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1.
Zinc (Zn) metal anode suffers from uncontrollable Zn dendrites and parasitic side reactions at the interface, which restrict the practical application of aqueous rechargeable zinc batteries (ARZBs). Herein, an amphoteric cellulose-based double-network is introduced as hydrogel electrolyte to overcome these obstacles. On one hand, the amphoteric groups build anion/cation transport channels to regulate electro-deposition behavior on Zn (002) crystal plane enabled by homogenizing Zn2+ ions flux. On the other hand, the strong bonding between negatively charged carboxyl groups and Zn2+ ions promote the desolvation process of [Zn(H2O)6]2+ to eliminate side reactions. Based on the above two functions, the hydrogel electrolyte enables an ultra-stable cycling with a cumulative capacity of 7 Ah cm−2 at 20 mA cm−2/20 mAh cm−2 for Zn||Zn cell. This work provides significant concepts for developing hydrogel electrolytes to realize stable anode for high-performance ARZBs.  相似文献   

2.
Metallic Zn is one of the most promising anodes, but its practical application has been hindered by dendritic growth and serious interfacial reactions in conventional electrolytes. Herein, ionic liquids are adopted to prepare intrinsically safe electrolytes via combining with TEP or TMP solvents. With this synergy effect, the blends of TEP/TMP with an IL fraction of ≈25 wt% are found to be promising electrolytes, with ionic conductivities comparable to those of standard phosphate-based electrolytes while electrochemical stabilities are considerably improved; over 1000 h at 2.0 mA cm−2 and ≈350 h at 5.0 mA cm−2 with a large areal capacity of 10 mAh cm−2. The use of functionalized IL turns out to be a key factor in enhancing the Zn2+ transport due to the interaction of Zn2+ ions with IL-zincophilic sites resulting in reduced interfacial resistance between the electrodes and electrolyte upon cycling leading to spongy-like highly porous, homogeneous, and dendrite-free zinc as an anode material.  相似文献   

3.
Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn2+, thus inhibiting hydrogen evolution and side reactions. The self-assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm−2/1.0 mAh cm−2.  相似文献   

4.
Aqueous Zn-Iodine (I2) batteries are attractive for large-scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode “shuttle” of polyiodines. Here we report a class of N-containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition of pyridine /imidazole regulates electrolyte pH, and inhibits HER and anode corrosion. In addition, pyridine and imidazole preferentially absorb on Zn metal, regulating non-dendritic Zn plating /stripping, and achieving a high Coulombic efficiency of 99.6 % and long-term cycling stability of 3200 h at 2 mA cm−2, 2 mAh cm−2. It is also confirmed that pyridine inhibits polyiodines shuttling and boosts conversion kinetics for I/I2. As a result, the Zn-I2 full battery exhibits long cycle stability of >25 000 cycles and high specific capacity of 105.5 mAh g−1 at 10 A g−1. We conclude organic pH buffer engineering is practical for dendrite-free and shuttle-free Zn-I2 batteries.  相似文献   

5.
Aqueous zinc-ion batteries (AZBs) show promises for large-scale energy storage. However, the zinc utilization rate (ZUR) is generally low due to side reactions in the aqueous electrolyte caused by the active water molecules. Here, we design a novel solvation structure in the electrolyte by introduction of sulfolane (SL). Theoretical calculations, molecular dynamics simulations and experimental tests show that SL remodels the primary solvation shell of Zn2+, which significantly reduces the side reactions of Zn anode and achieves high ZUR under large capacities. Specifically, the symmetric and asymmetric cells could achieve a maximum of ∼96 % ZUR at an areal capacity of 24 mAh cm−2. In a ZUR of ∼67 %, the developed Zn−V2O5 full cell can be stably cycled for 500 cycles with an energy density of 180 Wh kg−1 and Zn-AC capacitor is stable for 5000 cycles. This electrolyte structural engineering strategy provides new insight into achieving high ZUR of Zn anodes for high performance AZBs.  相似文献   

6.
The rampant dendrites and hydrogen evolution reaction (HER) resulting from the turbulent interfacial evolution at the anode/electrolyte are the main culprits of short lifespan and low Coulombic efficiency of Zn metal batteries. In this work, a versatile protective coating with excellent zincophilic and amphoteric features is constructed on the surface of Zn metal (ZP@Zn) as dendrite-free anodes. This kind of protective coating possesses the advantages of reversible proton storage and rapid desolvation kinetics, thereby mitigating the HER and facilitating homogeneous nucleation concomitantly. Furthermore, the space charge polarization effect promotes charge redistribution to achieve uniform Zn deposition. Accordingly, the ZP@Zn symmetric cell manifests excellent reversibility at an ultrahigh cumulative plating capacity of 4700 mAh cm−2 and stable cycling at 80 % depth of discharge (DOD). The ZP@Zn//V6O13 pouch cell also reveals superior cycling stability with a high capacity of 326.6 mAh g−1.  相似文献   

