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1.
Perovskite‐type solid‐state electrolytes exhibit great potential for the development of all‐solid‐state lithium batteries due to their high Li‐ion conductivity (approaching 10?3 S cm?1), wide potential window, and excellent thermal/chemical stability. However, the large solid–solid interfacial resistance between perovskite electrolytes and electrode materials is still a great challenge that hinders the development of high‐performance all‐solid‐state lithium batteries. In this work, a perovskite‐type Li0.34La0.51TiO3 (LLTO) membrane with vertically aligned microchannels is constructed by a phase‐inversion method. The 3D vertically aligned microchannel framework membrane enables more effective Li‐ion transport between the cathode and solid‐state electrolyte than a planar LLTO membrane. A significant decrease in the perovskite/cathode interfacial resistance, from 853 to 133 Ω cm2, is observed. It is also demonstrated that full cells utilizing LLTO with vertically aligned microchannels as the electrolyte exhibit a high specific capacity and improved rate performance.  相似文献   

2.
High ionic conductivity of up to 6.4 × 10?3 S cm?1 near room temperature (40 °C) in lithium amide‐borohydrides is reported, comparable to values of liquid organic electrolytes commonly employed in lithium‐ion batteries. Density functional theory is applied coupled with X‐ray diffraction, calorimetry, and nuclear magnetic resonance experiments to shed light on the conduction mechanism. A Li4Ti5O12 half‐cell battery incorporating the lithium amide‐borohydride electrolyte exhibits good rate performance up to 3.5 mA cm?2 (5 C) and stable cycling over 400 cycles at 1 C at 40 °C, indicating high bulk and interfacial stability. The results demonstrate the potential of lithium amide‐borohydrides as solid‐state electrolytes for high‐power lithium‐ion batteries.  相似文献   

3.
Stable and seamless interfaces among solid components in all‐solid‐state batteries (ASSBs) are crucial for high ionic conductivity and high rate performance. This can be achieved by the combination of functional inorganic material and flexible polymer solid electrolyte. In this work, a flexible all‐solid‐state composite electrolyte is synthesized based on oxygen‐vacancy‐rich Ca‐doped CeO2 (Ca–CeO2) nanotube, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and poly(ethylene oxide) (PEO), namely Ca–CeO2/LiTFSI/PEO. Ca–CeO2 nanotubes play a key role in enhancing the ionic conductivity and mechanical strength while the PEO offers flexibility and assures the stable seamless contact between the solid electrolyte and the electrodes in ASSBs. The as‐prepared electrolyte exhibits high ionic conductivity of 1.3 × 10?4 S cm?1 at 60 °C, a high lithium ion transference number of 0.453, and high‐voltage stability. More importantly, various electrochemical characterizations and density functional theory (DFT) calculations reveal that Ca–CeO2 helps dissociate LiTFSI, produce free Li ions, and therefore enhance ionic conductivity. The ASSBs based on the as‐prepared Ca–CeO2/LiTFSI/PEO composite electrolyte deliver high‐rate capability and high‐voltage stability.  相似文献   

4.
Rational structure design of the current collector along with further engineering of the solid‐electrolyte interphases (SEI) layer is one of the most promising strategies to achieve uniform Li deposition and inhibit uncontrolled growth of Li dendrites. Here, a Li2S layer as an artificial SEI with high compositional uniformity and high lithium ion conductivity is in situ generated on the surface of the 3D porous Cu current collector to regulate homogeneous Li plating/stripping. Both simulations and experiments demonstrate that the Li2S protective layer can passivate the porous Cu skeleton and balance the transport rate of lithium ions and electrons, thereby alleviating the agglomerated Li deposition at the top of the electrode or at the defect area of the SEI layer. As a result, the modified current collector exhibits long‐term cycling of 500 cycles at 1 mA cm?2 and stable electrodeposition capabilities of 4 mAh cm?2 at an ultrahigh current density of 4 mA cm?2. Furthermore, full batteries (LiFePO4 as cathode) paired with this designed 3D anode with only ≈200% extra lithium show superior stability and rate performance than the batteries paired with lithium foil (≈3000% extra lithium). These explorations provide new strategies for developing high‐performance Li metal anodes.  相似文献   

