Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on ...Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.展开更多
TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperat...TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.展开更多
Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of t...Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).展开更多
SnO_(2)-based anodes for lithium-ion batteries(LIBs)experience volume expansion,leading to rapid capacity decay and low conductivity.To address this problem,a composite consists of C/SnO_(2) with a core-shell structur...SnO_(2)-based anodes for lithium-ion batteries(LIBs)experience volume expansion,leading to rapid capacity decay and low conductivity.To address this problem,a composite consists of C/SnO_(2) with a core-shell structure and a carbonized nitrogen-doped Co-metal organic framework(Co-MOF)(NC)supported on carbon cloth(CC)was designed and prepared,which was denoted as C/SnO_(2)@NC@CC.C/SnO_(2)@NC@CC could be used directly as a flexible anode for LIBs.The combination of core-shell structure centered on carbon spheres,carbonized nitrogen-doped Co-MOF,and CC not only restricts the volume expansion but also functions as conductive networks to improve the electrical conductivity.C/SnO_(2)@NC@CC exhibits excellent electrochemical performance with charge and discharge specific capacities of 2066.0 and 2077.1 mAh/g,respectively,after 120 cycles at a current density of 0.5 A/g.展开更多
Lithium-ion batteries(LIBs)with high energy and power densities are extensively applied in various fields,such as portable electronic devices and electric vehicles.Compared with traditional inorganic electrode materia...Lithium-ion batteries(LIBs)with high energy and power densities are extensively applied in various fields,such as portable electronic devices and electric vehicles.Compared with traditional inorganic electrode materials,which confront the challenges of resource scarcity and restrained energy density,covalent organic frameworks(COFs)are attractive candidates as electrode materials for the next-generation LIBs.Herein,rational Schiff-base condensation of tetraphenyl-pphenylenediamine(TPPDA)and 5,12-bis(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione(QA-PCHO)yields a two-dimensional(2D)QT-COF as the cathode.2D QT-COF features a high crystalline nature with kgm topology and hierarchically micro-/meso-porous structure,which can strengthen the stability of the chemical structure and promote the fast Li^(+)diffusion under large current densities.These merits make the QT-COF cathode exhibit 110,000 ultralong cycling stability with~100%retention at 10,000 mA g^(-1)upon running for 150 days,exceeding all the thus far reported COF-based electrodes.Additionally,the combination of ex situ X-ray photoelectron spectroscopy,in-situ Raman investigation,and theoretical calculation exhaustively unveils the ion storage mechanism and the rationale underlying the exceptional property of QT-COF.The present result offers an advanced COF with enormous potential as organic electrodes for LIBs,hopefully solving the challenges of ultrahigh cycling stability with superb capacity preservation at high current densities.展开更多
The limited ion/electron transport kinetics and insufficient crystalline stability of TiNb_(2)O_(7)(TNO)present significant challenges to the development of high-performance lithium-ion batteries(LIBs)with fastchargin...The limited ion/electron transport kinetics and insufficient crystalline stability of TiNb_(2)O_(7)(TNO)present significant challenges to the development of high-performance lithium-ion batteries(LIBs)with fastcharging capabilities and long cycle life.Here we propose a dual-modification strategy combining Ndoped carbon(NC)coating and Co^(2+)/W^(6+)doping,which not only enhances ionic and electronic conductivity but also effectively regulates volume expansion during electrochemical cycling.Upon Li+ion insertion,a significant reduction in the unit cell expansion coefficient of doped TNO is observed,from 7.48%(pristine TNO)to 5.37%(with 3%W^(6+)doping)and 4.65%(with 3%Co^(2+)doping),alo ng with lowered lattice distortion and improved uniformity in internal strain release.Density functional theory(DFT)simulation demonstrates that Co^(2+)and W^(6+)ions preferentially substitute Ti^(4+)sites in the TNO crystal,leading to the improved electronic conductivity by narrowing the bandgap.Moreover,Co^(2+)doping creates lower electron density and wider Li+ion transport channels than W^(6+)doping.The optimized 3Co-TNO@NC anode delivers a remarkable power density of 11.0 kW kg^(-1)at 20 C while maintaining a high reversible capacity of 150.9 mAh g^(-1)at 10 C after 2000 cycles.It also exhibits excellent compatibility in full cells,paired well with LiFePO_(4)(137.9 mAh g^(-1)after 2000 cycles)and Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)(130.9 mAh g^(-1)after 500cycles)cathodes at 5 C,highlighting its potential as a high-safety,low-strain anode material for highpower LIBs.展开更多
