Conventional ion batteries utilizing metallic ions as the single charge carriers are limited by the insufficient abundance of metal resources. Although supercapacitors apply both cations and anions ...to store energy through absorption and/or Faradic reactions occurring at the interfaces of the electrode/electrolyte, the inherent low energy density hinders its application. The graphite‐cathode‐based dual‐ion battery possesses a higher energy density due to its high working potential of nearly 5 V. However, such a battery configuration suffers from severe electrolyte decomposition and exfoliation of the graphite cathode, rendering an inferior cycle life. Herein, a new surface‐modification strategy is developed to protect the graphite cathode from the anion salvation effect and the deposition derived from electrolyte decomposition by generating an artificial solid electrolyte interphase (SEI). Such SEI‐modified graphite exhibits superior cycling stability with 96% capacity retention after 500 cycles under 200 mA g−1 at the upper cutoff voltage of 5.0 V, which is much improved compared with the pristine graphite electrode. Through several ex situ studies, it is revealed that the artificial SEI greatly stabilizes the interfaces of the electrode/electrolyte after reconstruction and gradual establishment of the optimal anion‐transport path. The findings shed light on a new avenue toward promoting the performance of the dual‐ion battery (DIB) and hence to make it practical finally.
An artificial layer of a solid electrolyte interphase is fabricated on a graphite cathode for a dual‐ion battery (DIB). Such surface modification can alleviate the electrolyte decomposition at the high working voltage of the anion de‐/intercalation processes and the solvation effect of anions, much improving the cycling stability of the Li//graphite DIB.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Transition metal selenides have been attracting significant attention owing to their high conductivity and theoretical capacity. In this article, the N‐doped carbon (NDC)‐coated Ni1.8Co1.2Se4 ...nanoparticles encapsulated in NDC nanoboxes are prepared from the bi‐metal organic framework (Ni3Co(CN)62·6H2O, Ni‐Co BMOF) after the selenization reaction and carbon coating. When used as an anode material for sodium‐ion batteries, the prepared anode material delivers excellent rate performance (211 and 153 mA h g−1 at ultrahigh current densities of 30 and 50 A g−1, respectively) and good cycling performance (379.3 mA h g−1 at 0.5 A g−1 after 100 cycles). More importantly, it also exhibits superior sodium‐ion full cell (SIFC) performance when coupled with a high‐voltage Na3V2(PO4)2O2F cathode recently self‐made by the authors. The fabricated SIFC gives an energy density up to 227 W h kg−1 and the capacity retention of above 97.6% even after 60 cycles at 0.4 A g−1 in a voltage range of 1.2–4.3 V at 25 °C. Moreover, the low‐temperature (from 25 to −25 °C) Na‐storage performance of the fabricated SIFC is also studied.
An advanced anode material with outstanding high‐rate and low‐temperature properties is developed for sodium‐ion half/full batteries. In it, there exists a 3D conductive network composed of N‐doped dual carbon (NDDC) and abundant void spaces between NDDC and Ni1.8Co1.2Se4 nanoparticles, acting as not only a highway to achieve fast charge transfer but also an effective protector for active Ni1.8Co1.2Se4 material.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Hard carbon is regarded as a promising anode material for sodium‐ion batteries (SIBs). However, it usually suffers from the issues of low initial Coulombic efficiency (ICE) and poor rate performance, ...severely hindering its practical application. Herein, a flexible, self‐supporting, and scalable hard carbon paper (HCP) derived from scalable and renewable tissue is rationally designed and prepared as practical additive‐free anode for room/low‐temperature SIBs with high ICE. In ether electrolyte, such HCP achieves an ICE of up to 91.2% with superior high‐rate capability, ultralong cycle life (e.g., 93% capacity retention over 1000 cycles at 200 mA g−1) and outstanding low‐temperature performance. Working mechanism analyses reveal that the plateau region is the rate‐determining step for HCP with a lower electrochemical reaction kinetics, which can be significantly improved in ether electrolyte.