5.
All‐solid‐state batteries (ASSBs) with silicon anodes are promising candidates to overcome energy limitations of conventional lithium‐ion batteries. However, silicon undergoes severe volume changes during cycling leading to rapid degradation. In this study, a columnar silicon anode (col‐Si) fabricated by a scalable physical vapor deposition process (PVD) is integrated in all‐solid‐state batteries based on argyrodite‐type electrolyte (Li6PS5Cl, 3 mS cm?1) and Ni‐rich layered oxide cathodes (LiNi0.9Co0.05Mn0.05O2, NCM) with a high specific capacity (210 mAh g?1). The column structure exhibits a 1D breathing mechanism similar to lithium, which preserves the interface toward the electrolyte. Stable cycling is demonstrated for more than 100 cycles with a high coulombic efficiency (CE) of 99.7–99.9% in full cells with industrially relevant areal loadings of 3.5 mAh cm?2, which is the highest value reported so far for ASSB full cells with silicon anodes. Impedance spectroscopy revealed that anode resistance is drastically reduced after first lithiation, which allows high charging currents of 0.9 mA cm?2 at room temperature without the occurrence of dendrites and short circuits. Finally, in‐operando monitoring of pouch cells gave valuable insights into the breathing behavior of the solid‐state cell.  相似文献   

6.
As the theoretical limit of intercalation material‐based lithium‐ion batteries is approached, alternative chemistries based on conversion reactions are presently considered. The conversion of sulfur is particularly appealing as it is associated with a theoretical gravimetric energy density up to 2510 Wh kg?1. In this paper, three different carbon‐iron disulfide‐sulfur (C‐FeS2‐S) composites are proposed as alternative positive electrode materials for all‐solid‐state lithium‐sulfur batteries. These are synthesized through a facile, low‐cost, single‐step ball‐milling procedure. It is found that the crystalline structure (evaluated by X‐ray diffraction) and the morphology of the composites (evaluated by scanning electron microscopy) are greatly influenced by the FeS2:S ratio. Li/LiI‐Li3PS4/C‐FeS2‐S solid‐state cells are tested under galvanostatic conditions, while differential capacity plots are used to discuss the peculiar electrochemical features of these novel materials. These cells deliver capacities as high as 1200 mAh g(FeS2+S)?1 at the intermediate loading of 1 mg cm?2 (1.2 mAh cm?2), and up to 3.55 mAh cm?2 for active material loadings as high as 5 mg cm?2 at 20 °C. Such an excellent performance, rarely reported for (sulfur/metal sulfide)‐based, all solid‐state cells, makes these composites highly promising for real application where high positive electrode loadings are required.  相似文献   

7.
Driven by increasing demand for high‐energy‐density batteries for consumer electronics and electric vehicles, substantial progress is achieved in the development of long‐life lithium–sulfur (Li–S) batteries. Less attention is given to Li–S batteries with high volume energy density, which is crucial for applications in compact space. Here, a series of elastic sandwich‐structured cathode materials consisting of alternating VS2‐attached reduced graphene oxide (rGO) sheets and active sulfur layers are reported. Due to the high polarity and conductivity of VS2, a small amount of VS2 can suppress the shuttle effect of polysulfides and improve the redox kinetics of sulfur species in the whole sulfur layer. Sandwich‐structured rGO–VS2/S composites exhibit significantly improved electrochemical performance, with high discharge capacities, low polarization, and excellent cycling stability compared with their bare rGO/S counterparts. Impressively, the tap density of rGO–VS2/S with 89 wt% sulfur loading is 1.84 g cm?3, which is almost three times higher than that of rGO/S with the same sulfur content (0.63 g cm?3), and the volumetric specific capacity of the whole cell is as high as 1182.1 mA h cm?3, comparable with the state‐of‐the‐art reported for energy storage devices, demonstrating the potential for application of these composites in long‐life and high‐energy‐density Li–S batteries.  相似文献   

8.
Na batteries are seen as a feasible alternative technology to lithium ion batteries due to the greater abundance of sodium and potentially similar electrochemical behavior. In this work, mixed phase electrolyte materials based on solid‐state compositions of a tri methylisobutylphosphonium (P111i4) bis(tri fluromethanesulphonyl)amide (NTf2) organic ionic plastic crystal (OIPC) and high concentration of NaNTf2 that support safe, sodium metal electrochemistry are demonstrated. A Na symmetric cell can be cycled efficiently, even in the solid state (at 50 °C and 60 °C), for a 25 mol% (P111i4NTf2)–75 mol% NaNTf2 composition at 0.1 mA cm?2 for 100 cycles. Thus, these mixed phase materials can be potentially used in Na‐based devices under moderate temperature conditions. It is also investigated that the phase behavior, conductivity, and electrochemical properties of mixtures of NaNTf2 with this OIPC. It is observed that these mixtures have complex phase behavior. For high compositions of the Na salt, the materials are solid at room temperature and retain a soft solid consistency even at 50 °C with remarkably high conductivity, approaching that of the pure ionic liquid at 50 °C, i.e., 10?3–10?2 S cm?1.  相似文献   

