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1.
Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g?1 specific capacity, twice of the capacity (≈100 mAh g?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g?1 current density (4 C rate, 1 C = 250 mA g?1) with a specific capacity of ≈150 mAh g?1, ≈15 times of the capacity (10 mAh g?1) in carbonate. The full cell of Na3V2(PO4)3‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g?1 based on Na3V2(PO4)3 cathode, ≈2.5 times of the value (≈40 mAh g?1) with nontreated HC. This work provides new perception on the anode development for SIBs.  相似文献   

2.
A novel combination of hard carbon anode sodium pre‐loading and a tailored electrolyte is used to prepare room temperature sodium‐sulfur full cell batteries. The electrochemical loading with sodium ions is realized in a specific mixture of diethyl carbonate, ethylene carbonate, and fluoroethylene carbonate electrolyte in order to create a first solid electrolyte interface (SEI) on the anode surface. Combining such anodes with a porous carbon/sulfur composite cathode results in full cells with a significantly decreased polysulfide shuttle when compared to half cells combined with metallic sodium anodes. Further optimization involves the use of Na2S/P2S5 doped tetraethylene glycol dimethyl ether based electrolyte in the full cell for the formation of a second SEI, reducing polysulfide shuttle even further. More importantly, the electrochemical discharge processes in the cell are improved by adding this dissolved complexation agent to the electrolyte. As a result of this combination sodium‐sulfur cells with tailored cathode materials and electrolytes can achieve high discharge capacities up to 980 mAh g?1sulfur and 1000 cycles with 200 mAh g?1sulfur remaining capacity, at room temperature.  相似文献   

3.
Room‐temperature (RT) sodium–sulfur (Na–S) batteries are attractive cost‐effective platforms as the next‐generation energy storage systems by using all earth‐abundant resources as electrode materials. However, the slow kinetics of Na–S chemistry makes it hard to achieve high‐rate performance. Herein, a facile and scalable approach has been developed to synthesize hollow sodium sulfide (Na2S) nanospheres embedded in a highly hierarchical and spongy conductive carbon matrix, forming an intriguing architecture similar to the morphology of frogspawn coral, which has shown great potential as a cathode for high‐rate performance RT Na–S batteries. The shortened Na‐ion diffusion pathway benefits from the hollow structures together with the fast electron transfer from the carbon matrix contributes to high electrochemical reactivity, leading to superior electrochemical performance at various current rates. At high current densities of 1.4 and 2.1 A g?1, high initial discharge capacities of 980 and 790 mAh g?1sulfur can be achieved, respectively, with reversible capacities stabilized at 600 and 400 mAh g?1sulfur after 100 cycles. As a proof of concept, a Na‐metal‐free Na–S battery is demonstrated by pairing the hollow Na2S cathode with tin‐based anode. This work provides guidance on rational materials design towards the success of RT high‐rate Na–S batteries.  相似文献   

4.
Herein, P′2‐type Na0.67[Ni0.1Fe0.1Mn0.8]O2 is introduced as a promising new cathode material for sodium‐ion batteries (SIBs) that exhibits remarkable structural stability during repetitive Na+ de/intercalation. The O? Ni? O? Mn? O? Fe? O bond in the octahedra of transition‐metal layers is used to suppress the elongation of the Mn? O bond and to improve the electrochemical activity, leading to the highly reversible Na storage mechanism. A high discharge capacity of ≈220 mAh g?1 (≈605 Wh kg?1) is delivered at 0.05 C (13 mAg?1) with a high reversible capacity of ≈140 mAh g?1 at 3 C and excellent capacity retention of 80% over 200 cycles. This performance is associated with the reversible P′2–OP4 phase transition and small volume change upon charge and discharge (≈3%). The nature of the sodium storage mechanism in a full cell paired with a hard carbon anode reveals an unexpectedly high energy density of ≈542 Wh kg?1 at 0.2 C and good capacity retention of ≈81% for 500 cycles at 1 C (260 mAg?1).  相似文献   