Symmetric secondary batteries are expected to become promising storage devices on account of their low cost,environmentally friendly and high safety.Nevertheless,the further development of symmetric batteries needs to...Symmetric secondary batteries are expected to become promising storage devices on account of their low cost,environmentally friendly and high safety.Nevertheless,the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance.Cation-disordered rocksalt(DRX)Li_(2)FeTiO_(4)shows promising properties as symmetric electrodes,based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window.Unfortunately,this cation-disordered structure would not provide a cross-path for the rapid migration of Li^(+),ultimately resulting in inferior electrochemical dynamics and cycle stability.Herein,Li_(2)FeTiO_(4)nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants.Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic(e.g.,stable Fe^(2+)/Fe^(3+),Ti^(3+)/Ti^(4+)and moderated Fe^(3+)/Fe^(4+))and anionic redox,and maintain the DRX structure well during the cycling process.The half cells with nano-sized Li_(2)FeTiO_(4)as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g,respectively.Besides,the Li_(2)FeTiO_(4)//Li_(2)FeTiO_(4)symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles.This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.展开更多
In this paper,the ammonia leaching process and high-energy ball milling method were adapted to recover spent LiCoO_(2) material.The ammonia reduction leaching mechanism of LiCoO_(2) material in the ammonia-sodium sulf...In this paper,the ammonia leaching process and high-energy ball milling method were adapted to recover spent LiCoO_(2) material.The ammonia reduction leaching mechanism of LiCoO_(2) material in the ammonia-sodium sulfite-ammonium chloride system was elucidated.Compared with untreated LiCoO_(2) material,the leaching equilibrium time of LiCoO_(2) after ball-milled for 5 h was reduced from 48 h to 4 h,and the leaching efficiency of lithium and cobalt was improved from 69.86%and 70.80%to 89.86%and98.22%,respectively.Importantly,the apparent activation energy and leaching kinetic equation of the reaction was calculated by the shrinking core reaction model,indicating that the reaction was controlled by the chemical reaction.展开更多
As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting t...As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.展开更多
Li[NixCoyMn2]O2(0.6≤x≤0.8) cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of(003) to(104) observ...Li[NixCoyMn2]O2(0.6≤x≤0.8) cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of(003) to(104) observed from X-ray diffraction(XRD)increases with decreasing the Ni content or increasing the Co content.The scanning electron microscopy(SEM) images reveal that the small primary particles are agglomerated to form the secondary ones.As the Mn content increases,the primary and secondary particles become larger and the resulted particle size for the Li[Ni(0.6)Co(0.2)Mn(0.2)]O2 is uniformly distributed in the range of100-300 nm.Although the initial discharge capacity of the Li/Li[NixCoyMn2]O2 cells reduces with decreasing the Ni content,the cyclic performance and rate capability are improved with higher Mn or Co content.The Li[Ni(0.6)Co(0.2)Mn(0.2)]O2 can deliver excellent cyclability with a capacity retention of 97.1%after 50 cycles.展开更多
Nanosphere-like Li2FeSiO4/C was synthesized via a solution method using sucrose as carbon sources under a mild condition of time-saving and energy-saving, followed by sintering at high temperatures for crystallization...Nanosphere-like Li2FeSiO4/C was synthesized via a solution method using sucrose as carbon sources under a mild condition of time-saving and energy-saving, followed by sintering at high temperatures for crystallization. The amount of carbon in the composite is less than 10% (mass fraction), and the X-ray diffraction result confirms that the sample is of pure single phase indexed with the orthorhombic Pmn21 space group. The particle size of the Li2FeSiO4/C synthesized at 700 °C for 9 h is very fine and spherical-like with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, were tested. The cell of this sample can deliver a discharge capacity of 166 mA-h/g at C/20 rate in the first three cycles. After 30 cycles, the capacity decreases to 158 mA-h/g, and the capacity retention is up to 95%. The results show that this method can prepare nanosphere-like Li2FeSiO4/C composite with good electrochemical performance.展开更多