9.
Artificial solid‐electrolyte interphase (SEI) is one of the key approaches in addressing the low reversibility and dendritic growth problems of lithium metal anode, yet its current effect is still insufficient due to insufficient stability. Here, a new principle of “simultaneous high ionic conductivity and homogeneity” is proposed for stabilizing SEI and lithium metal anodes. Fabricated by a facile, environmentally friendly, and low‐cost lithium solid‐sulfur vapor reaction at elevated temperature, a designed lithium sulfide protective layer successfully maintains its protection function during cycling, which is confirmed by both simulations and experiments. Stable dendrite‐free cycling of lithium metal anode is realized even at a high areal capacity of 5 mAh cm?2, and prototype Li–Li4Ti5O12 cell with limited lithium also achieves 900 stable cycles. These findings give new insight into the ideal SEI composition and structure and provide new design strategies for stable lithium metal batteries.  相似文献   

10.
Aqueous Ni/Fe batteries have great potential as flexible energy storage devices, owing to their low cost, low toxicity, high safety, and high energy density. However, the poor cycling stability has limited the widely expected application of Ni/Fe batteries, while the use of heavy metal substrates cannot meet the basic requirement for flexible devices. In this work, a flexible type of solid‐state Ni/Fe batteries with high energy and power densities is rationally developed using needle‐like Fe3O4 and flake‐like NiO directly grown on carbon cloth/carbon nanofiber (CC–CF) matrix as the anode and cathode, respectively. The hierarchical CC–CF substrate with high electric conductivity and good flexibility serves as an ideal support for guest active materials of nanocrystalline Fe3O4 and NiO, which can effectively buffer the volume change giving rise to good cycling ability. By utilizing a gel electrolyte, a robust and mechanically flexible quasi‐solid‐state Ni/Fe full cell can be assembled. It demonstrates optimal electrochemical performance, such as high energy density (5.2 mWh cm?3 and 94.5 Wh Kg?1), high power density (0.64 W cm?3 and 11.8 KW Kg?1), together with excellent cycling ability. This work provides an example of solid‐state alkaline battery with high electrochemical performance and mechanical flexibility, holding great potential for future flexible electronic devices.  相似文献   

11.
Solid‐state electrolytes are widely anticipated to enable the revival of high energy density and safe metallic Li batteries, however, their lower ionic conductivity at room temperature, stiff interfacial contact, and severe polarization during cycling continue to pose challenges in practical applications. Herein, a dual‐composite concept is applied to the design of a bilayer heterostructure solid electrolyte composed of Li+ conductive garnet nanowires (Li6.75La3Zr1.75Nb0.25O12)/polyvinylidene fluoride‐co‐hexafluoropropylene (PVDF‐HFP) as a tough matrix and modified metal organic framework particles/polyethylene oxide/PVDF‐HFP as an interfacial gel. The integral ionic conductivity of the solid electrolyte reaches 2.0 × 10?4 S cm?1 at room temperature. In addition, a chemically/electrochemically stable interface is rapidly formed, and Li dendrites are well restrained by a robust inorganic shield and matrix. As a result, steady Li plating/stripping for more than 1700 h at 0.25 mA cm?2 is achieved. Solid‐state batteries using this bilayer heterostructure solid electrolyte deliver promising battery performance (efficient capacity output and cycling stability) at ambient temperature (25 °C). Moreover, the pouch cells exhibit considerable flexibility in service and unexpected endurance under a series of extreme abuse tests including hitting with a nail, burning, immersion under water, and freezing in liquid nitrogen.  相似文献   

12.
The application of lithium (Li) metal anodes in Li metal batteries has been hindered by growth of Li dendrites, which lead to short cycling life. Here a Li‐ion‐affinity leaky film as a protection layer is reported to promote a dendrite‐free Li metal anode. The leaky film induces electrokinetic phenomena to enhance Li‐ion transport, leading to a reduced Li‐ion concentration polarization and homogeneous Li‐ion distribution. As a result, the dendrite‐free Li metal anode during Li plating/stripping is demonstrated even at an extremely high deposition capacity (6 mAh cm?2) and current density (40 mA cm?2) with improved Coulombic efficiencies. A full cell battery with the leaky‐film protected Li metal as the anode and high‐areal‐capacity LiNi0.8Co0.1Mn0.1O2 (NCM‐811) (≈4.2 mAh cm?2) or LiFePO4 (≈3.8 mAh cm?2) as the cathode shows improved cycling stability and capacity retention, even at lean electrolyte conditions.  相似文献   