5.
Solid‐state sodium batteries (SSSBs) are promising electrochemical energy storage devices due to their high energy density, high safety, and abundant resource of sodium. However, low conductivity of solid electrolyte as well as high interfacial resistance between electrolyte and electrodes are two main challenges for practical application. To address these issues, pure phase Na3Zr2Si2PO12 (NZSP) materials with Ca2+ substitution for Zr4+ are synthesized by a sol‐gel method. It shows a high ionic conductivity of more than 10?3 S cm?1 at 25 °C. Moreover, a robust SSSB is developed by integrating sodium metal anodes into NZSP‐type monolithic architecture, forming a 3D electronic and ionic conducting network. The interfacial resistance is remarkably reduced and the monolithic symmetric cell displays stable sodium platting/striping cycles with low polarization for over 600 h. Furthermore, by combining sodium metal anode with Na3V2(PO4)3 cathode, an SSSB is demonstrated with high rate capability and excellent cyclability. After 450 cycles, the capacity of the cell is still kept at 94.9 mAh g?1 at 1 C. This unique design of monolithic electrolyte architecture provides a promising strategy toward realizing high‐performance SSSBs.  相似文献   

6.
Li2S is a fully lithiated sulfur‐based cathode with a high theoretical capacity of 1166 mAh g?1 that can be coupled with lithium‐free anodes to develop high‐energy‐density lithium–sulfur batteries. Although various approaches have been pursued to obtain a high‐performance Li2S cathode, there are still formidable challenges with it (e.g., low conductivity, high overpotential, and irreversible polysulfide diffusion) and associated fabrication processes (e.g., insufficient Li2S, excess electrolyte, and low reversible capacity), which have prevented the realization of high electrochemical utilization and stability. Here, a new cathode design composed of a homogeneous Li2S‐TiS2‐electrolyte composite that is prepared by a simple two‐step dry/wet‐mixing process is demonstrated, allowing the liquid electrolyte to wet the powder mixture consisting of insulating Li2S and conductive TiS2. The close‐contact, three‐phase boundary of this system improves the Li2S‐activation efficiency and provides fast redox‐reaction kinetics, enabling the Li2S‐TiS2‐electrolyte cathode to attain stable cyclability at C/7 to C/3 rates, superior long‐term cyclability over 500 cycles, and promising high‐rate performance up to 1C rate. More importantly, this improved performance results from a cell design attaining a high Li2S loading of 6 mg cm?2, a high Li2S content of 75 wt%, and a low electrolyte/Li2S ratio of 6.  相似文献   

7.
The design of a sodium‐ion rechargeable battery with an antimony anode, a Na3V2(PO4)3 cathode, and a low‐cost composite gel‐polymer electrolyte based on cross‐linked poly(methyl methacrylate) is reported. The application of an antimony anode, on replacement of the sodium metal that is commonly used in sodium‐ion half‐cells, reduces significantly the interfacial resistance and charge transfer resistance of a sodium‐ion battery, which enables a smaller polarization for a sodium‐ion full‐cell Sb/Na3V2(PO4)3 running at relatively high charge and discharge rates. The incorporation of the gel‐polymer electrolyte is beneficial to maintain stable interfaces between the electrolyte and the electrodes of the sodium‐ion battery at elevated temperature. When running at 60 °C, the sodium‐ion full‐cell Sb/Na3V2(PO4)3 with the gel‐polymer electrolyte exhibits superior cycling stability compared to a battery with the conventional liquid electrolyte.  相似文献   

