Manganese-containing NASICON-type phosphate cathodes have shown a great potential for sodium ion batteries (SIBs) due to robust structure, 3D ion transport channels, and relatively low toxicity. However, their practical applications are limited owing to poor electron/ion transportation kinetics and large structural strain upon Na+ extraction/insertion processes. Herein, taking Na3.5V1.5Mn0.5(PO4)3 as an example, a Mn vacancy (VMn) regulation strategy has been developed for constructing VMn-containing Na3.5V1.5Mn0.5-x square x(PO4)3 in which VMncan not only efficiently alter the coordination environments of transition metals (TMs) in Na3.5V1.5Mn0.5(PO4)3 for facilitating Na+ migration and charge distribution, but also provide more flexible VO6/MnO6 octahedra environments for guaranteeing robust structural stability upon cycling. Based on theoretical calculation and characterizations, the optimized Na3.5V1.5Mn0.4 square 0.1(PO4)3 shows the optimized sodium storage performance than those of Na3.5V1.5Mn0.5(PO4)3 without VMn, and Na3.5V1.5Mn0.45 square 0.05(PO4)3, Na3.5V1.5Mn0.35 square 0.15(PO4)3. X-ray absorption near-edge structure and density functional theory calculations reveal that the introduction of VMncan not only reduce the band gap from 0.89 eV to 0.53 eV, but also weaken the interaction of Na2-TM and lower the sodium ion diffusion energy barrier near VMn, thus leading to enhanced intrinsic electron/ion conductivity. Importantly, Na3.5V1.5Mn0.4 square 0.1(PO4)3 exhibits smaller distortions of TMO6 octahedra with VO6 reduced by 21.7% and MnO6 reduced by 47.1% compared to the counterpart without VMn. When evaluated as cathode for SIBs, such cathode delivers a reversible capacity of 119.7 at 0.1 C, a rate capability of 96.6 mAh g-1 at 20 C, and a capacity retention of 88% after 5000 cycles at 20 C.

Developing a heterostructure for alloying-based anode for sodium-ion batteries (SIBs) is an efficient solution to accommodate volume change upon sodiation/desodiation and boost sodium storage since it combines the merits of each component. Herein, we report a metallic and microphone-like Sn-Zn0.9Mn0.1O heterostructure via an in-situ Mn doping strategy. Based on theoretical calculations and experimental results, the introduction of Mn into ZnO (a small amount of Mn also diffuses into the Sn lattice) can not only enhance intrinsic electronic conductivity but also reduce the Na+ diffusion barrier inside the Sn phase. When evaluated as anode for SIBs, the obtained heterostructures show a high reversible capacity of 395.1 mAh/g at 0.1 A/g, rate capability of 332 mAh/g at 5 A/g, and capacity retention of almost 100% after 850 cycles at 5 A/g, indicating its great potential for high-power application of SIBs.

Dendrites and water-induced side reactions impose greatly challenge on the implementation of aqueous zinc ion batteries. To tackle these problems, an artificial rectified layer (ARL) with hydrophobic, zincophilic and insulating features was in situ synthesized on Zn surface rapidly to prevent the electron leakage from Zn anode to aqueous electrolyte, which is the underlying logic for uneven Zn deposition and parasitic side reactions. The ARL also displays a high Zn 2+ transference number of 0.71 and can build fast Zn 2+ transport channels to homogenize the interfacial ion flux and electric field according to the calculated work function and multi-physics phase simulation results. Therefore, the Zn anode with ARL shows preferred plating along with (002) crystal facet and an admirable Coulombic efficiency of 99.86 % over 3200 cycles. Zn symmetric cells can withstand large current density up to 40 mA cm −2 and operate stably at 44.2 % depth of discharge for 250 hours, surpassing most of published reports. The ARL also enables the Zn||MnO 2 full batteries to circulate over 2600 cycles with a high-capacity retention of 80.1 % and low self-discharge at 1 A g −1 . This work provides a different perspective to comprehend and design satisfactory solid electrolyte interphase for Zn metal anodes.