13.
Due to unprecedented features including high‐energy density, low cost, and light weight, lithium–sulfur batteries have been proposed as a promising successor of lithium‐ion batteries. However, unresolved detrimental low Li‐ion transport rates in traditional carbon materials lead to large energy barrier in high sulfur loading batteries, which prevents the lithium–sulfur batteries from commercialization. In this report, to overcome the challenge of increasing both the cycling stability and areal capacity, a metallic oxide composite (NiCo2O4@rGO) is designed to enable a robust separator with low energy barrier for Li‐ion diffusion and simultaneously provide abundant active sites for the catalytic conversion of the polar polysulfides. With a high sulfur‐loading of 6 mg cm?2 and low sulfur/electrolyte ratio of 10, the assembled batteries deliver an initial capacity of 5.04 mAh cm?2 as well as capacity retention of 92% after 400 cycles. The metallic oxide composite NiCo2O4@rGO/PP separator with low Li‐ion diffusion energy barrier opens up the opportunity for lithium–sulfur batteries to achieve long‐cycle, cost‐effective operation toward wide applications in electric vehicles and electronic devices.  相似文献   

14.
Fast ionic conductors constitute a family of materials exhibiting high values of the ionic conductivity while their crystal structure remains rather rigid. Perovskite‐like compounds are known to be good ionic conductors with applications as solid electrolytes. In hybrid halide perovskites both intrinsic (native) and extrinsic defect migration are regarded to occur. Ion diffusivity analysis is inherently ambiguous in all‐solid‐state configurations because of the multicomponent environment. Here, a liquid electrolyte in contact to the perovskite material forms a reservoir of Li+ that is forced to intercalate and migrate within the perovskite electrode. This approach decouples different contributions to transport in such a way that ion diffusion kinetics is easily accessible by means of impedance methods. The room‐temperature chemical diffusion coefficient of lithium ion within the perovskite lattice exhibits values as high as D μ ≈ 10?7 cm2 s?1, which implies conductivities within the range of 10?3 Ω?1 cm?1 for highly lithiated electrodes. This confirms the superionic intrinsic property of organohalide perovskites from a direct and unambiguous measurement that does not rely upon simulation tools.  相似文献   

15.
Herein, a composite polymer electrolyte with a viscoelastic and nonflammable interface is designed to handle the contact issue and preclude Li dendrite formation. The composite polymer electrolyte (cellulose acetate/polyethylene glycol/Li1.4Al0.4Ti1.6P3O12) exhibits a wide electrochemical window of 5 V (vs Li+/Li), a high Li+ transference number of 0.61, and an excellent ionic conductivity of above 10?4 S cm?1 at 60 °C. In particular, the intimate contact, low interfacial impedance, and fast ion‐transport process between the electrodes and solid electrolytes can be simultaneously achieved by the viscoelastic and nonflammable layer. Benefiting from this novel design, solid lithium metal batteries with either LiFePO4 or LiCoO2 as cathode exhibit superior cyclability and rate capability, such as a discharge capacity of 157 mA h g?1 after 100 cycles at C/2 and 97 mA h g?1 at 5C for LiFePO4 cathode. Moreover, the smooth and uniform Li surface after long‐term cycling confirms the successful suppression of dendrite formation. The viscoelastic and nonflammable interface modification of solid electrolytes provides a promising and general strategy to handle the interfacial issues and improves the operative safety of solid lithium metal batteries.  相似文献   

16.
The low Coulombic efficiency and serious security issues of lithium (Li) metal anode caused by uncontrollable Li dendrite growth have permanently prevented its practical application. A novel SiO2 hollow nanosphere‐based composite solid electrolyte (SiSE) for Li metal batteries is reported. This hierarchical electrolyte is fabricated via in situ polymerizing the tripropylene gycol diacrylate (TPGDA) monomer in the presence of liquid electrolyte, which is absorbed in a SiO2 hollow nanosphere layer. The polymerized TPGDA framework keeps the prepared SiSE in a quasi‐solid state without safety risks caused by electrolyte leakage, meanwhile the SiO2 layer not only acts as a mechanics‐strong separator but also provides the SiSE with high room‐temperature ionic conductivity (1.74 × 10?3 S cm?1) due to the high pore volume (1.49 cm3 g?1) and large liquid electrolyte uptake of SiO2 hollow nanospheres. When the SiSE is in situ fabricated on the cathode and applied to LiFePO4/SiSE/Li batteries, the obtained cells show a significant improvement in cycling stability, mainly attributed to the stable electrode/electrolyte interface and remarkable suppression for Li dendrite growth by the SiSE. This work can extend the application of hollow nanooxide and enable a safe, efficient operation of Li anode in next generation energy storage systems.  相似文献   