2LiFe1-xCoxPO4-Li3V2(P04)3/C was synthesized using Fel-2xCo2xVO4 as precursor which was prepared by a simple co-precipitation method. 2LiFej-xCoxPO4-Li3V2(PO4)3/C samples were characterized by X-ray diffraction (...2LiFe1-xCoxPO4-Li3V2(P04)3/C was synthesized using Fel-2xCo2xVO4 as precursor which was prepared by a simple co-precipitation method. 2LiFej-xCoxPO4-Li3V2(PO4)3/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. All 2LiFel-xCoxPOa-Li3V2(PO4)3/C composites are of the similar crystal structure. The XRD analysis and SEM images show that 2LiFe0.96Co0.04PO4-Li3V2(PO4)3/C sample has the best-ordered structure and the smallest particle size. The charge-discharge tests demonstrate that these powders have the best electrochemical properties with an initial discharge capacity of 144.1 mA.h/g and capacity retention of 95.6% after 100 cycles when cycled at a current density of 0.1C between 2.5 and 4.5 V.展开更多
MXenes,a new family of two-dimensional(2D)materials with excellent electronic conductivity and hydrophilicity,have shown distinctive advantages as a highly conductive matrix material for lithium-ion battery anodes.Her...MXenes,a new family of two-dimensional(2D)materials with excellent electronic conductivity and hydrophilicity,have shown distinctive advantages as a highly conductive matrix material for lithium-ion battery anodes.Herein,a facile electrostatic self-assembly of SnO2 quantum dots(QDs)on Ti3C2Tx MXene sheets is proposed.The as-prepared SnO2/MXene hybrids have a unique 0D-2D structure,in which the 0D SnO2 QDs(~4.7 nm)are uniformly distributed over 2D Ti3C2Tx MXene sheets with controllable loading amount.The SnO2 QDs serve as a high capacity provider and the“spacer”to prevent the MXene sheets from restacking;the highly conductive Ti3C2Tx MXene can not only provide efficient pathways for fast transport of electrons and Li ions,but also buffer the volume change of SnO2 during lithiation/delithiation by confining SnO2 QDs between the MXene nanosheets.Therefore,the 0D-2D SnO2 QDs/MXene hybrids deliver superior lithium storage properties with high capacity(887.4 mAh g?1 at 50 mA g?1),stable cycle performance(659.8 mAh g?1 at 100 mA g?1 after 100 cycles with a capacity retention of 91%)and excellent rate performance(364 mAh g?1 at 3 A g?1),making it a promising anode material for lithium-ion batteries.展开更多
Samples of LiNi0.95-xCoxAl0.05O2 (x = 0.10 and 0.15) and LiNiO2, synthesized by the solid-state reaction at 725℃ for 24 h from LiOH-H2O, Ni2O3, Co2O3, and AI(OH)3 under an oxygen stream, were characterized by TG-...Samples of LiNi0.95-xCoxAl0.05O2 (x = 0.10 and 0.15) and LiNiO2, synthesized by the solid-state reaction at 725℃ for 24 h from LiOH-H2O, Ni2O3, Co2O3, and AI(OH)3 under an oxygen stream, were characterized by TG-DTA, XRD, SEM, and electrochemical tests. Simultaneous doping of cobalt and aluminum at the Ni-site in LiNiO2 was tried to improve the cathode performance for lithium-ion batteries. The results showed that co-doping (especially, 5 at.% A1 and 10 at.% Co) definitely had a large beneficial effect in increasing the capacity (186.2 mA.h/g of the first discharge capacity for LiNio.s.42OoaoAlo.0502) and cycling behavior (180.1 mA-h/g after 10 cycles for LiNio.85CooaoAlo.osO2) compared with 180.7 mA.h/g of the first discharge capacity and 157.7 mA.h/g of the tenth discharge capacity for LiNiO2, respectively. Differen- tial capacity versus voltage curves showed that the co-doped LiNio.95_xCoxmlo.osO2 had less intensity of the phase transitions than the pristine LiNiO2.展开更多
A new LiCoO2 recovery technology for Li-ion batteries was studied in this paper. LiCoO2 was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the...A new LiCoO2 recovery technology for Li-ion batteries was studied in this paper. LiCoO2 was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li2CO3, LiOH-H20 and LiAc-2H2O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO2 was obtained by calcining the mixture at 850℃ for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO2 synthesized by adding Li2CO3 is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g^-1 between 3.0-4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g^-1.展开更多
Vertical MoS2nanosheets were controllably patterned onto graphene as nanoflowers through a two-step hydrothermal method. The interconnected network and intimate contact between MoS2nanosheets and graphene by vertical ...Vertical MoS2nanosheets were controllably patterned onto graphene as nanoflowers through a two-step hydrothermal method. The interconnected network and intimate contact between MoS2nanosheets and graphene by vertical channels enabled a high mechanical integrity of electrode and cycling stability. In particular, MoS2/graphene nanoflowers anode delivered an ultrahigh specific capacity of 901.8 mA·h/g after 700 stable cycles at 1000 mA/g and a corresponding capacity retention as 98.9% from the second cycle onwards.展开更多