A pseudocapacitance dominated anode material assembled from Li3VO4 nanocrystals encapsulated in the interlayers of N-doped graphene has been developed via a facile 2D nanospace confined strategy for lithium ion capacitors (LICs). In this contribution, the N-doped graphene synthesized by a faicle solid state reaction using C3N4 nanosheets as template and glucose as carbon source provides sufficient 2D nanospace for the confined and homogeneous growth of Li3VO4 at the nanoscale, and simultaneously efficiently anchors each nanobuilding block inside the interlayers, thus realizing the utilizaiton of full potential of active components. The so-formed 3D hybrids not only ensure intimate electronic coupling between active materials and N-doped graphene, but also realize robust structure integrity. Owing to these unique advantages, the resulting hybrids show pseudocapacitance dominated lithium storage behaviors with capacitive contributions of over 90% at both low and high current rates. The LVO@C@NG delivers reversible capacities of 206 mAh/g at 10 A/g, capacity retention of 92.7% after 1000 cycles at 2 A/g, and a high energy density of 113.6 Wh/kg at 231.8 W/kg for LICs.

Effectively recycling spent lithium-ion batteries (S-LIBs) has considerable economic and environmental benefits. In this study, a novel approach for simultaneously synthesizing Li2CO3 2 CO 3 and remediating LiCoO2 2 from S-LIBs via slurry electrolysis is proposed, employing glycine-LiOH as the electrolyte. The operating conditions were optimized to a solid-to-liquid ratio of 20 g/L, slurry electrolysis time of 8 h, current density of 50 mA/cm2, 2 , reaction temperature of 80 degrees C, and glycine concentration of 1.0 mol/L. Li2CO3 2 CO 3 was directly synthesized in the anode region, with a purity of up to 99.52 %. Additionally, LiCoO2 2 was partially remediated in the cathode, increasing Li-Co molar ratio from 0.659 to 0.93. The obtained Li2CO3 2 CO 3 and the electrolysis residue LiCoO2 2 then underwent additional calcination, yielding a layered LiCoO2. 2 . At a Li-Co molar ratio of 1.1, the initial specific capacity of the calcined LiCoO2 2 material was 129.9 mAh/g, exhibiting a capacity retention rate of 50.48 % over 100 cycles. Therefore, a novel, cost-effective, and energy-saving strategy for recycling S-LIBs is proposed.

Mn-containing sodium superionic conductor (NASICON) compounds have shown considerable potential as cathode for sodium-ion batteries (SIBs) owing to higher working voltage (V5+/V4+: 3.9 V), lower cost, and lower toxicity compared to full vanadium-based NASICON Na3V2(PO4)3. Taking Na3.3V1.7Mn0.3(PO4)3 (NVMP) as an example, its practical application is still restricted by poor electronic conductivity, sluggish intrinsic Na+ diffusion, and poor high-voltage stability. In this work, a high entropy strategy is proposed to develop Na3.3V1.613Mn0.3(Cr, Fe, Co, Ni, Zr)0.1(PO4)3 (HE-NVMP) cathode for not only enabling more and rapid Na+ migration but also significantly improving deep desodiation stability. Based on theoretical calculations and experimental findings, such high entropy modification can efficiently alter the coordination environments of both V/Mn and Na sites for reducing Na+ diffusion energy barrier, increasing the occupancy of Na+ at Na(2) sites, and consolidating the structure stability. Thus, the obtained HE-NVMP delivers superior high-rate capability (91.7 mAh g-1) up to 50 C and excellent cycling performance (capacity retention: 81.2%) after 10 000 cycles at 20 C at the cutoff voltage of 4.1 V. More importantly, such cathode also exhibits superior sodium storage properties at a higher cutoff voltage (4.5 V) with electrochemical polarization with 75% reduction at 1 C and higher capacity retention of 80.3% after 2000 cycles at 20 C compared to pristine counterpart, indicating a great potential for practical rechargeable batteries with excellent overcharge resistance capability.

Delivery of high energy density in polyanion compound-Na3V2(PO4)3 based on three-electron redox is still challenging because of their controversial multi-electron reaction mechanism and unsatisfactory electrochemical reversibility. Herein, the reversible V4+/V5+ redox (ca. 4.0 V) could be successfully activated in Na4VFe(PO4)3 cathode material through a Na-rich strategy, demonstrating a reversible specific capacity of 154.7mAh g- 1 at 0.1C and 90.3mAh g- 1 after 800 cycles at 20C, with 80 % of the initial capacity retained. The entire electrochemical reaction undergoes a highly recoverable phase transition by in-situ X-ray diffraction. Impressively, the Na-rich strategy could not only allow Na2 site to be occupied to activate the V4+/V5+ redox pair confirmed by Xray absorption near-edge structure spectroscopy, but also enable Na+ transportation across the generated vacancies rather than synergistic Na+ diffusion. This work provides rational design strategy of multi-electron transfer reaction in high-energy sodium-ion batteries.