8.
A practical, low‐cost synthesis of hollow mesoporous organic polymer (HMOP) spheres is reported. The electrochemical properties of Li+/Na+‐electrolyte membranes with these spheres substituting for oxide filler particles in poly(ethylene oxide) (PEO)‐filler composite are explored. The electrolyte membranes are mechanically robust, thermally stable to over 250 °C, and block dendrites from a metallic‐lithium/sodium anode. The Li+/Na+ transfer impedance across the lithium/sodium–electrolyte interface is initially acceptable at 65 °C and scavenging of impurities by the porous‐spheres filler lowers this impedance relative to that with Al2O3. All‐solid‐state Li/LiFePO4 and Na/NaTi2(PO4)3 cells give stable discharge capacity of ≈130 and 80 mAh g?1, respectively, at 0.5 C and 65 °C for 100 cycles.  相似文献   

9.
Sodium‐ion batteries (SIBs) that operate in a wide temperature range are in high demand for practical large‐scale electric energy storage. Herein, a novel full SIB is composed of a bulk Bi anode, a Na3V2(PO4)3/carbon nanotubes composite (NVP‐CNTs) cathode and a NaPF6‐diglyme electrolyte. The Bi anode gradually evolves into a porous network in the ether‐based electrolyte during initial cycles, and in the NVP‐CNTs cathode the NVP is cross linked by CNTs to show large exchange current density. These unique features merit the full SIB of Bi//NVP‐CNTs with high Na+ diffusion coefficient and low reaction activation energy, and hence fast Na+ transport and facile redox reaction kinetics. The resultant full SIB presents high power density of 2354.6 W kg?1 and energy density of 150 Wh kg?1 and superior cycling stability in a wide temperature range from ?15 to 45 °C. This will shed light on battery design, and promote their development for practical applications in various weather conditions.  相似文献   

10.
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   

11.
The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN)2?LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li2S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g?1 at cycle 100 (330 mAh g?1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li2S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li2S loading, Li2S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.  相似文献   

12.
Rechargeable aqueous Zn‐based batteries are attractive candidates as energy storage technology, but the uncontrollable Zn dendrites, low stripping/plating coulombic efficiency, and inefficient utilization of Zn metal limit the battery reliability and energy density. Herein, for the first time, a novel presodiated TiS2 (Na0.14TiS2) is proposed and investigated as an intercalated anode for aqueous Zn‐ion batteries, showing a capacity of 140 mAh g?1 with a suitable potential of 0.3 V (vs Zn2+/Zn) at 0.05 A g?1 and superior cyclability of 77% retention over 5000 cycles at 0.5 A g?1. The remarkable performance originates from the buffer phase formation of Na0.14TiS2 after chemically presodiating TiS2, which not only improves the structural reversibility and stability but also enhances the diffusion coefficient and electronic conductivity, and lowers cation migration barrier, as evidenced by a series of experimental and theoretical studies. Moreover, an aqueous “rocking‐chair” Zn‐ion full battery is successfully demonstrated by this Na0.14TiS2 anode and ZnMn2O4 cathode, which delivers a capacity of 105 mAh g?1 (for anode) with an average voltage of 0.95 V at 0.05 A g?1 and preserves 74% retention after 100 cycles at 0.2 A g?1, demonstrating the feasibility of Zn‐ion full batteries for energy storage applications.  相似文献   

13.
Antimony (Sb) is a promising anode material for sodium‐ion batteries owing to its large capacity of 660 mAh g?1. However, its practical application is restricted by the rapid capacity decay resulted from a large volume expansion up to 390% upon Na alloying. Herein, construction of a self‐supported Sb array that has enough space allowing for effective accommodation of the volume change is reported. The array of Sb prisms is directly grown on a Cu substrate via a template‐free electrodeposition, followed by mild heating to consolidate the structural integrity between Sb and Cu. The resulting 3D architecture endows the Sb array with excellent sodium storage performance, exhibiting a reversible capacity of 578 mAh g?1 and retaining 531 mAh g?1 over 100 cycles at 0.5 C. The potential of Sb array in sodium‐ion full cells by pairing it with a Na0.67(Ni0.23Mg0.1Mn0.67)O2 cathode is further demonstrated. This full cell affords a specific energy of 197 Wh kg?1 at 0.2 C and a specific power of 1280 W kg?1 at 5 C. Considering its low cost and scale‐up capability, the template‐free route may find extensive applications in designing electrode architectures.  相似文献   