In this work,nickel/T-Nb_(2)O_(5)nanoparticles encapsulated in mesoporous carbon nanofibers(denoted as Ni/T-Nb_(2)O_(5)@CNFs)are successfully prepared through a simple electrospinning route and succedent heating treat...In this work,nickel/T-Nb_(2)O_(5)nanoparticles encapsulated in mesoporous carbon nanofibers(denoted as Ni/T-Nb_(2)O_(5)@CNFs)are successfully prepared through a simple electrospinning route and succedent heating treatment.The presence of Ni in carbon nanofibers is beneficial for enhancing the electronic conductivity and the initial Coulombic efficiency.Ni/T-Nb_(2)O_(5)nanoparticles are homogeneously incorporated in carbon nanofibers to form a nanocomposite system,which provides effective buffering during the lithiation/delithiation process for cycling stability.The Ni/TNb_(2)O_(5)@CNFs show high surface area(26.321 m^(2)·g^(-1))and mesoporous microstructure,resulting in higher capacity and excellent rate performance.The Ni/T-Nb_(2)O_(5)@CNFs exhibit a remarkable capacity of 437 mAh·g^(-1)at a current density of0.5 A·g^(-1)after 230 cycles and a capacity of 173 mAh·g^(-1)at a current density up to 10.0 A·g^(-1)after 1400 cycles.This work indicates that nickel/T-Nb_(2)O_(5)nanoparticles encapsulated in carbon nanofibers can be a promising candidate for anode material in high-power LIBs.展开更多
In this work, we report a facile route for the synthesis of Li3V2(PO4)3/C cathode material via freezedrying and then calcination. The effect of calcination temperature on the electrochemical properties of the Li3V2(PO...In this work, we report a facile route for the synthesis of Li3V2(PO4)3/C cathode material via freezedrying and then calcination. The effect of calcination temperature on the electrochemical properties of the Li3V2(PO4)3/C is also investigated. When used as a lithium-ion battery cathode, the optimized Li3V2(PO4)3/C (LVP-800) through calcination at 800 ℃ exhibits a high initial charge and discharge capacity. The excellent electrochemical performance of LVP-800 is attributed to the good crystallinity and uniform morphology of the electrode material. In addition, the residual carbon can also improve the conductivity and buffer the volume expansion during the Li-ion extraction/reinsertion. Meanwhile, charge compensation also plays an important role in excellent electrochemical performance.展开更多
As the earliest commercial cathode material for lithium-ion batteries,lithium cobalt oxide(LiCoO_(2)) shows various advantages,including high theoretical capacity,excellent rate capability,compressed electrode density...As the earliest commercial cathode material for lithium-ion batteries,lithium cobalt oxide(LiCoO_(2)) shows various advantages,including high theoretical capacity,excellent rate capability,compressed electrode density,etc.Until now,it still plays an important role in the lithium-ion battery market.Due to these advantages,further increasing the charging cutoff voltage of LiCoO_(2)to guarantee higher energy density is an irresistible development trend of LiCoO_(2)cathode materials in the future.However,using high charging cutoff voltage may induce a lot of negative effects,especially the rapid decay of cycle capacity.These are mainly caused by rapid destruction of crystal structure and aggravation of interface side reaction at high voltage during the cycle.Therefore,how to maintain a stable crystal structure of LiCoO_(2)to ensure the excellent long cycle performance at high voltage is a hot research issue in the further application of LiCoO_(2).In this review,we summarized the failure causes and extensive solutions of LiCoO_(2)at high voltage and promoted some new modification strategies.Moreover,the development trend of solving the failure problem of high-voltage LiCoO_(2)in the future such as defect engineering and high-temperature shock technique is also discussed.展开更多
In this work,a sponge-like polysulfonamide(PSA)/SiO_2 composite membrane is unprecedentedly prepared by the phase inversion method,and successfully demonstrated as a novel separator of lithium-ion batteries(LIBs).Comp...In this work,a sponge-like polysulfonamide(PSA)/SiO_2 composite membrane is unprecedentedly prepared by the phase inversion method,and successfully demonstrated as a novel separator of lithium-ion batteries(LIBs).Compared to the commercial polypropylene(PP) separator,the sponge-like PSA/SiO_2 composite possesses better physical and electrochemical properties,such as higher porosity,ionic conductivity,thermal stability and flame retarding ability.The LiCoO_2/Li half-cells using the sponge-like composite separator demonstrate superior rate capability and cyclability over those using the commercial PP separator.Moreover,the sponge-like composite separator can ensure the normal operation of LiCoO_2/Li half-cell at an extremely high temperature of 90 °C,while the commercial PP separator cannot.All these encouraging results suggest that this phase inversion based sponge-like PSA/SiO_2 composite separator is really a promising separator for high performance LIBs.展开更多
基金supported by the Foundation of Yunnan Province(Nos.202301AU070021,202201BE070001-027)the Test Foundation of KUST(No.2022T20210208).