Open AccessRenewablesRESEARCH ARTICLES20 Feb 2024An Amphipathic Ionic Sieve Membrane for Durable and Dendrite-Free Zinc-Ion Batteries Xian-Xiang Zeng, Shu Zhang, Tao Long, Qing-Yuan Zhao, Hong-Rui Wang, Wei Ling, Xiong-Wei Wu, Aiping Yu and Zhongwei Chen Xian-Xiang Zeng *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Shu Zhang School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Tao Long School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Qing-Yuan Zhao School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Hong-Rui Wang School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Wei Ling School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Xiong-Wei Wu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128 , Aiping Yu Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1 and Zhongwei Chen *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] National Key Laboratory of Catalytic Energy Conversion, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 https://doi.org/10.31635/renewables.024.202300045 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Rechargeable aqueous zinc-ion batteries are expected to be widely deployed for grind-scale energy storage due to the merits of low expenditure, safety, and so on. However, challenges on the Zn anode, including dendrite growth and parasitic reactions with aqueous electrolytes hinder its advancement. Hereby, an amphipathic ionic sieve (AIS) membrane was designed to screen Zn2+ from the bulk of aqueous electrolyte by ruling out water solvent and assisting Zn2+ to deposit with a smooth morphology under a confined shielding. These benign characteristics enabled AIS to run Zn symmetric cells over 2300 h with a voltage of 1 mA h·cm−2 at each cycle and tolerated long-term standby for more than 3 months. A low self-discharge rate and outstanding cycling stability were realized in V2O5/Zn batteries at equal weight for cathode and anode (N/P ratio ≈ 1.39). This asymmetrical wetting separator proved a facile strategy to solve interfacial dendrites and parasitic reactions in Zn metal-based batteries. Download figure Download PowerPoint Introduction Zinc, as a kind of nontoxic and low-cost metal, possesses high theoretical capacity (820 mA h·g−1 or 5851 mA h·cm−3) and low redox potential of Zn2+/Zn (−0.76 V vs standard hydrogen electrode), and has been utilized as the anode in primary battery for a long history.1–6 However, challenges such as the dendrite growth,7 parasitic reactions with water, no matter if it is alkaline, neutral, or acid,8–10 stand in the way of developing practical rechargeable zinc batteries.11,12 To deal with these issues, countermeasures mainly include the development of artificial solid electrolyte interphase (SEI),13–15 anode reconstruction,16–18 new liquid electrolytes with different additives,19–22 solvents,23,24 salts,25,26 and concentration,27,28 and solidified electrolytes.29–31 These strategies unveil a common denominator to prevent solvated water from direct or restricted contact with the Zn anode, which is beneficial to suppress water decomposition and Zn corrosion. However, these choices are more or less subjected to high-cost issues, poor contact, or unsatisfactory mechanical strength. As a frequently oblivious but essential component, the broadly used separators such as cellulose and glass fiber are hard to achieve the abovementioned functions in electrode and electrolyte, since they are either too thick (∼600 μm for glass fiber) or mechanically fragile during long-term operation.32–35 Additionally, these separators cannot suppress the parasitic reaction or dendrite growth in the aqueous electrolyte.33 The fundamental roots in the function of isolating water from the bulk electrolyte and only permitting Zn2+ to pass through for electroplating, minimizing the occurrence of parasitic reaction.36,37 Some polymer-based separators might enable selective Zn2+ permeation but encounter degradation in water or discounted desolvation and electrochemical kinetics.34,38 Therefore, the regulation of interface chemistry with thin and mechanically robust separators is of great importance.39,40 Strictly speaking, there has been almost no research focusing on separators with Zn2+ desolvation regulation or Zn2+ sieving capability in rechargeable zinc-ion batteries (ZIBs). Besides, the performance verification in the full batteries with fabricated separators is based on excessive Zn. Herein, we prepared a heterogeneous and thin composite polymer separator with an amphipathic ionic sievie (AIS) feature based on a