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1.
Uncontrolled growth of Zn dendrites is the main reason for the short-circuit failure of aqueous Zn-ion batteries. Using electrolyte additives to manipulate the crystal growth is one of the most convenient strategies to mitigate the dendrite issue. However, most additives would be unstable during cycling due to the structural reconstruction of the deposition layer. Herein, it is proposed to use 1-butyl-3-methylimidazolium cation (BMIm+ ion) as an electrolyte additive, which could steadily induce the preferential growth of (002) plane and inhibit the formation of Zn dendrites. Specifically, BMIm+ ion will be preferentially adsorbed on (100) and (101) planes of Zn anodes, forcing Zn2+ ion to deposit on the (002) plane, thus inducing the preferential growth of the (002) plane and forming a flat and compact deposition layer. As a result, the Zn anode cycles for 1000 h at10 mA cm−2 and 10 mAh cm−2 as well as a high Coulombic efficiency of 99.8%. Meanwhile, the NH4V4O10||Zn pouch cell can operate stably for 240 cycles at 0.4 A g−1. The BMIm+ ion additive keeps a stable effect on the structural reconstruction of the Zn anode during the prolonged cycling.  相似文献   

2.
Aqueous zinc ion batteries (AZIBs) are steadily gaining attention based on their attractive merits regarding cost and safety. However, there are many obstacles to overcome, especially in terms of finding suitable cathode materials and elucidating their reaction mechanisms. Here, a mixed‐valence vanadium oxide, V6O13, that functions as a stable cathode material in mildly acidic aqueous electrolytes is reported. Paired with a zinc metal anode, this material exhibits performance metrics of 360 mAh g?1 at 0.2 A g?1, 92% capacity retention after 2000 cycles, and 145 mAh g?1 at a current density of 24.0 A g?1. A combination of experiments and density functional theory calculations suggests that hydrated intercalation, where water molecules are cointercalated with Zn ions upon discharge, accounts for the aforementioned electrochemical performance. This intercalation mechanism facilitates Zn ion diffusion throughout the host lattice and electrode–electrolyte interface via electrostatic shielding and concurrent structural stabilization. Through a correlation of experimental data and theoretical calculations, the promise of utilizing hydrated intercalation as a means to achieve high‐performance AZIBs is demonstrated.  相似文献   

3.
The progress of aqueous zinc batteries (AZBs) is limited by the poor cycling life due to Zn anode instability, including dendrite growth, surface corrosion, and passivation. Inspired by the anti-corrosion strategy of steel industry, a compounding corrosion inhibitor (CCI) is employed as the electrolyte additive for Zn metal anode protection. It is shown that CCI can spontaneously generate a uniform and ≈30 nm thick solid-electrolyte interphase (SEI) layer on Zn anode with a strong adhesion via Zn O bonding. This SEI layer efficiently prohibits water corrosion and guides homogeneous Zn deposition without obvious dendrite formation. This enables reversible Zn deposition and dissolution for over 1100 h under the condition of 1 mA cm−2 and 1 mAh cm−2 in symmetric cells. The Zn-MnO2 full cells with CCI-modified electrolyte deliver an ultralow capacity decay rate (0.013% per cycle) at 0.5 A g−1 over 1000 cycles. Such an innovative strategy paves a low-cost way to achieve AZBs with long lifespan.  相似文献   

4.
The engineering of anode-electrolyte interphase for highly reversible and dendrite-free Zn plating-stripping continues to pose a significant challenge in the progression of aqueous Zn-ion batteries (AZIBs). In this study, a novel approach is introduced that involves the design of a hierarchical carbon nanotube (CNT)-based host through functionalization with cetyltrimethylammonium cations (CTA+). This hierarchical host enables dynamically switchable repulsive shielding to regulate Zn plating. The CNT scaffold, featured with high flexibility and conductivity, facilitates expandable accommodation of continuous Zn plating. Concurrently, the entangled CTA+ cations, acting as manipulators to form switchable repulsive shields, dynamically suppress the growth of Zn dendrites, and result in uniform Zn plating within cationic CNT (C-CNT) hosts. The cationic shielding effect is further elucidated through density functional theory calculations. By incorporating the self-adaptive C-CNT host, Zn symmetric cells exhibit an impressively stable cycling lifespan exceeding 6500 h at 1 mA·cm−2 and achieve a cumulative capacity of 6000 mAh·cm−2 at 4 mA·cm−2. Full batteries, by coupling the C-CNT@Zn anode and MnO2 cathode, demonstrate an 88% capacity retention after 2000 cycles at 2 A·g−1. The design of the self-adaptive C-CNT host offers a promising approach in electrode-electrolyte interphase engineering toward the practical applications of Zn-based energy storage systems.  相似文献   