文摘Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(22279026,2247090373)the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX1401)+2 种基金the China Postdoctoral Science Foundation(2024M764198)the National Natural Science Foundation of China(22509044)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.
文摘Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01~0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).
基金National Natural Science Foundation of China(No.61376017)。
文摘SnO_(2)-based anodes for lithium-ion batteries(LIBs)experience volume expansion,leading to rapid capacity decay and low conductivity.To address this problem,a composite consists of C/SnO_(2) with a core-shell structure and a carbonized nitrogen-doped Co-metal organic framework(Co-MOF)(NC)supported on carbon cloth(CC)was designed and prepared,which was denoted as C/SnO_(2)@NC@CC.C/SnO_(2)@NC@CC could be used directly as a flexible anode for LIBs.The combination of core-shell structure centered on carbon spheres,carbonized nitrogen-doped Co-MOF,and CC not only restricts the volume expansion but also functions as conductive networks to improve the electrical conductivity.C/SnO_(2)@NC@CC exhibits excellent electrochemical performance with charge and discharge specific capacities of 2066.0 and 2077.1 mAh/g,respectively,after 120 cycles at a current density of 0.5 A/g.
基金financially supported by the Natural Science Foundation of China(22235001,22175020 and 22001015)the Fundamental Research Funds for the Central Universities(No.2050205)+2 种基金the Guizhou Provincial Key Laboratory Platform Project(ZSYS[2025]008)the Talent Program of Guizhou University(No.[2024]11)the Science and Technology Project of Jiangsu Province(BZ2022056)。
文摘Lithium-ion batteries(LIBs)with high energy and power densities are extensively applied in various fields,such as portable electronic devices and electric vehicles.Compared with traditional inorganic electrode materials,which confront the challenges of resource scarcity and restrained energy density,covalent organic frameworks(COFs)are attractive candidates as electrode materials for the next-generation LIBs.Herein,rational Schiff-base condensation of tetraphenyl-pphenylenediamine(TPPDA)and 5,12-bis(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione(QA-PCHO)yields a two-dimensional(2D)QT-COF as the cathode.2D QT-COF features a high crystalline nature with kgm topology and hierarchically micro-/meso-porous structure,which can strengthen the stability of the chemical structure and promote the fast Li^(+)diffusion under large current densities.These merits make the QT-COF cathode exhibit 110,000 ultralong cycling stability with~100%retention at 10,000 mA g^(-1)upon running for 150 days,exceeding all the thus far reported COF-based electrodes.Additionally,the combination of ex situ X-ray photoelectron spectroscopy,in-situ Raman investigation,and theoretical calculation exhaustively unveils the ion storage mechanism and the rationale underlying the exceptional property of QT-COF.The present result offers an advanced COF with enormous potential as organic electrodes for LIBs,hopefully solving the challenges of ultrahigh cycling stability with superb capacity preservation at high current densities.
基金support from the BRICS STI Framework Programme(No.52261145703)National Research Foundation+2 种基金Singapore under Award No.NRF-CRP24-2020-0002the Italy-Singapore Science and Technology Cooperation(Grant No.R23101R040)the use of computing resources at the A*STAR Computational Centre and National Supercomputer Centre,Singapore。
文摘The limited ion/electron transport kinetics and insufficient crystalline stability of TiNb_(2)O_(7)(TNO)present significant challenges to the development of high-performance lithium-ion batteries(LIBs)with fastcharging capabilities and long cycle life.Here we propose a dual-modification strategy combining Ndoped carbon(NC)coating and Co^(2+)/W^(6+)doping,which not only enhances ionic and electronic conductivity but also effectively regulates volume expansion during electrochemical cycling.Upon Li+ion insertion,a significant reduction in the unit cell expansion coefficient of doped TNO is observed,from 7.48%(pristine TNO)to 5.37%(with 3%W^(6+)doping)and 4.65%(with 3%Co^(2+)doping),alo ng with lowered lattice distortion and improved uniformity in internal strain release.Density functional theory(DFT)simulation demonstrates that Co^(2+)and W^(6+)ions preferentially substitute Ti^(4+)sites in the TNO crystal,leading to the improved electronic conductivity by narrowing the bandgap.Moreover,Co^(2+)doping creates lower electron density and wider Li+ion transport channels than W^(6+)doping.The optimized 3Co-TNO@NC anode delivers a remarkable power density of 11.0 kW kg^(-1)at 20 C while maintaining a high reversible capacity of 150.9 mAh g^(-1)at 10 C after 2000 cycles.It also exhibits excellent compatibility in full cells,paired well with LiFePO_(4)(137.9 mAh g^(-1)after 2000 cycles)and Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)(130.9 mAh g^(-1)after 500cycles)cathodes at 5 C,highlighting its potential as a high-safety,low-strain anode material for highpower LIBs.