hydrophobic microporous substrate. By elaborately grafting a copolymer of acrylic acid (AA) and acrylamide (AM) as the functional moiety, the surface wettability of the AIS substrate was engineered from near hydrophobicity to hydrophilicity, and thanks to the discrepant wettability, the zinc hexahydrate ([Zn(H2O)6]2+) underwent desolvation by preferentially binding between the water molecule and hydrophilic segment before its transfer to Zn surface for flat deposition, which also contributed to an augmented Zn2+ transference number in contrast to a fully hydrophilic separator, while the nearly hydrophobic surface of AIS restrained the continuous formation of passivating layer triggered by desolvated water molecules and possible water solvent from the bulk phase of an electrolyte. Under this context, the side reactions and Zn dendrite, after 3 months' standby have been greatly restrained, and Zn symmetric cells cycled with 2300 h at 1 mA h·cm−2 and V2O5/Zn batteries with a negative/positive capacity ratio of 1.39 (N/P ratio ≈ 1.39) were also demonstrated, which is one of the lowest value reported to date. Results and Discussion The amphipathic ionic sieve (AIS) was prepared through the dip coating method, during which the AM and AA monomers were initiated by ammonium persulfate to polymerize, and cladded on hydrophobic polytetrafluoroethylene (PTFE) porous substrate (Scheme 1a,b and Supporting Information Figure S1). Fourier transform infrared (FTIR) spectra showed typical peaks of N–H near 3400 ∼ 3200 cm−1, 2933 cm−1 for the C–H stretching vibration, strong peaks around 1655 and 1443 cm−1 of C=O in AM and AA monomers, and C–F peaks (1204 and 1144 cm−1) in PTFE (Scheme 1c). For comparison, a pure gel electrolyte membrane (Gel) was also prepared. Basic physics and chemistry characters for PTFE, AIS, and Gel are listed in Supporting Information Table S1. Notably, the thickness of AIS was merely about 20 μm (Figure 1a), much thinner than the dense and fragile dry gel electrolyte membrane (∼136 μm) ( Supporting Information Figure S2a,b). From the uniform element N and O mappings of the AIS surface (Figure 1b,c), the PTFE was covered successfully by a crosslinked network. Besides, it was feasible to scale up the AIS membrane by selecting a large-size PTFE substrate ( Supporting Information Figure S3). It is noteworthy that the AIS membrane showed much higher mechanical strength than the Gel as the electrolyte although its thickness was thinner compared with reported separators and solid-state electrolytes so far ( Supporting Information Figure S4 and Table S2), thereby proving its potential application prospect in ZIBs. Scheme 1 | (a) Reaction mechanism and formation process of the amphipathic membrane. (b) Scheme, illustrating the ion sieve process in the amphipathic membrane for Zn-ion batteries. (c) Fourier transform infrared (FTIR) spectra of polytetrafluoroethylene (PTFE) and the AIS membrane were obtained. Download figure Download PowerPoint More importantly, the AIS showed different wetting behaviors in contrast to PTFE and Gelas an electrolyte. We observed that the PTFE microporous membrane showed a contact angle of 130° with water (Figure 1d) while the dry gel electrolyte membrane showed a super-hydrophilic behavior on both sides ( Supporting Information Figure S2c,d). In contrast, the AIS showed asymmetric wettability, the contact angle at one side was ∼90° and the other was ∼45° (Figure 1e). The intensity and location change of the hydroxide group could be applied to indicate the interaction between the substrate and water molecule. Additional Raman tests for the AIS membrane and dry gel electrolyte were conducted to distinguish the discrepancy ( Supporting Information Figure S5). We found that the intensity of water molecules at the nearly hydrophobic side was lower than that of the hydrophilic side, and both intensities were lower than that of the dry gel electrolyte. The result was reasonable as the hydrophobic side, expelled water molecules from its surface and displayed lower intensity caused by a hydroxide group. Such amphipathic property catered for the purpose of Zn2+ migration from the bulk electrolyte to the Zn surface without compromising the reaction kinetic but constraining side reactions caused by free water molecules. Figure 1 | (a) SEM image of cross-section and (b) surface area for amphipathic membrane, and (c) corresponding nitrogen and oxygen element mapping. Contact angle test (up) and photograph (down) for (d) PTFE and (e) AIS membrane. SEM, scanning electron