7.
Lithium metal is a promising anode material for next-generation high-energy-density batteries but suffers from low stripping/plating Coulombic efficiency and dendritic growth particularly at sub-zero temperatures. Herein, a poorly-flammable, locally concentrated ionic liquid electrolyte with a wide liquidus range extending well below 0 °C is proposed for low-temperature lithium metal batteries. Its all-anion Li+ solvation and phase-nano-segregation solution structure are sustained at low temperatures, which, together with a solid electrolyte interphase rich in inorganic compounds, enable dendrite-free operation of lithium metal anodes at −20 °C and 0.5 mA cm−2, with a Coulombic efficiency of 98.9 %. As a result, lithium metal batteries coupling thin lithium metal anodes (4 mAh cm−2) and high-loading LiNi0.8Co0.15Al0.05O2 cathodes (10 mg cm−2) retain 70 % of the initial capacity after 100 cycles at −20 °C. These results, as a proof of concept, demonstrate the applicability of locally concentrated ionic liquid electrolytes for low-temperature lithium metal batteries.  相似文献   

8.
In aqueous electrolytes, the uncontrollable interfacial evolution caused by a series of factors such as pH variation and unregulated Zn2+ diffusion would usually result in the rapid failure of metallic Zn anode. Considering the high correlation among various triggers that induce the anode deterioration, a synergistic modulation strategy based on electrolyte modification is developed. Benefitting from the unique pH buffer mechanism of the electrolyte additive and its capability to in situ construct a zincophilic solid interface, this synergistic effect can comprehensively manage the thermodynamic and kinetic properties of Zn anode by inhibiting the pH variation and parasitic side reactions, accelerating de-solvation of hydrated Zn2+, and regulating the diffusion behavior of Zn2+ to realize uniform Zn deposition. Thus, the modified Zn anode can achieve an impressive lifespan at ultra-high current density and areal capacity, operating stably for 609 and 209 hours at 20 mA cm−2, 20 mAh cm−2 and 40 mA cm−2, 20 mAh cm−2, respectively. Based on this exceptional performance, high loading Zn||NH4V4O10 batteries can achieve excellent cycle stability and rate performance. Compared with those previously reported single pH buffer strategies, the synergistic modulation concept is expected to provide a new approach for highly stable Zn anode in aqueous zinc-ion batteries.  相似文献   

9.
Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO4)2 was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm−2, and the Zn/PANI battery can provide ultra-high stable specific capacity of 79.6 mAh g−1 for more than 70 000 cycles at 15 A g−1. This can be mainly ascribed to the −SO3H+ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton-supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.  相似文献   

10.
The high thermodynamic instability and side reactions of Zn-metal anode (ZMA), especially at high current densities, greatly impede the commercialization of aqueous zinc-ion batteries (AZIBs). Herein, a fluorine-rich double protective layer strategy is proposed to obtain the high reversibility of AZIBs through the introduction of a versatile tetradecafluorononane-1,9-diol (TDFND) additive in aqueous electrolyte. TDFND molecule with large adsorption energy (−1.51 eV) preferentially absorbs on the Zn anode surface to form a Zn(OR)2 (R=−CH2−(CF2)7−CH2−) cross-linking complex network, which balances space electric field and controls the Zn2+ ion flux, thus enabling the uniform and compact deposition of Zn (002) crystal planes. Meanwhile, TDFND with low Lowest unoccupied molecular orbital (LUMO, 0.10 eV) energy level is priorly decomposed to regulate the interfacial chemistry of ZMA by building a ZnF2-rich solid electrode/electrolyte interface (SEI) layer. It is found that a 14 nm-thick SEI layer delivers excellent structural integrity to suppress parasitic reactions by blocking the direct contact of active water and ZMA. Consequently, the Zn electrode exhibits a superior cycling life over 430 h at 10 mA cm−2 and a high average Coulombic efficiency of 99.8 % at 5 mA cm−2. Furthermore, a 68 mAh pouch cell delivers 80.3 % capacity retention for 1000 cycles.  相似文献   