基金supported by the National Natural Science Foundation of China(No.22278347)the Excellent Doctoral Student Research Innovation Project of Xinjiang University of China(No.XJU2022BS048)the Postgraduate Innovation Project of Xinjiang Uygur Autonomous Region of China(No.XJ2023G027)。
文摘Symmetric secondary batteries are expected to become promising storage devices on account of their low cost,environmentally friendly and high safety.Nevertheless,the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance.Cation-disordered rocksalt(DRX)Li_(2)FeTiO_(4)shows promising properties as symmetric electrodes,based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window.Unfortunately,this cation-disordered structure would not provide a cross-path for the rapid migration of Li^(+),ultimately resulting in inferior electrochemical dynamics and cycle stability.Herein,Li_(2)FeTiO_(4)nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants.Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic(e.g.,stable Fe^(2+)/Fe^(3+),Ti^(3+)/Ti^(4+)and moderated Fe^(3+)/Fe^(4+))and anionic redox,and maintain the DRX structure well during the cycling process.The half cells with nano-sized Li_(2)FeTiO_(4)as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g,respectively.Besides,the Li_(2)FeTiO_(4)//Li_(2)FeTiO_(4)symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles.This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.51822812,51778627)the Fundamental Research Funds for the Central Universities of Central South University(No.2020zzts474)。
文摘In this paper,the ammonia leaching process and high-energy ball milling method were adapted to recover spent LiCoO_(2) material.The ammonia reduction leaching mechanism of LiCoO_(2) material in the ammonia-sodium sulfite-ammonium chloride system was elucidated.Compared with untreated LiCoO_(2) material,the leaching equilibrium time of LiCoO_(2) after ball-milled for 5 h was reduced from 48 h to 4 h,and the leaching efficiency of lithium and cobalt was improved from 69.86%and 70.80%to 89.86%and98.22%,respectively.Importantly,the apparent activation energy and leaching kinetic equation of the reaction was calculated by the shrinking core reaction model,indicating that the reaction was controlled by the chemical reaction.
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)Guangdong Provincial International Joint Research Center for Energy Storage Materials(2023A0505090009)。
文摘As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.
基金Project(21473258)supported by the National Natural Science Foundation of ChinaProject(13JJ1004)supported by the Distinguished Young Scientists of Hunan Province,ChinaProject(NCET-11-0513)supported by the New Century Excellent Talents in University,China
文摘Li[NixCoyMn2]O2(0.6≤x≤0.8) cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of(003) to(104) observed from X-ray diffraction(XRD)increases with decreasing the Ni content or increasing the Co content.The scanning electron microscopy(SEM) images reveal that the small primary particles are agglomerated to form the secondary ones.As the Mn content increases,the primary and secondary particles become larger and the resulted particle size for the Li[Ni(0.6)Co(0.2)Mn(0.2)]O2 is uniformly distributed in the range of100-300 nm.Although the initial discharge capacity of the Li/Li[NixCoyMn2]O2 cells reduces with decreasing the Ni content,the cyclic performance and rate capability are improved with higher Mn or Co content.The Li[Ni(0.6)Co(0.2)Mn(0.2)]O2 can deliver excellent cyclability with a capacity retention of 97.1%after 50 cycles.
基金Project supported by Ministry of Education Key Laboratory of Synthetic and Natural Functional Molecular Chemistry, China Project (2010JK765) supported by the Education Department of Shaanxi Province, China
文摘Nanosphere-like Li2FeSiO4/C was synthesized via a solution method using sucrose as carbon sources under a mild condition of time-saving and energy-saving, followed by sintering at high temperatures for crystallization. The amount of carbon in the composite is less than 10% (mass fraction), and the X-ray diffraction result confirms that the sample is of pure single phase indexed with the orthorhombic Pmn21 space group. The particle size of the Li2FeSiO4/C synthesized at 700 °C for 9 h is very fine and spherical-like with a size of 200 nm. The electrochemical performance of this material, including reversible capacity, cycle number, and charge-discharge characteristics, were tested. The cell of this sample can deliver a discharge capacity of 166 mA-h/g at C/20 rate in the first three cycles. After 30 cycles, the capacity decreases to 158 mA-h/g, and the capacity retention is up to 95%. The results show that this method can prepare nanosphere-like Li2FeSiO4/C composite with good electrochemical performance.