microscopy; PTFE, polytetrafluoroethylene; AIS, amphipathic ionic sieve. Download figure Download PowerPoint Thermal stability was a vital index for the separator. Four stages of weight loss appeared in the thermogravimetric curve of AIS ( Supporting Information Figure S6). The first step occurred below 120 °C, corresponding to the loss of water adsorbed, the second stage represented the decomposition of –NH– in AM from 200 to 300 °C, the third stage, which occurred from 370–480 °C was attributable to the overall degradation of the polyacrylamide/polyacrylamide (PAM/PAA) polymer backbone,41 and finally overlaps with PTFE substrate at 500 °C. These results indicate that AM and AA crosslinked on the PTFE substrate and altered the wetting ability. The validity of AIS on the electrochemical stability of electrolytes was further testified, which was long trapped by the electrolysis of H2O and restricted the application of aqueous ZIBs. Firstly, the AIS impacted the desolvation process of Zn2+ and further on Zn redox in aqueous electrolytes. The electrostatic potential (EP) was analyzed by density functional theory (DFT) calculations and used to compare the adsorption effect between [Zn(H2O)6]2+ and diverse substrates. As shown in Figure 2a, the charge distribution in PTFE is neutral, demonstrating its difficulty in absorbing [Zn(H2O)6]2+, and without interaction with water molecules. However, the [Zn(H2O)6]2+ could be absorbed by the copolymer of AM and AA as there existed a distinctly discrete area of positive and negative charges, and the binding energy of the copolymer with [Zn(H2O)6]2+ (−2.41 eV) was much larger than sole AM (−1.80 eV) and AA (−1.34 eV) (Figure 2b and Supporting Information Figures S7 and S8), revealing synergic bonding effects between AM and AA toward [Zn(H2O)6]2+. Figure 2 | (a) Electrostatic surface potential of PTFE and copolymer of acrylamide (AM) and acrylate acid (AA). (b) Binding energy of between with [Zn(H2O)6]2+ and AM, AA, and the copolymer of AM and AA. (c) Binding energy between H2O (up) and [Zn(H2O)6]2+ (down) with copolymer of AM and AA. (d) Electrochemical impedance spectra of Zn symmetric cell before and after polarization. (e) Activation of stainless steel symmetric cells at different temperatures. The atom sizes of AM and AA, scaled up for aesthetic reasons. AIS, amphipathic ionic sieve; PTFE, polytetrafluoroethylene. Download figure Download PowerPoint Further, to unravel the reaction mechanism, we investigated the binding energy to explore whether the introduced functional polymer on the PTFE substrate would participate in the desolvation process of [Zn(H2O)6]2+ (Figure 2c and Supporting Information Table S3). To our surprise, the copolymer of AM and AA initially combined with H2O surrounding Zn2+ with low binding energy (−15.23 eV), confirming that their copolymer improved the hydrophilicity of PTFE substrate and helped [Zn(H2O)6]2+ to desolvate, with the binding energy between H2O and Zn2+ (8.41 eV) being greater than 0, revealing that this reaction was nonspontaneous. Thus, the PTFE membrane modified by the copolymer was analogous to the molecular sieve to lock H2O but permitted the Zn2+ infiltration with an enhanced ion transference number (0.42) (Figure 2d), which was higher than the typical value of aqueous electrolyte (generally below 0.4),42,43 and the heterogeneous wettability in AIS was benefited to [Zn(H2O)6]2+ desolvation, verified by the reduced desolvation energy of hydrated zinc ion from 61.6 kJ mol−1 for the dry gel electrolyte to 52.3 kJ mol−1 for the AIS membrane ( Supporting Information Figure S9). Further, the activation energy of AIS (0.04 eV) was much lower than that of the Gel (0.1 eV) (Figure 2e and Supporting Information Figures S10 and S11). The above-mentioned merits of AIS were verified by Zn symmetric cells with 3 M ZnSO4 electrolyte. As shown in Figure 3a, the AIS maintained the polarization voltage within 150 mV after 2340 h. The polarization voltages were 45, 60, 70, 85, and 110 mV for AIS-based Zn symmetric cells from 0.1 to 1 mA cm−2, respectively (Figure 3b). By contrast, Zn symmetric cells assembled with PTFE could not work at the initial stage and the Gel-based cells failed after cycling for only about 300 h. It should be noted that the Gel electrolyte with comparable thickness to AIS was mechanically damageable and suffered from decomposition in water ( Supporting Information Figure S12). When the areal capacity was increased to 1 mA h cm−2, the polarization voltage was almost unchanged, even slightly lower than the original value, which