14.
Minimizing electrolyte use is essential to achieve high practical energy density of lithium–sulfur (Li–S) batteries. However, the sulfur cathode is more readily passivated under a lean electrolyte condition, resulting in low sulfur utilization. In addition, continuous electrolyte decomposition on the Li metal anode aggravates the problem, provoking rapid capacity decay. In this work, the dual functionalities of NO3? as a high‐donor‐number (DN) salt anion is presented, which improves the sulfur utilization and cycling stability of lean‐electrolyte Li–S batteries. The NO3? anion elevates the solubility of the sulfur species based on its high electron donating ability, achieving a high sulfur utilization of above 1200 mA h g?1. Furthermore, the anion suppresses electrolyte decomposition on the Li metal by regulating the lithium ion (Li+) solvation sheath, enhancing the cycle performance of the lean electrolyte cell. By understanding the anionic effects, this work demonstrates the potential of the high‐DN electrolyte, which is beneficial for both the cathode and anode of Li–S batteries.  相似文献   

15.
Metal phosphides are promising anode candidates for sodium‐ion batteries (SIBs) due to their high specific capacity and low operating potential but suffer from poor cycling stability caused by huge volume expansion and poor solid‐state ion transfer rate. Herein, a new strategy to grow a new class of mesoporous metal phosphide nanoarrays on carbon felt (CF) as binder‐free anodes for SIBs is reported. The resultant integrated electrodes demonstrate excellent cycling life up to 1000 times (>90% retention rate) and high rate capability of 535 mAh g?1 at a current density of 4 A g?1. Detailed characterization reveals that the synergistic effect of unique mesoporous structure for accommodating huge volume expansion during sodiation/desodiation process, ultrasmall primary particle size (≈10 nm) for providing larger electrode/electrolyte contact area and shorter ion diffusion distance, and 3D conductive networks for facilitating the electrochemical reaction, leads to the extraordinary battery performance. Remarkably, a full SIB using the new CoP4/CF anode and a Na3V2(PO4)2F3 cathode delivers an average operating voltage of ≈3.0 V, a reversible capacity of 553 mAh g?1, and very high energy density of ≈280 Wh kg?1 for SIBs. A flexible SIB with outstanding mechanical strength based on this binder‐free new anode is also demonstrated.  相似文献   

16.
Conversion reaction cells afford the ability to explore new energy storage paradigms that transcend the dogma of small, low‐charge cations essential to intercalative processes. Here we report the use of earth‐abundant and green calcium and sulfur in unprecedented conversion reaction Ca–S primary cells. Using S‐infiltrated mesoporous carbon (abbreviated S@meso‐C) cathodes, we achieve discharge capacities as high as 600 mAh g?1 (S basis) within the geometry Ca|Ca(ClO4)2/CH3CN|S@meso‐C, at a discharge rate of C/3.5. The electrolyte system in the Ca–S battery is of paramount importance as the solid electrolyte interface (SEI) formed on the Ca anode limits the capacity and stability of the cell. We determine that 0.5 M Ca(ClO4)2 in CH3CN forms an SEI that advantageously breaks down under anodic bias to allow oxidation of the anode. This same SEI, however, exhibits high impedance which increases over time at open circuit limiting the shelf life of the cell.  相似文献   