A self‐supporting, flexible, additive‐free and scalable hard carbon paper (HCP) derived from tissue is rationally developed, and it achieves outstanding Na‐storage properties in terms of high initial Coulombic efficiency (91.2%), superior high‐rate capability, ultralong cyclic stability, as well as outstanding low‐T performance in ether electrolyte. More significantly, the Na‐storage and capacity attenuation mechanism of the HCP anode is revealed.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Presently, commercialization of sodium‐ion batteries (SIBs) is still hindered by the relatively poor energy‐storage performance. In addition, low‐temperature (low‐T) Na storage is another principal ...concern for the wide application of SIBs. Unfortunately, the Na‐transfer kinetics is extremely sluggish at low‐T, as a result, there are few reports on low‐T SIBs. Here, an advanced low‐T sodium‐ion full battery (SIFB) assembled by an anode of 3D Se/graphene composite and a high‐voltage cathode (Na3V2(PO4)2O2F) is developed, exhibiting ultralong lifespan (over even 15 000 cycles, the capacity retention is still up to 86.3% at 1 A g−1), outstanding low‐T energy storage performance (e.g., all values of capacity retention are >75% after 1000 cycles at temperatures from 25 to −25 °C at 0.4 A g−1), and high‐energy/power properties. Such ultralong lifespan signifies that the developed sodium‐ion full battery can be used for longer than 60 years, if batteries charge/discharge once a day and 80% capacity retention is the standard of battery life. As a result, the present study not only promotes the practicability and commercialization of SIBs but also points out the new developing directions of next‐generation energy storage for wider range applications.
An outstanding anode material with superior low‐temperature Na‐storage performance is first prepared, and then an advanced sodium‐ion full battery is assembled and studied via coupling such anode with Na3V2(PO4)2O2F cathode. The assembled full battery exhibits ultralong cycle life, superior low‐temperature, and high‐power energy‐storage performances.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
With the rapidly growing demand for low‐cost and safe energy storage, the advanced battery concepts have triggered strong interests beyond the state‐of‐the‐art Li‐ion batteries (LIBs). Herein, a ...novel hybrid Li/Na‐ion full battery (HLNIB) composed of the high‐energy and lithium‐free Na3V2(PO4)2O2F (NVPOF) cathode and commercial graphite anode mesophase carbon micro beads is for the first time designed. The assembled HLNIBs exhibit two high working voltage at about 4.05 and 3.69 V with a specific capacity of 112.7 mA h g−1. Its energy density can reach up to 328 W h kg−1 calculated from the total mass of both cathode and anode materials. Moreover, the HLNIBs show outstanding high‐rate capability, long‐term cycle life, and excellent low‐temperature performance. In addition, the reaction kinetics and Li/Na‐insertion/extraction mechanism into/out NVPOF is preliminarily investigated by the galvanostatic intermittent titration technique and ex situ X‐ray diffraction. This work provides a new and profound direction to develop advanced hybrid batteries.
A novel Li/Na‐ion hybrid battery with high working voltage and superior electrochemical and low‐temperature properties is designed and assembled by using lithium‐free Na3V2(PO4)2O2F (NVPOF) and commercial graphite as cathode and anode, respectively. The electrode kinetics and Li/Na‐insertion/extraction processes into/out the NVPOF cathode are preliminarily studied by the galvanostatic intermittent titration technique and ex situ X‐ray diffraction.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The graphite material from exhausted Li-ion batteries (LIBs) is reused as a favorable anode for Na-ion batteries (NIBs) and K-ion batteries (KIBs) through a recycling treatment. The optimized ...electrode delivers improved electrochemical performance, such as 162 mA h g −1 in NIBs at 0.2 A g −1 and 320 mA h g −1 in KIBs at 0.05 A g −1 . In addition, the insights into Na/K-ion de-/intercalation model evolution and corresponding electrochemical analysis are conducted through in operando X-ray diffraction and a series of other characterization methods, discovering a visible transitional stage for NIBs and an irreversible initial cycle phase transformation for KIBs. In a word, we not only provide a new recycling concept for waste graphite anodes but also carry out a series of significant intercalation mechanism studies, which contribute to anode recycling and shed light on the development of graphite material for promising alternative ion batteries.