was a common behavior in zinc ion batteries.11 Figure 3 | (a) Voltage-time profiles of Zn symmetric cells with AIS, Gel, and PTFE as separators. The inserts are curves after restarting for 135 days' stand-by (left) and voltage variation versus temperature (right), respectively. Magnified view of voltage-time curves at different current densities with AIS, Gel, and PTFE as the separator (a) at different current densities and (b) long-term cycling with a capacity of 1 mA h cm−2. AIS, amphipathic ionic sieve; PTFE, polytetrafluoroethylene. Download figure Download PowerPoint Wondrously, the Zn symmetric cells could restart and operate normally after resting for 135 days (the left inset in Figure 3a), and no short circuit was found after continuous operation for 2000 h. Meanwhile, the polarization voltage was gradually reduced from 90 to 50 mV when the temperature increased from 25 to 40 °C and gradually recovered after temperature restoration (the right inset in Figure 3a), clearly illustrating satisfactory temperature tolerance of the AIS. The polarization voltage after cycling for 2000 h was maintained at 100 mV (Figure 3c), indicating the long-term stability of AIS. However, Zn symmetric cells assembled with cellulose separator became short-circuited ( Supporting Information Figure S13). One possible reason is that due to the poor mechanical strength of the separator, it failed to withstand the dendrite piercing caused by uneven Zn deposition. The abovementioned results consistently indicated that the AIS membrane was involved in the solvation process and that the asymmetric wettability design reduced the occurrence of parasitic reactions and dendrite growth. Post-mortem of the cycled Zn anode with different separators were recorded. Other Zn anodes with cellulose at a comparable thickness and Gel are chosen as control. The Zn presents an irregular flower-like surface after 57-h operation compared with the pristine Zn anode (Figure 4a and Supporting Information Figure S14a,b), which easily pierced the separator and caused cell failure. While the Zn surface with the Gel electrolyte exhibited an uneven and irregular layered structure after 280 h, some of the radially vertical Zn flakes might have been caused by the short circuit failure of the battery (Figure 4b and Supporting Information Figure S14c). In stark contrast to the cellulose separator and Gel as an electrolyte, the Zn anode with the AIS separator showed a dense and flat plane without apparent dendrites and pores after cycling for 2340 h (Figure 4c and Supporting Information Figure S14d). Based on these Zn morphology and separator attributes, possible mechanisms for the three separator types were proposed (Figure 4d–f). The Zn2+ flux in the thin and porous cellulose separator was arbitrary and uncontrollable during plating while the Zn2+ was partly confined under the totally hydrophilic Gel as an electrolyte. Meanwhile, the AIS membrane showed a heterogeneous wetting ability to pre-sieve Zn2+ from the bulk of electrolyte with suppressed side reactions between the Zn anode and water molecule and exhibited spatially confined dendrite growth as well. Figure 4 | Scheme illustration of ion transfer process within (a) cellulose, (b) Gel as an electrolyte, and (c) AIS separator. SEM images of Zn anode after cycling for (d) 57 h with cellulose, (e) 280 h with Gel as an electrolyte, and (f) 2340 h with AIS separator. (g) Zn 2p, (h) O 1s, and (i) S 2p XPS spectra of Zn anode after cycling for 2340 h (up) and Zn metal stored in air (down) at the same time. AIS, amphipathic ionic sieve; SEM, scanning electron microscopy; XPS, X-ray photoelectron spectroscopy. Download figure Download PowerPoint Through the X-ray photoelectron spectroscopy (XPS) analysis, the main composition of the Zn anode with AIS separator was Zn4(OH)6SO4·xH2O after 2340-h operation,21,44,45 which was distinctively different compared with by-products such as Zn–O (∼529.8 eV) and O–H (. ∼531.7 eV) on the Zn anode stored in air for same time frame (Figure 4g–i). Under the protection of these passivation layers, the Zn/AIS/Cu cell showed an average Coulombic efficiency of 90%, which was generally observed in aqueous electrolytes without anode or electrolyte modification but with dramatic fluctuation, reaching as low as 20%;33 also, much longer lifespan and smaller overpotential (1500 h, 35 mV) were realized concurrently compared with Zn/Gel/Cu cells (500 h, 40 mV) under the sufficient Zn supply ( Supporting Information Figure S15), signifying that the AIS membrane could minimize