5.
Zinc metal batteries (ZMBs) hold great promise for large-scale energy storage in renewable solar and wind farms. However, their widespread application is hindered by poor stability and unsatisfactory low-temperature performance, attributed to issues such as dendrite formation, strong Zn2+-H2O coordination, and electrolyte freezing. Herein, a deep eutectic sol electrolyte (DESE) is proposed by mixing SiO2 nanoparticles with a solution composed of 1,3-dioxolane (DOL) and Zn(ClO4)2·6H2O for stable low-temperature ZMBs. By substituting the strong Zn2+- H2O coordination with favorable Zn2+-DOL coordination, the DESE exhibits exceptional antifreezing capability at temperatures beyond −40 °C. The formation of Si-O-Zn2+ bond near SiO2 nanoparticles further improves the low-temperature performance of the DESE by decreasing Zn2+ desolvation energy. Moreover, the SiO2 nanoparticles co-plating/co-stripping with Zn metal, forming a reversible and homogeneous SiO2-enriched interphase to protect the Zn anode from dendrite growth and interfacial side reactions. Remarkably, the DESE-based ZMB full cells exhibit significantly prolonged cycle life of 8000 cycles at 1 A g−1 at 25 °C and 700 cycles at 0.2 A g−1 at -40 °C. This work provides a promising strategy to design advanced electrolytes for practical low-temperature ZMBs.  相似文献   

6.
A key challenge to apply aqueous zinc metal batteries (AZMBs) as next-generation energy storage device is to improve the rechargeability at high current densities, which is needed to circumvent slowly ion diffusion in anode and sluggish charge transfer of Zn2+. Herein, a zincophilic accordion array derived from MOF is developed as zinc host for simultaneously boosted ion diffusion and charge transfer. The designed host is prepared by etching and disproportionation reactions, the abundant zincophilic Sn sites with nano-size uniform disperse on accordion arrays nanosheets (Sn-AA). Then a composite Zn anode (Sn-AA@Zn) is obtained by compacting Sn-AA host with zinc power (Zn-P). The Sn-AA@Zn anode has an ultra-low activation energy (37.1 kJ mol−1) and nucleation overpotential (10 mV), achieving fast charge transfer of Zinc deposition. In addition, the cycle life of the symmetric cell with Sn-AA@Zn anode exceeds 13 000 cycles at 50 mA cm−2, which is 32 times than that of the Zn-P anode. And the full cell with Sn-AA@Zn anode and MnO2 cathode maintains a capacity of 122 mAh g−1 after 5000 cycles at 5 Ag−1. Hopefully, the 3D anode based on Sn-AA@Zn accordion array and Zn-P has significantly improved the rechargeability of AZMB at high current density.  相似文献   

7.
Polyethylene oxide (PEO)-based solid polymer electrolytes (SPE) have garnered recognition as highly promising candidates for advanced lithium-metal batteries. However, the practical application of PEO-based SPE is hindered by its low critical current density (CCD) resulting from undesired dendrite growth. In this study, a PEO-based SPE that exhibits an ultra-high CCD (4 mA cm−2) is presented and enhanced lithium ionic conductivity through the incorporation of small amounts of P2S5 (PS). The crystalline Li2O-rich and P/S-containing solid electrolyte interphase (SEI) is revealed by cryo-electron microscope (cryo-EM) and Time of flight secondary ion mass spectrometry (TOF-SIMS), which inhibits dendrite growth and adverse reactions between SPE and reductive lithium, thus offering a spherical growth behavior for dendrite-free lithium metal anode. Consequently, utilizing the PS-integrated SPE, a Li-Li symmetric cell demonstrates reduced resistance during operation, enabling stable cycles exceeding 200 hours at 0.5 mA cm−2 and 0.5 mAh cm−2, a stringent test condition for PEO-based electrolytes. Moreover, a Li/SPE/LiFePO4 (LFP) pouch cell exhibits 80% capacity retention after 100 cycles with 50 µm Li and 30 µm PEO electrolyte, showcasing its potential for practical applications.  相似文献   