17.
Narrow electrochemical stability window (1.23 V) of aqueous electrolytes is always considered the key obstacle preventing aqueous sodium‐ion chemistry of practical energy density and cycle life. The sodium‐ion water‐in‐salt electrolyte (NaWiSE) eliminates this barrier by offering a 2.5 V window through suppressing hydrogen evolution on anode with the formation of a Na+‐conducting solid‐electrolyte interphase (SEI) and reducing the overall electrochemical activity of water on cathode. A full aqueous Na‐ion battery constructed on Na0.66[Mn0.66Ti0.34]O2 as cathode and NaTi2(PO4)3 as anode exhibits superior performance at both low and high rates, as exemplified by extraordinarily high Coulombic efficiency (>99.2%) at a low rate (0.2 C) for >350 cycles, and excellent cycling stability with negligible capacity losses (0.006% per cycle) at a high rate (1 C) for >1200 cycles. Molecular modeling reveals some key differences between Li‐ion and Na‐ion WiSE, and identifies a more pronounced ion aggregation with frequent contacts between the sodium cation and fluorine of anion in the latter as one main factor responsible for the formation of a dense SEI at lower salt concentration than its Li cousin.  相似文献   

18.
Li‐rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g?1. However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well‐known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full‐cell performance degradation. Herein, an artificial surface prereconstruction (ASR) for Li1.2Mn0.6Ni0.2O2 particles with a molten‐molybdate leaching is conducted, which creates a crystal‐dense anion‐redox‐free LiMn1.5Ni0.5O4 shell that completely encloses the LXMO lattice (ASR‐LXMO). Differential electrochemical mass spectroscopy and soft X‐ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR‐LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR‐LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g?1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full‐cell matched with a commercial graphite anode and lean (2 g A?1 h?1) electrolyte, ASR‐LXMO shows high capacity retention of 76% after 125 cycles in full‐cell cycling.  相似文献   

19.
Use of a protective coating on a lithium metal anode (LMA) is an effective approach to enhance its coulombic efficiency and cycling stability. Here, a facile approach to produce uniform silver nanoparticle‐decorated LMA for high‐performance Li metal batteries (LMBs) is reported. This effective treatment can lead to well‐controlled nucleation and the formation of a stable solid electrolyte interphase (SEI). Ag nanoparticles embedded in the surface of Li anodes induce uniform Li plating/stripping morphologies with reduced overpotential. More importantly, cross‐linked lithium fluoride‐rich interphase formed during Ag+ reduction enables a highly stable SEI layer. Based on the Ag‐LiF decorated anodes, LMBs with LiNi1/3Mn1/3Co1/3O2 cathode (≈1.8 mAh cm?2) can retain >80% capacity over 500 cycles. The similar approach can also be used to treat sodium metal anodes. Excellent stability (80% capacity retention in 10 000 cycles) is obtained for a Na||Na3V2(PO4)3 full cell using a Na‐Ag‐NaF/Na anode cycled in carbonate electrolyte. These results clearly indicate that synergetic control of the nucleation and SEI is an efficient approach to stabilize rechargeable metal batteries.  相似文献   

20.
Potassium ion hybrid capacitors have great potential for large‐scale energy devices, because of the high power density and low cost. However, their practical applications are hindered by their low energy density, as well as electrolyte decomposition and collector corrosion at high potential in potassium bis(fluoro‐sulfonyl)imide‐based electrolyte. Therefore, anode materials with high capacity, a suitable voltage platform, and stability become a key factor. Here, N‐doping carbon‐coated FeSe2 clusters are demonstrated as the anode material for a hybrid capacitor, delivering a reversible capacity of 295 mAh g?1 at 100 mA g?1 over 100 cycles and a high rate capability of 158 mAh g?1 at 2000 mA g?1 over 2000 cycles. Meanwhile, through density functional theory calculations, in situ X‐ray diffraction, and ex situ transmission electron microscopy, the evolution of FeSe2 to Fe3Se4 for the electrochemical reaction mechanism is successfully revealed. The battery‐supercapacitor hybrid using commercial activated carbon as the cathode and FeSe2/N‐C as the anode is obtained. It delivers a high energy density of 230 Wh kg?1 and a power density of 920 W kg?1 (the energy density and power density are calculated based on the total mass of active materials in the anode and cathode).  相似文献   

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