the parasitic reaction of ZIBs and prolonged the lifespan at working and standby status. After activating with 300 mA g−1 for 3 cycles, the voltage of fully charged ZIB with an AIS separator dropped from 1.6 to 1.15 V, and the capacity retention rate reached 91.12%, corresponding to a self-discharge rate of 0.37% h−1 ( Supporting Information Figure S16). In comparison, Zn/Gel/Cu cells showed much lower capacity retention (70.83%) although with a similar voltage drop, and two folds self-discharge ratio (0.88% h–1), showing the superiority of AIS in stabilizing Zn anode. The electrochemical performance of Zn/V2O5 batteries with AIS membrane was further studied. Cyclic voltammetry tests were conducted at 0.1 mV s−1 from 0.2 to 1.6 V. Two pairs of redox peaks indicated that pentavalent vanadium underwent a two-electron redox process ( Supporting Information Figure S17). The potential difference of Zn/AIS/V2O5 was 168 and 120 mV, respectively, significantly lower than that of a Gel-based battery (255 and 318 mV). The Zn/AIS/V2O5 cell also showed more excellent rate performance (Figure 5a). The specific capacity attained 455 mA h g−1 at 0.3 A g−1, while the capacity was still maintained at 140 mA h g−1 at 10 A g−1 (Figure 5b). By contrast, the Zn/Gel/V2O5 battery merely released less than 100 mA h g−1 at 10 A g−1 ( Supporting Information Figure S18). Moreover, to check the AIS under a more realistic condition, the mass ratio of Zn anode and V2O5 was fixed at 1 (N/P = 1.39), which was one of the lowest N/P ratios; the assembled battery also showed both excellent rate and long-term cycling performances (Figure 5c and Supporting Information Figure S19), which also surpassed the performance of the Gel as an electrolyte, cellulose, and Whatman separators-based full batteries with a proportionable N/P ratio ( Supporting Information Figure S20). Figure 5 | (a) Rate performance comparison of Zn/V2O5 batteries with Gel as an electrolyte and AIS separator. (b) Charge–discharge curve of AIS-based Zn/V2O5 batteries, and (c) cycling stability comparison for Gel and AIS membrane-based ZIBs different excessive Zn amount. AIS, amphipathic ionic sieve; ZIBs, zinc-ion batteries. Download figure Download PowerPoint Conclusion An amphipathic membrane was prepared by impregnating hydrophobic substrate into the hydrophilic polymer with a facile method and realized the purpose of sieving zinc ions for dendrite-free plating from zinc hexahydrate via competitive bonding of water with hydrophilic moieties. Restraining parasitic reactions resulted from zinc anode and free water molecule in solvation sheath. Thanks to the asymmetric wettability, the amphipathic membrane assisted in constructing a sturdy interface protection layer that could tolerate temperature variation and operate stably after long-term standby. In addition, the improved capacity retention and rate performance of the full battery demonstrated the superiority of AIS in rechargeable ZIBs. This AIS might also enlighten a promising design guideline to solve the problem of dendrites and parasitic reactions in other metal batteries. Supporting Information Supporting Information is available and includes the scanning electron microscopy (SEM) images and photographs of PTFE, Gel as an electrolyte, AIS membrane, and zinc anode after cycling, mechanical tests, Raman spectra, thermogravimetric (TG) curves, calculation results for electrostatic potential (EP) and binding energy, EIS spectra and desolvation energy, electrochemical measurements for Coulombic efficiency, self-discharge, rate performance, and long-term cycling tests. Tables of basic physiochemical properties for separators and electrolytes, binding energies, and batteries' performance comparison with published reports are also incorporated. 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 2Issue 1Page: 52-60Supporting Information Copyright & Permissions© 2024 Chinese Chemical SocietyKeywordszinc anodedendriteamphipathicitydesolvationseparatorAcknowledgmentsThis work was supported by the National Natural Science Foundation of China (grant no. 51803054), the Science and Technology Innovation Program of Hunan Province, China (grant no. 2023RC3154), the Natural Science Foundation of Hunan Province (grant no. 2020JJ3022), the scientific research projects of Education Department of Hunan Province (grant nos. 23A0188 and 23B0221), the Natural Sciences and Engineering Research Council of Canada, University of Waterloo and Waterloo Institute for Nanotechnology, Canada. Downloaded 184 times PDF downloadLoading ...