11.
Rechargeable aqueous zinc batteries (RAZB) have been re-evaluated because of the superiority in addressing safety and cost concerns. Nonetheless, the limited lifespan arising from dendritic electrodeposition of metallic Zn hinders their further development. Herein, a metal–organic framework (MOF) was constructed as front surface layer to maintain a super-saturated electrolyte layer on the Zn anode. Raman spectroscopy indicated that the highly coordinated ion complexes migrating through the MOF channels were different from the solvation structure in bulk electrolyte. Benefiting from the unique super-saturated front surface, symmetric Zn cells survived up to 3000 hours at 0.5 mA cm−2, near 55-times that of bare Zn anodes. Moreover, aqueous MnO2–Zn batteries delivered a reversible capacity of 180.3 mAh g−1 and maintained a high capacity retention of 88.9 % after 600 cycles with MnO2 mass loading up to 4.2 mg cm−2.  相似文献   

12.
The energetic chemical reaction between Zn(NO3)2 and Li is used to create a solid-state interface between Li metal and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) electrolyte. This interlayer, composed of Zn, ZnLix alloy, Li3N, Li2O, and other species, possesses strong affinities with both Li metal and LLZTO and affords highly efficient conductive pathways for Li+ transport through the interface. The unique structure and properties of the interlayer lead to Li metal anodes with longer cycle life, higher efficiency, and better safety compared to the current best Li metal electrodes operating in liquid electrolytes while retaining comparable capacity, rate, and overpotential. All-solid-state Li||Li cells can operate at very demanding current–capacity conditions of 4 mA cm−2–8 mAh cm−2. Thousands of hours of continuous cycling are achieved at Coulombic efficiency >99.5 % without dendrite formation or side reactions with the electrolyte.  相似文献   

13.
Constructing multifunctional interphases to suppress the rampant Zn dendrite growth and detrimental side reactions is crucial for Zn anodes. Herein, a phytic acid (PA)-ZnAl coordination compound is demonstrated as a versatile interphase layer to stabilize Zn anodes. The zincophilic PA-ZnAl layer can manipulate Zn2+ flux and promote rapid desolvation kinetics, ensuring the uniform Zn deposition with dendrite-free morphology. Moreover, the robust PA-ZnAl protective layer can effectively inhibit the hydrogen evolution reaction and formation of byproducts, further contributing to the reversible Zn plating/stripping with high Coulombic efficiency. As a result, the Zn@PA-ZnAl electrode shows a lower Zn nucleation overpotential and higher Zn2+ transference number compared with bare Zn. The Zn@PA-ZnAl symmetric cell exhibits a prolonged lifespan of 650 h tested at 5 mA cm−2 and 5 mAh cm−2. Furthermore, the assembled Zn battery full cell based on this Zn@PA-ZnAl anode also delivers decent cycling stability even under harsh conditions.  相似文献   

14.
Aqueous Zn batteries are attracting extensive attentions, but their application is still hindered by H2O-induced Zn-corrosion and hydrogen evolution reactions. Addition of organic solvents into aqueous electrolytes to limit the H2O activity is a promising solution, but at the cost of greatly reduced Zn anode kinetics. Here we propose a simple strategy for this challenge by adding 50 mM iodine ions into an organic-water (1,2-dimethoxyethane (DME)+water) hybrid electrolyte, which enables the electrolyte simultaneously owns the advantages of low H2O activity and accelerated Zn kinetics. We demonstrate that the DME breaks the H2O hydrogen-bond network and exclude H2O from Zn2+ solvation shell. And the I is firmly adsorbed on the Zn anode, reducing the Zn2+ de-solvation barrier from 74.33 kJ mol−1 to 32.26 kJ mol−1 and inducing homogeneous nucleation behavior. With such electrolyte, the Zn//Zn symmetric cell exhibits a record high cycling lifetime (14.5 months) and achieves high Zn anode utilization (75.5 %). In particular, the Zn//VS2@SS full cell with the optimized electrolyte stably cycles for 170 cycles at a low N : P ratio (3.64). Even with the cathode mass-loading of 16.7 mg cm−2, the full cell maintains the areal capacity of 0.96 mAh cm−2 after 1600 cycles.  相似文献   

15.
Passivation of the sulfur cathode by insulating lithium sulfide restricts the reversibility and sulfur utilization of Li−S batteries. 3D nucleation of Li2S enabled by radical conversion may significantly boost the redox kinetics. Electrolytes with high donor number (DN) solvents allow for tri-sulfur (S3) radicals as intermediates, however, the catastrophic reactivity of such solvents with Li anodes pose a great challenge for their practical application. Here, we propose the use of quaternary ammonium salts as electrolyte additives, which can preserve the partial high-DN characteristics that trigger the S3 radical pathway, and inhibit the growth of Li dendrites. Li−S batteries with tetrapropylammonium bromide (T3Br) electrolyte additive deliver the outstanding cycling stability (700 cycles at 1 C with a low-capacity decay rate of 0.049 % per cycle), and high capacity under a lean electrolyte of 5 μLelectrolyte mgsulfur−1. This work opens a new avenue for the development of electrolyte additives for Li−S batteries.  相似文献   