In order to develop promising anode materials for sodium-ion batteries (SIBs), a novel pie-like FeS@C (P-FeS@C) nanohybrid, in which all ultrasmall FeS nanocrystals (NCs) are completely embedded into ...the carbon network and sealed by a protective carbon shell, has been prepared. The unique pie-like structure can effectively speed up the kinetics of electrode reactions, while the carbon shell stabilizes the FeS NCs inside. Studies show that the electrochemical reaction processes of P-FeS@C electrodes are dominated by the pseudocapacitive behavior, leading to an ultrafast Na+-insertion/extraction reaction. Hence, the prepared P-FeS@C nanohybrid exhibits superior Na-storage properties especially high rate capability in half cells. For example, it can deliver reversible capacities of 555.1 mA h g-1 at 0.2 A g-1 over 150 cycles and about 60.4 mA h g-1 at 80 A g-1 (an ultrahigh current density even higher than that of the capacitor test). Furthermore, an advanced P-FeS@C//Na3V2(PO4)2O2F full cell has been assembled out, which delivers a stable specific capacity of 441.2 mA h g-1 after 80 cycles at 0.5 A g-1 with a capacity retention of 91.8%.
In this study, the double transition metal selenide Ni1.5CoSe5 with cube-like nanoaggregate morphology was successfully embedded into a three-dimensional (3D) dual N-doped carbon network, developing ...an advanced anode material for sodium-ion batteries (SIBs). In the prepared composite, Ni1.5CoSe5 nanoparticles were first coated by N-doped carbon (NC), which further aggregated to form nanocubes, and finally embedded into interconnected N-doped reduced graphene oxide (rGO) nanosheets; hence, the material was abbreviated as Ni1.5CoSe5@NC@rGO. It delivered a reversible Na-storage capacity of 582.5 mA h g−1 at a low current density of 0.05 A g−1 and exhibited ultra-fast rate properties (e.g., with the specific capacities of 180.8 and 96.3 mA h g−1 at high current densities of 30 and 50 A g−1, respectively). The much enhanced Na-storage properties were ascribed to the highly conductive 3D network constructed by dual N-doped carbonaceous materials, which acted not only as a highway for ultrafast charge transfer but also as an effective protector for the active Ni1.5CoSe5 material and cube-like nanoaggregates with nanometer-sized primary particles. More significantly, the Ni1.5CoSe5@NC@rGO electrode also exhibited superior energy storage performance in sodium-ion full cells when coupled with a high-voltage Na3V2(PO4)2O2F cathode, making it a promising anode material for practical SIBs.
Dual-carbon enhanced Si-based composite (Si/C/G) has been prepared via employing the widely distributed, low-cost and environmentally friendly Diatomite mineral as silicon raw material. The ...preparation processes are very simple, non-toxic and easy to scale up. Electrochemical tests as anode material for lithium ion batteries (LIBs) demonstrate that this Si/C/G composite exhibits much improved Li-storage properties in terms of superior high-rate capabilities and excellent cycle stability compared to the pristine Si material as well as both single-carbon modified composites. Specifically for the Si/C/G composite, it can still deliver a high specific capacity of about 470 mAh g−1 at an ultrahigh current density of 5 A g−1, and exhibit a high capacity of 938 mAh g−1 at 0.1 A g−1 with excellent capacity retention in the following 300 cycles. The significantly enhanced Li-storage properties should be attributed to the co-existence of both highly conductive graphite and amorphous carbon in the Si/C/G composite. While the former can enhance the electrical conductivity of the obtained composite, the latter acts as the adhesives to connect the porous Si particulates and conductive graphite flakes to form robust and stable conductive network.
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•Dual-carbon enhanced Si-based composite (Si/C/G) was prepared.•It exhibits the best Li-storage properties compared to two single-carbon ones.•Low-cost and abundant Diatomite mineral was employed as Si raw material.•The preparation processes are simple, non-toxic and easy to scale up.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
In order to develop promising anode materials for lithium-ion batteries (LIBs), a unique nanocomposite abbreviated as G⊥FP@C-NA, in which a carbon-coated FeP nanorod array (FP@C-NA) is vertically ...grown on a conductive reduced graphene oxide (G) network, has been successfully prepared via a scalable strategy. Benefiting from the distinctive structure, G⊥FP@C-NA exhibits much improved conductivity, structural stability and pseudocapacitance-boosted ultrafast electrochemical kinetics for Li storage. As a result, the G⊥FP@C-NA delivers a high Li-storage capacity (1106 mA h g-1 at 50 mA g-1), outstanding rate capability (565 mA h g-1 at 5000 mA g-1) and long-term cycling stability (1009 mA h g-1 at 500 mA g-1 after 500 cycles and 310 mA h g-1 at 2000 mA g-1 after 2000 cycles) when used as an anode material for LIBs. As expected, this kind of nanoarray structure is attractive and can also be extended to other electrode materials for various energy storage systems.