8.
Traditional challenges of poor cycling stability and low Coulombic efficiency in Zinc (Zn) metal anodes have limited their practical application. To overcome these issues, this work introduces a single metal-atom design featuring atomically dispersed single copper (Cu) atoms on 3D nitrogen (N) and oxygen (O) co-doped porous carbon (CuNOC) as a highly reversible Zn host. The CuNOC structure provides highly active sites for initial Zn nucleation and further promotes uniform Zn deposition. The 3D porous architecture further mitigates the volume changes during the cycle with homogeneous Zn2+ flux. Consequently, CuNOC demonstrates exceptional reversibility in Zn plating/stripping processes over 1000 cycles at 2 and 5 mA cm−2 with a fixed capacity of 1 mAh cm−2, while achieving stable operation and low voltage hysteresis over 700 h at 5 mA cm−2 and 5 mAh cm−2. Furthermore, density functional theory calculations show that co-doping N and O on porous carbon with atomically dispersed single Cu atoms creates an efficient zincophilic site for stable Zn nucleation. A full cell with the CuNOC host anode and high loading V2O5 cathode exhibits outstanding rate-capability up to 5 A g−1 and a stable cycle life over 400 cycles at 0.5 A g−1.  相似文献   

9.
A novel fluorine-free electrolyte comprising a solution of lithium bis(oxalato)borate in ethyl isopropyl sulfone is presented. It is characterized by its safety and non-toxic properties, along with the capability to effectively suppress the anodic dissolution of aluminum. Successful high-temperature application of this electrolyte in combination with various capacitor- and battery-like electrode materials is shown. Further utilization in a lithium-ion capacitor and a lithium-ion battery is demonstrated. To the best of the knowledge, the lithium-ion capacitor presented in this work represents the first entirely fluorine-free device suitable for high-temperature applications. When operating at 60 °C, this device delivers a maximum energy output of 169 Wh kg−1AM at a power of 200 W kg−1AM and even 80 Wh kg1AM at 10 kW kg-1AM, along with the ability to retain 80% of its initial capacitance after 3500 cycles at 5 A g−1. As such, this novel electrolyte is a promising alternative to conventional fluorine-containing configurations since its performance is capable to match or even surpass that of most similar laboratory-scale LICs.  相似文献   

10.
The mechanically and electrochemically stable and ionically conducting solid electrolyte interphase (SEI) is important for the stabilization of metal anodes. Since SEIs are originally absent in aqueous zinc metal batteries (AZMBs), it is very challenging to suppress water-induced side reactions and dendrite growth of Zn metal anodes (ZMAs). Herein, a gradient-structured and robust solid gradient SEI, consisting of B,O-inner and F,O-exterior layer, in situ formed by hydrated eutectic electrolyte for the homogeneous and reversible Zn deposition, is demonstrated. Moreover, the molar ratio of acetamide to Zn salt is modulated to prohibit the water activity and the hydrolysis of BF4 as well as to achieve high ionic conductivity owing to the regulation of the solvation sheath of Zn2+. Consequently, the eutectic electrolyte allows Zn||Zn symmetric cells to achieve a cycling lifespan of over 4400 h at 0.5 mA cm−2 as well as Zn||PANI full cells to deliver a high capacity retention of 73.2% over 4000 cycles at 1 A g−1 and to demonstrate the stable operation at low temperatures. This work provides the rational design for the hydrated eutectic electrolyte and the corresponding gradient SEIs for dendrite-free and stable Zn anodes even under harsh conditions.  相似文献   