16.
Rechargeable Zinc batteries (RZBs) are considered a potent competitor for next-generation electrochemical devices, due to their multiple advantages. Nevertheless, traditional aqueous electrolytes may cause serious hazards to long-term battery cycling through fast capacity fading and poor Coulombic efficiency (CE), which happens due to complex reaction kinetics in aqueous systems. Herein, we proposed the novel adoption of the protic amide solvent, N-methyl formamide (NMF) as a Zinc battery electrolyte, which possesses a high dielectric constant and high flash point to promote fast kinetics and battery safety simultaneously. Dendrite-free and granular Zn deposition in Zn-NMF electrolyte assures ultra-long lifespan of 2000 h at 2.0 mA cm−2/2.0 mAh cm−2, high CE of 99.57 %, wide electrochemical window (≈3.43 V vs. Zn2+/Zn), and outstanding durability up to 10.0 mAh cm−2. This work sheds light on the efficient performance of the protic non-aqueous electrolyte, which will open new opportunities to promote safe and energy-dense RZBs.  相似文献   

17.
Constructing a solid electrolyte interface (SEI) is a highly effective approach to overcome the poor reversibility of lithium (Li) metal anodes. Herein, an adhesive and self-healable supramolecular copolymer, comprising of pendant poly(ethylene oxide) (PEO) segments and ureido-pyrimidinone (UPy) quadruple-hydrogen-bonding moieties, is developed as a protection layer of Li anode by a simple drop-coating. The protection performance of in-situ-formed LiPEO–UPy SEI layer is significantly enhanced owing to the strong binding and improved stability arising from a spontaneous reaction between UPy groups and Li metal. An ultrathin (approximately 70 nm) LiPEO–UPy layer can contribute to stable and dendrite-free cycling at a high areal capacity of 10 mAh cm−2 at 5 mA cm−2 for 1000 h. This coating together with the promising electrochemical performance offers a new strategy for the development of dendrite-free metal anodes.  相似文献   

18.
Sulfur–carbon nano-composite with elemental sulfur incorporated in porous carbon was prepared by thermal treatment of a mixture of sulfur and active carbon. The new material was characterized by X-ray diffraction, BET and scanning electron microscopy. The nano-composite, tested at room temperature as cathode in a nonaqueous lithium cell based on PVDF gel electrolyte, exhibited a reversible capacity of 440 mAh g−1 at a current density of 0.3 mA cm−2. The utilization of electrochemically active sulfur was about 90% assuming a complete reaction to the product of Li2S during cycling.  相似文献   

19.
Crystallography modulation of zinc (Zn) metal anode is promising to promote Zn reversibility in aqueous electrolytes, but efficiently constructing Zn with specific crystallographic texture remains challenging. Herein, we report a current-controlled electrodeposition strategy to texture the Zn electrodeposits in conventional aqueous electrolytes. Using the electrolytic cell with low-cost Zn(CH3COO)2 electrolyte and Cu substrate as a model system, the texture of as-deposited Zn gradually transforms from (101) to (002) crystal plane as increasing the current density from 20 to 80 mA cm−2. Moreover, the high current accelerates the Zn nucleation rate with abundant nuclei, enabling uniform deposition. The (002) texture permits stronger resistance to dendrite growth and interfacial side reactions than the (101) texture. The resultant (002)-textured Zn electrode achieves deep cycling stability and supports the stable operation of full batteries with conventional V/Mn-based oxide cathodes.  相似文献   

20.
Li−O2 batteries with bis(trifluoromethanesulfonyl)imide-based ionic liquid (TFSI-IL) electrolyte are promising because TFSI-IL can stabilize O2 to lower charge overpotential. However, slow Li+ transport in TFSI-IL electrolyte causes inferior Li deposition. Here we optimize weak solvating molecule (anisole) to generate anisole-doped ionic aggregate in TFSI-IL electrolyte. Such unique solvation environment can realize not only high Li+ transport parameters but also anion-derived solid electrolyte interface (SEI). Thus, fast Li+ transport is achieved in electrolyte bulk and SEI simultaneously, leading to robust Li deposition with high rate capability (3 mA cm−2) and long cycle life (2000 h at 0.2 mA cm−2). Moreover, Li−O2 batteries show good cycling stability (a small overpotential increase of 0.16 V after 120 cycles) and high rate capability (1 A g−1). This work provides an effective electrolyte design principle to realize stable Li deposition and high-performance Li−O2 batteries.  相似文献   

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