17.
Solid‐state electrolytes are a promising candidate for the next‐generation lithium‐ion battery, as they have the advantages of eliminating the leakage hazard of liquid solvent and elevating stability. However, inherent limitations such as the low ionic conductivity of solid polymer electrolytes and the high brittleness of inorganic ceramic electrolytes severally impede their practical application. Here, an inexpensive, facile, and scalable strategy to fabricate a hybrid Li7La3Zr2O12 (LLZO) and poly(ethylene oxide)‐based electrolyte by exploiting bacterial cellulose as a template is reported. The well‐organized LLZO network significantly enhances the ionic conductivity by extending long transport pathways for Li ions, exhibiting an elevated conductivity of 1.12 × 10?4 S cm?1. In addition, the hybrid electrolyte presents a structural flexibility, with minor impedance increase after bending. The facile and applicable approach establishes new principles for the strategy of designing scalable and flexible hybrid polymer electrolytes that can be utilized for high‐energy‐density batteries.  相似文献   

18.
The high‐polarity β‐phase poly(vinylidene difluoride) (β‐PVDF), which has all trans conformation with F and H atoms located on the opposite sides of the polymer backbone, is demonstrated to be a promising artificial solid‐electrolyte interphase coating on both Cu and Li metal anodes for dendrite‐free Li deposition/stripping and enhanced cycling performance. A thin (≈4 µm) β‐PVDF coating on Cu enables uniform Li deposition/stripping at high current densities up to 5 mA cm?2, Li‐plating capacity loadings of up to 4 mAh cm?2, and excellent cycling stability over hundreds of cycles under practical conditions (1 mA cm?2 with 2 mAh cm?2). Full cells containing an LiFePO4 cathode and an anode of either β‐PVDF coated Cu or Li also exhibit excellent cycling stability. The profound effects of the high‐polarity PVDF coating on dendrite suppression are attributed to the electronegative F‐rich interface that favors layer‐by‐layer Li deposition. This study offers a new strategy for the development of dendrite‐free metal anode technology.  相似文献   

19.
Sodium‐ion batteries (NIBs) have attracted more and more attention as economic alternatives for lithium‐ion batteries (LIBs). Sodium super ionic conductor (NASICON) structure materials, known for high conductivity and chemical diffusion coefficient of Na+ (≈10?14 cm2 s?1), are promising electrode materials for NIBs. However, NASICON structure materials often suffer from low electrical conductivity (<10?4 S cm?1), which hinders their electrochemical performance. Here high performance sodium storage performance in Na3V2(PO4)3 (NVP) is realized by optimizing nanostructure and rational surface engineering. A N, B codoped carbon coated three‐dimensional (3D) flower‐like Na3V2(PO4)3 composite (NVP@C‐BN) is designed to enable fast ions/electrons transport, high‐surface controlled energy storage, long‐term structural integrity, and high‐rate cycling. The conductive 3D interconnected porous structure of NVP@C‐BN greatly releases mechanical stress from Na+ extraction/insertion. In addition, extrinsic defects and active sites introduced by the codoping heteroatoms (N, B) both enhance Na+ and e? diffusion. The NVP@C‐BN displays excellent electrochemical performance as the cathode, delivering reversible capacity of 70% theoretical capacity at 100 C after 2000 cycles. When used as anode, the NVP@C‐BN also shows super long cycle life (38 mA h g?1 at 20 C after 5000 cycles). The design provides a novel approach to open up possibilities for designing high‐power NIBs.  相似文献   

20.
Nanostructured V2O5 is emerging as a new cathode material for lithium ion batteries for its distinctly high theoretic capacity over the current commercial cathodes. The main challenges associated with nanostructured V2O5 cathodes are structural degradation, instability of the solid‐electrolyte interface layer, and poor electron conductance, which lead to low capacity and rapid decay of cyclic stability. Here, a novel composite structure of V2O5 nanoparticles encapsulated in 3D networked porous carbon matrix coated on carbon fibers (V2O5/3DC‐CFs) is reported that effectively addresses the mentioned problems. Remarkably, the V2O5/3DC‐CF electrode exhibits excellent overall lithium‐storage performance, including high Coulombic efficiency, excellent specific capacity, outstanding cycling stability and rate property. A reversible capacity of ≈183 mA h g?1 is obtained at a high current density of 10 C, and the battery retains 185 mA h g?1 after 5000 cycles, which shows the best cycling stability reported to date among all reported cathodes of lithium ion batteries as per the knowledge. The outstanding overall properties of the V2O5/3DC‐CF composite make it a promising cathode material of lithium ion batteries for the power‐intensive energy storage applications.  相似文献   

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