基金Project(51072233) supported by National Natural Science Foundation of China
文摘2LiFe1-xCoxPO4-Li3V2(P04)3/C was synthesized using Fel-2xCo2xVO4 as precursor which was prepared by a simple co-precipitation method. 2LiFej-xCoxPO4-Li3V2(PO4)3/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. All 2LiFel-xCoxPOa-Li3V2(PO4)3/C composites are of the similar crystal structure. The XRD analysis and SEM images show that 2LiFe0.96Co0.04PO4-Li3V2(PO4)3/C sample has the best-ordered structure and the smallest particle size. The charge-discharge tests demonstrate that these powders have the best electrochemical properties with an initial discharge capacity of 144.1 mA.h/g and capacity retention of 95.6% after 100 cycles when cycled at a current density of 0.1C between 2.5 and 4.5 V.
基金supported by the National Key Research and Development Program of China“New Energy Project for Electric Vehicle”(2016YFB0100204)the National Natural Science Foundation of China(Nos.51772030,21805011,51572011,51802012)+2 种基金the Joint Funds of the National Natural Science Foundation of China(U1564206)Beijing Key Research and Development Plan(Z181100004518001)China Postdoctoral Science Foundation(Nos.2017M620637,2018M643697,2019T120930).
文摘MXenes,a new family of two-dimensional(2D)materials with excellent electronic conductivity and hydrophilicity,have shown distinctive advantages as a highly conductive matrix material for lithium-ion battery anodes.Herein,a facile electrostatic self-assembly of SnO2 quantum dots(QDs)on Ti3C2Tx MXene sheets is proposed.The as-prepared SnO2/MXene hybrids have a unique 0D-2D structure,in which the 0D SnO2 QDs(~4.7 nm)are uniformly distributed over 2D Ti3C2Tx MXene sheets with controllable loading amount.The SnO2 QDs serve as a high capacity provider and the“spacer”to prevent the MXene sheets from restacking;the highly conductive Ti3C2Tx MXene can not only provide efficient pathways for fast transport of electrons and Li ions,but also buffer the volume change of SnO2 during lithiation/delithiation by confining SnO2 QDs between the MXene nanosheets.Therefore,the 0D-2D SnO2 QDs/MXene hybrids deliver superior lithium storage properties with high capacity(887.4 mAh g?1 at 50 mA g?1),stable cycle performance(659.8 mAh g?1 at 100 mA g?1 after 100 cycles with a capacity retention of 91%)and excellent rate performance(364 mAh g?1 at 3 A g?1),making it a promising anode material for lithium-ion batteries.
基金The project is financially supported by the National Natural Science Foundation of China (No. 20371038).
文摘Samples of LiNi0.95-xCoxAl0.05O2 (x = 0.10 and 0.15) and LiNiO2, synthesized by the solid-state reaction at 725℃ for 24 h from LiOH-H2O, Ni2O3, Co2O3, and AI(OH)3 under an oxygen stream, were characterized by TG-DTA, XRD, SEM, and electrochemical tests. Simultaneous doping of cobalt and aluminum at the Ni-site in LiNiO2 was tried to improve the cathode performance for lithium-ion batteries. The results showed that co-doping (especially, 5 at.% A1 and 10 at.% Co) definitely had a large beneficial effect in increasing the capacity (186.2 mA.h/g of the first discharge capacity for LiNio.s.42OoaoAlo.0502) and cycling behavior (180.1 mA-h/g after 10 cycles for LiNio.85CooaoAlo.osO2) compared with 180.7 mA.h/g of the first discharge capacity and 157.7 mA.h/g of the tenth discharge capacity for LiNiO2, respectively. Differen- tial capacity versus voltage curves showed that the co-doped LiNio.95_xCoxmlo.osO2 had less intensity of the phase transitions than the pristine LiNiO2.
基金supported by the National Natural Science Foundation of China (Nos. 50762004 and 50864004)
文摘A new LiCoO2 recovery technology for Li-ion batteries was studied in this paper. LiCoO2 was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li2CO3, LiOH-H20 and LiAc-2H2O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO2 was obtained by calcining the mixture at 850℃ for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO2 synthesized by adding Li2CO3 is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g^-1 between 3.0-4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g^-1.
基金The financial support of the Natural Science Foundation of Changsha,China(No.kq2202094)National Key R&D Program of China(No.2021YFB3701400)。
文摘Vertical MoS2nanosheets were controllably patterned onto graphene as nanoflowers through a two-step hydrothermal method. The interconnected network and intimate contact between MoS2nanosheets and graphene by vertical channels enabled a high mechanical integrity of electrode and cycling stability. In particular, MoS2/graphene nanoflowers anode delivered an ultrahigh specific capacity of 901.8 mA·h/g after 700 stable cycles at 1000 mA/g and a corresponding capacity retention as 98.9% from the second cycle onwards.
