.The reflection values of−39.1 dB at 6.95 GHz and−25.7 dB at 9.4 GHz are achieved with an ultra-low loading of 5 wt.%.This work provides a flexible approach for tuning the components and structures of magnetic EG hybrids,which may contribute to the development of microwave absorption materials with superior performances.
基金financially supported by the National Natural Science Foundation of China(52372191)the Natural Science Foundation of Fujian Province(2023J05047)+1 种基金the Natural Science Foundation of Xiamen,China(3502Z202372036)the support of the High-Performance Computing Center(HPCC)at Harbin Institute of Technology on first-principles calculations.
文摘Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.
基金financial support from the following sources:the National Natural Science Foundation of China(NSFC)(grants 52171206,52271209)the Key Project of Hebei Natural Science Foundation(F2024201031,E2020201030)+1 种基金the Science Research Project of Hebei Education Department(JCZX2025019)the Interdisciplinary Research Program of Hebei University(DXK202401)。
文摘The stability and safety of aqueous aluminum metal batteries(AAMBs)have garnered an enormous amount of attention.However,severe corrosion during cycling and inefficient deposition behavior at the Al anode hinder their application.In this paper,CeCl_(3)was selected as a water inhibition additive to achieve active water confinement,which dramatically improved the corrosion behavior and prolonged the cycle life of the Al electrode.A combination of spectroscopic characterization and computational analysis showed that Cl^(-)breaks hydrogen bonds in the electrolyte and has higher adsorption energy on Al,thus inhibiting water-induced corrosion.Meanwhile,Ce^(3+)has a stronger affinity for Al than H_(2)O,thus promoting the formation of the surface protective layer.Cl^(-)in the modified electrolyte results in less hydration around Al^(3+).Due to the excellent water inhibition effect of CeCl_(3),the corrosion phenomenon of Al electrodes was significantly improved,and the dominant growth of the Al(111)crystal plane was achieved.Al//Prussian blue analogue(PBA)full cells with CeCl_(3)exhibit significantly improved voltage polarization(0.342 V),cycle life(550 cycles),discharge specific capacity(112 mAh g^(-1)),and selfdischarge behavior(87.97%).The Ce^(3+)in the additive is also able to be co-intercalated into the PBA with Al^(3+),improving the stability of the PBA.However,the conductivity reduction of this strategy at higher concentrations needs to be further addressed.Compared with organic electrolyte and molten salt systems,the cycle life of the aqueous electrolyte in this work still falls short.This modification method paves the way for further development of efficient AAMBs.
基金the financial support from the National Natural Science Foundation of China, China (22005207, 52261160384)the Guangdong Basic and Applied Basic Research Foundation, Guangdong Province, China (2019A1515011819)+2 种基金the Outstanding Youth Basic Research Project of Shenzhen, Shenzhen, China (RCYX20221008092934093)the Joint Funds of the National Natural Science Foundation of China, China (U22A20140)the Science and Technology Development Fund, Macao SAR (0090/2021/A2 and 0049/2021/AGJ)
文摘Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.
基金the National Natural Sci-ence Foundation of China(Grant Nos.21673064,51902072 and 22109033)Heilongjiang Touyan Team(Grant No.HITTY-20190033)+1 种基金Fundamental Research Funds for the Central Universities(Grant Nos.HIT.NSRIF.2019040 and 2019041)State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(Grant No.2020 DX11).
文摘Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature(low-T).However,sluggish kinetics and aggravated dendrites present two major challenges for anodes to achieve the goal at low-T.Herein,we propose an interlayer confined strategy for tailoring nitrogen terminals on Ti_(3)C_(2) MXene(Ti_(3)C_(2)-N_(funct)) to address these issues.The introduction of nitrogen terminals endows Ti_(3)C_(2)-N_(funct) with large interlayer space and charge redistribution,improved conductivity and sufficient adsorption sites for Na^(+),which improves the possibility of Ti_(3)C_(2) for accommodating more Na atoms,further enhancing the Na^(+) storage capability of Ti_(3)C_(2).As revealed,Ti_(3)C_(2)-N_(funct) not only possesses a lower Na-ion diffusion energy barrier and charge trans-fer activation energy,but also exhibits Na^(+)-solvent co-intercalation behavior to circumvent a high de-solvation energy barrier at low-T.Besides,the solid electrolyte interface dominated by inorganic com-pounds is more beneficial for the Na^(+)transfer at the electrode/electrolyte interface.Compared with of the unmodified sample,Ti_(3)C_(2)-Nfunct exhibits a twofold capacity(201 mAh g^(-1)),fast-charging ability(18 min at 80% capacity retention),and great superiority in cycle life(80.9%@5000 cycles)at -25℃.When coupling with Na_(3)V_(2)(PO_(4))_(2)F_(3) cathode,the Ti_(3)C_(2)-N_(funct)//NVPF exhibits high energy density and cycle stability at -25℃.