11.
The rapid growth of lithium dendrites has seriously hindered the development and practical application of high-energy-density all-solid-state lithium metal batteries (ASSLMBs). Herein, a soft carbon (SC)-nano Li6.4La3Zr1.4Ta0.6O12 (LLZTO) (with high ionic conductivity and diffusion coefficient) mixed ionic and electronic conducting interface layer is designed to promote the rapid migration of Li+ at the interfacial layer, induce the uniform deposition of lithium metal on nanoscale (nano) LLZTO ion-conducting network inside the interface layer, effectively suppress the growth of lithium dendrites, and significantly improve the electrochemical performance of ASSLMBs. LiZrO2@LiCoO2(LZO@LCO)/Li6PS5Cl(LPSCl)-nano LLZTO/Li ASSLMB achieves high current density (12.5 mA cm−2), ultra-high areal capacity (15 mAh cm−2, corresponding to LZO@LCO mass loadings of 111.11 mg cm−2), and ultra-long cycle life (20 000 cycles). Therefore, the introduction of SC-nano LLZTO mixed conducting interface layer can greatly improve the interfacial stability between solid-state electrolyte (SSE) and lithium metal anode to enable dendrite-free ASSLMBs.  相似文献   

12.
Rechargeable aqueous Zn/MnO2 batteries are very attractive large‐scale energy storage technologies, but still suffer from limited cycle life and low capacity. Here the novel adoption of a near‐neutral acetate‐based electrolyte (pH ≈ 6) is presented to promote the two‐electron Mn4+/Mn2+ redox reaction and simultaneously enable a stable Zn anode. The acetate anion triggers a highly reversible MnO2/Mn2+ reaction, which ensures high capacity and avoids the issue of structural collapse of MnO2. Meanwhile, the anode‐friendly electrolyte enables a dendrite‐free Zn anode with outstanding stability and high plating/stripping Coulombic efficiency (99.8%). Hence, a high capacity of 556 mA h g?1, a lifetime of 4000 cycles without decay, and excellent rate capability up to 70 mA cm?2 are demonstated in this new near‐neutral aqueous Zn/MnO2 battery by simply manipulating the salt anion in the electrolyte. The acetate anion not only modifies the surface properties of MnO2 cathode but also creates a highly compatible environment for the Zn anode. This work provides a new opportunity for developing high‐performance Zn/MnO2 and other aqueous batteries based on the salt anion chemistry.  相似文献   

13.
Uncontrolled transport of anions leads to many issues, including concentration polarization, excessive interface side reactions, and space charge-induced lithium dendrites at the anode/electrolyte interface, which severely deteriorates the cycling stability of lithium metal batteries. Herein, an asymmetrical polymer electrolyte modified by a boron-containing single-ion conductor (LiPVAOB), is designed to inhibit the nonuniform aggregation of free anions in the vicinity of the lithium anode through the repulsion effect improving the lithium-ion transference number to 0.63. This LiPVAOB exerts a repulsion interaction with free anions even at a long distance and a selective effect for free anions transport, which diminishes uneven aggregation of free anions at the interface and suppresses space charges-induced lithium dendrites growth. Consequently, the assembled Li||Li cell delivers an ultra-long cycle for over 5400 h. The Li||LiFePO4 cell exhibits outstanding cycle performance with a capacity retention of 93% over 4500 cycles. In particular, the assembled high-voltage Li||Li1.2Ni0.2Mn0.6O2 cell (charged to 4.8 V) exhibits good cycle stability with a high specific capacity of 245 mAh g−1. This designed polymer electrolyte provides a promising strategy for regulating ion transport to inhibit space charge-induced lithium dendrite growth for high-performance lithium metal batteries.  相似文献   

14.
The practical use of Zn metal anodes in aqueous zinc batteries is impeded by the growth of dendrites, anode corrosion, and hydrogen evolution reaction in aqueous electrolytes. In this study, a simple, energy-efficient, and scalable approach is reported to mitigate these detrimental issues effectively. Using 1-hexanethiol (HT), a hydrophobic self-assembled mercaptan layer (SAML) with a highly ordered structure is in situ created on the surface of the Zn anode. This ultrathin interfacial structure guides uniform Zn deposition and shields the Zn anode from water and oxygen-induced corrosion, thus effectively inhibiting dendrite formation and side reactions. Consequently, the HT-Zn electrode showcases impressive electrochemical stability and reversibility, and the as-assembled HT-Zn||I2 full cell delivers increased specific capacity (from 112 to 155 mAh g−1 at 1 A g−1) and ultra-stable cyclability (zero capacity decay during the extended 1500 cycles at 4 A g−1). To validate the effectiveness of this simple and scalable method, a large-sized pouch cell is prepared, which can be stably operated for 1000 cycles with a capacity decay of merely 0.0098% per cycle and Coulombic efficiency exceeding 99.1%. The presented SAML strategy highlights the potential of molecular engineering in improving the performance of aqueous zinc batteries.  相似文献   