基金the National Natural Science Foundation of China(Nos.51771236,51901249,U1904216)the Science Fund for Distinguished Young Scholars of Hunan Province(No.2018JJ1038)。
文摘In this work,nickel/T-Nb_(2)O_(5)nanoparticles encapsulated in mesoporous carbon nanofibers(denoted as Ni/T-Nb_(2)O_(5)@CNFs)are successfully prepared through a simple electrospinning route and succedent heating treatment.The presence of Ni in carbon nanofibers is beneficial for enhancing the electronic conductivity and the initial Coulombic efficiency.Ni/T-Nb_(2)O_(5)nanoparticles are homogeneously incorporated in carbon nanofibers to form a nanocomposite system,which provides effective buffering during the lithiation/delithiation process for cycling stability.The Ni/TNb_(2)O_(5)@CNFs show high surface area(26.321 m^(2)·g^(-1))and mesoporous microstructure,resulting in higher capacity and excellent rate performance.The Ni/T-Nb_(2)O_(5)@CNFs exhibit a remarkable capacity of 437 mAh·g^(-1)at a current density of0.5 A·g^(-1)after 230 cycles and a capacity of 173 mAh·g^(-1)at a current density up to 10.0 A·g^(-1)after 1400 cycles.This work indicates that nickel/T-Nb_(2)O_(5)nanoparticles encapsulated in carbon nanofibers can be a promising candidate for anode material in high-power LIBs.
基金supported by the National Key R&D Program of China(No.2016YFB0100500)
文摘In this work, we report a facile route for the synthesis of Li3V2(PO4)3/C cathode material via freezedrying and then calcination. The effect of calcination temperature on the electrochemical properties of the Li3V2(PO4)3/C is also investigated. When used as a lithium-ion battery cathode, the optimized Li3V2(PO4)3/C (LVP-800) through calcination at 800 ℃ exhibits a high initial charge and discharge capacity. The excellent electrochemical performance of LVP-800 is attributed to the good crystallinity and uniform morphology of the electrode material. In addition, the residual carbon can also improve the conductivity and buffer the volume expansion during the Li-ion extraction/reinsertion. Meanwhile, charge compensation also plays an important role in excellent electrochemical performance.
基金financially supported by the National Natural Science Foundation of China(Nos.52171219 and 91963113)
文摘As the earliest commercial cathode material for lithium-ion batteries,lithium cobalt oxide(LiCoO_(2)) shows various advantages,including high theoretical capacity,excellent rate capability,compressed electrode density,etc.Until now,it still plays an important role in the lithium-ion battery market.Due to these advantages,further increasing the charging cutoff voltage of LiCoO_(2)to guarantee higher energy density is an irresistible development trend of LiCoO_(2)cathode materials in the future.However,using high charging cutoff voltage may induce a lot of negative effects,especially the rapid decay of cycle capacity.These are mainly caused by rapid destruction of crystal structure and aggravation of interface side reaction at high voltage during the cycle.Therefore,how to maintain a stable crystal structure of LiCoO_(2)to ensure the excellent long cycle performance at high voltage is a hot research issue in the further application of LiCoO_(2).In this review,we summarized the failure causes and extensive solutions of LiCoO_(2)at high voltage and promoted some new modification strategies.Moreover,the development trend of solving the failure problem of high-voltage LiCoO_(2)in the future such as defect engineering and high-temperature shock technique is also discussed.
基金Supported by the funding from "135" Projects Fund of CAS-QIBEBT Director Innovation FoundationThink-Tank Mutual Fund of Qingdao Energy Storage Industry Scientific Research+3 种基金Qingdao Key Lab of Solar Energy Utilization and Energy Storage Technologythe Strategic Priority Research Program of the Chinese Academy of Sciences(XDA09010105)National Natural Science Foundation of China(51502319)Shandong Provincial Natural Science Foundation(ZR2016BQ18)
文摘In this work,a sponge-like polysulfonamide(PSA)/SiO_2 composite membrane is unprecedentedly prepared by the phase inversion method,and successfully demonstrated as a novel separator of lithium-ion batteries(LIBs).Compared to the commercial polypropylene(PP) separator,the sponge-like PSA/SiO_2 composite possesses better physical and electrochemical properties,such as higher porosity,ionic conductivity,thermal stability and flame retarding ability.The LiCoO_2/Li half-cells using the sponge-like composite separator demonstrate superior rate capability and cyclability over those using the commercial PP separator.Moreover,the sponge-like composite separator can ensure the normal operation of LiCoO_2/Li half-cell at an extremely high temperature of 90 °C,while the commercial PP separator cannot.All these encouraging results suggest that this phase inversion based sponge-like PSA/SiO_2 composite separator is really a promising separator for high performance LIBs.