基金financially supported by the National Natural Science Foundation of China (Nos. 51672071, 51802085, 51772296 and 51902090)“111 Project” (No. D17007)+2 种基金the National students' platform for innovation and entrepreneurship training program (No. 201910476010)the China Postdoctoral Science Foundation (No. 2019 M652546)the Henan Province Postdoctoral StartUp Foundation (No. 1901017)。
文摘Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries(DISBs) possess higher energy density,especially owning high power density for its higher operating voltage(> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier(artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG(covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage.Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.
基金supported by the Natural Science Foundation of Hunan Province,China(No.2020JJ1007)the Key Deployed Projects of the Chinese Academy of Sciences(No.ZDRW-CN-2021-3).
文摘The practical application of Na metal anode is plagued by the dendrite growth,unstable solid electrolyte interphase(SEI)formation and volume change during the cycling process.Herein,poly(tetrafluoroethylene)(noted as PTFE)coating microcrystalline graphite is designed as the sodium metal anode host by a facile and cost-effective strategy.The isotropous microcrystalline graphite(MG)is conducive to guiding Na+to form a co-intercalation structure into MG.And the PTFE coating layer can form NaF as artificial SEI film for uniform ion transport and deposition.As a result,the gained PTFE coating MG electrode can deliver a long-life span over 1,200 cycles with an average Coulombic efficiency(CE)of 99.88%.To note,almost the CE in each cycle is around 99.8%–100%.When assembled with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode as full cells,the full cell paired with PTFE coating MG electrode can operate much stable than that of MG electrode for the existence of PTFE coating layer.Even utilized as sodium-free Na metal anode paired with Na_(3)V_(2)(PO_(4))_(2)F_(3)cathode,it can also deliver a high initial CE of 76.27%at 0.5 C.After 100 cycles,it still has a high discharge capacity of 83.5 mAh·g^(−1).
基金Large Instrument and Equipment Open Foundation of Dalian University of Technology and Natural Science Foundation。
文摘Aqueous ammonium-ion(NH_(4)^(+))hybrid supercapacitor(AA-HSC),as a new type of energy storage device with great potential,is in the initial stage of rapid development.Based on its special energy storage mechanism,exploiting novel NH_(4)^(+)-hostingmaterials is still a great challenge.Herein,vanadium oxide hydration(VOH)tuned by interlayer engineering of K+/PANI co-intercalation,named KVO/PANI,is designed for AA-HSC.Intercalated PANI can shield interaction between NH_(4)^(+)and V–O layers to some extent and enlarge interlayer space,which improves the efficiency of reversible NH_(4)^(+)(de)insertion.However,K+enhances redox activity and electronic conductivity.The synergistic effect of co-intercalation optimizes intercalation pseudocapacitive behavior during the(de)ammonization process,which is reported in NH_(4)^(+)storage for the first time.Theoretical calculations reveal that the lowered electron transport barrier and enhanced electronic conductivity improveNH_(4)^(+)kinetics and exhibit high capacitance for charge storage.The KVO/PANI can deliver the specific capacitance of 340 F g^(−1) at 0.5 A g^(−1) and retain 177 F g^(−1) at 10 A g^(−1).Pairing with activated carbon,the AA-HSC can achieve a decent energy density of 31.8 Wh kg^(−1).This work gives inorganic/organic co-intercalation that can enhance the NH_(4)^(+)storage of VOH by interlayer engineering.The strategy can be used to design other materials for aqueous energy storage systems.