15.
Aqueous batteries are facing big challenges in the context of low working voltages and energy density, which are dictated by the narrow electrochemical window of aqueous electrolytes and low specific capacities of traditional intercalation‐type electrodes, even though they usually represent high safety, low cost, and simple maintenance. For the first time, this work demonstrates a record high‐energy‐density (1503 Wh kg?1 calculated from the cathode active material) aqueous battery system that derives from a novel electrolyte design to expand the electrochemical window of electrolyte to 3 V and two high‐specific‐capacity electrode reactions. An acid‐alkaline dual electrolyte separated by an ion‐selective membrane enables two dissolution/deposition electrode redox reactions of MnO2/Mn2+ and Zn/Zn(OH)42? with theoretical specific capacities of 616 and 820 mAh g?1, respectively. The newly proposed Zn–Mn2+ aqueous battery shows a high Coulombic efficiency of 98.4% and cycling stability of 97.5% of discharge capacity retention for 1500 cycles. Furthermore, in the flow battery based on Zn–Mn2+ pairs, more excellent stability of 99.5% of discharge capacity retention for 6000 cycles is achieved due to greatly improved reversibility of the Zn anode. This work provides a new path for the development of novel aqueous batteries with high voltage and energy density.  相似文献   

16.
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   

17.
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   

18.
The safety hazards and low Coulombic efficiency originating from the growth of lithium dendrites and decomposition of the electrolyte restrict the practical application of Li metal batteries (LMBs). Inspired by the low cost of low concentration electrolytes (LCEs) in industrial applications, dual‐salt LCEs employing 0.1 m Li difluorophosphate (LiDFP) and 0.4 m LiBOB/LiFSI/LiTFSI are proposed to construct a robust and conductive interphase on a Li metal anode. Compared with the conventional electrolyte using 1 m LiPF6, the ionic conductivity of LCEs is reduced but the conductivity decrement of the separator immersed in LCEs is moderate, especially for the LiDFP–LiFSI and LiDFP–LiTFSI electrolytes. The accurate Coulombic efficiency (CE) of the Li||Cu cells increases from 83.3% (electrolyte using 1 m LiPF6) to 97.6%, 94.5%, and 93.6% for LiDFP–LiBOB, LiDFP–LiFSI, and LiDFP–LiTFSI electrolytes, respectively. The capacity retention of Li||LiFePO4 cells using the LiDFP–LiBOB electrolyte reaches 95.4% along with a CE over 99.8% after 300 cycles at a current density of 2.0 mA cm?2 and the capacity reaches 103.7 mAh g?1 at a current density of up to 16.0 mA cm?2. This work provides a dual‐salt LCE for practical LMBs and presents a new perspective for the design of electrolytes for LMBs.  相似文献   

19.
Pseudocapacitors are now reaching the energy density limits set by the surface redox reaction of their electrode materials, requiring new cation paradigms for a fast cation Faradaic reaction with high capacitance. In this work, a flexible and ultrahigh energy density capacitor is reported via enhancing surface/interface of active colloids and supported carbon cloth. A flexible asymmetrical capacitor assembled with Ni2+ colloidal cathode and Fe3+ colloidal anode displays a high energy density of 353 W h kg?1 at the power density of 2250 W kg?1, outperforming recent reported pseudocapacitors, and shows superior cycling stability after 10 000 charge–discharge cycles at current density of 30 A g?1. This work demonstrates that the optimized surface/interface of carbon cloth and colloids can lead to the enhancement of both stability and activity of colloidal electrode.  相似文献   

20.
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   

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