Realizing high -rate capability and high -efficiency utilization of polyanionic cathode materials is of great importance for practical sodium -ion batteries (SIBs) since they usually suffer from extremely low electronic conductivity and limited ionic diffusion kinetics. Herein, taking Na3.5V1.5Mn0.5(PO4)3 (NVMP) as an example, a reinforced concrete -like hierarchical and porous hybrid (NVMP@C@3DPG) built from 3D graphene ("rebar") frameworks and in situ generated carbon coated NVMP ("concrete") has been developed by a facile polymer assisted self -assembly and subsequent solid-state method. Such hybrids deliver superior rate capability (73.9 mAh/g up to 20 C) and excellent cycling stability in a wide temperature range with a high specific capacity of 88.4 mAh/g after 50 0 0 cycles at 15 C at room temperature, and a high capacity retention of 97.1% after 500 cycles at 1 C (-20 degrees C), and maintaining a high reversible capacity of 110.3 mAh/g in full cell. This work offers a facile and efficient strategy to develop advanced polyanionic cathodes with high -efficiency utilization and 3D electron/ion transport systems. (c) 2024 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Reversible and dendrite-free zinc (Zn) circulation is essential for longevous aqueous zinc-ion batteries (ZIBs) and greatly impacted by the property of Zn interface and electrolyte, especially when confronted with high current density and large area capacity. Herein, a hierarchical Zn interface is constructed by the preferential anion surfactant adsorption and reaction, and assists to reduce the interfacial energy and side reactions for enhanced diffusion kinetics and reversibility during Zn plating/stripping. Thus, highly reversible and smooth Zn anodes are achieved with a long-term stability of 5500 h at 1 mA cm-2/1 mAh cm-2, an impressive rate up to 40 mA cm-2 for 10 mAh cm-2 and a large cumulative plating capacity of 4.45 Ah cm-2 at 10 mA cm-2 in Zn symmetric cells. Even under a high depth of discharge of 60% (5.85/7.65 mAh cm-2), Zn symmetric batteries can still maintain ca. 800 h's life. The proposed countermeasure has also proved to be valid in prolonging the lifespan and stability of Zn-MnO2 full batteries at both low and high cycling current densities. An interfacial regulation strategy of preferential adsorption via anionic surfactants, 2-acrylamide-2-methylpropanesulfonic (AMPS), is proposed to reduce side reactions and enhance the diffusion kinetics of zinc-ion at the zinc/electrolyte interface, thereby achieving highly reversible and flat zinc anode at large area capacity and depth of discharge.image

Fast charging and all-climate electrochemical behaviors are two of the most important issues of olivine cathodes for lithium ion batteries (LIBs) owing to inferior Li + and electron conduction at a high current density or low temperature. Taking Mn-containing olivine cathode (LiFe 0.8 Mn 0.2 PO 4 , LFMP) as an example, herein, we report a facile interconnected, hierarchically porous and highly conductive framework design strategy to construct an advanced bulk LFMP@graphene hybrid, realizing superior fast charging capability and wide temperature performance (-20-80 degrees C). Such hybrids not only offer well-interconnected and highly conductive graphene networks, but also possess hierarchical porous interiors where the former ensures high-efficiency charge transfer between active components while the latter facilitates Li + diffusion. Benefiting from these advantages, the obtained hybrids deliver superior rate capability (85.0 mAh g-1 up to 20C) and high capacity retentions of 94.1 % after 3000 cycles at 10C (50 degrees C), and 91.7 % after 500 cycles at 5C (80 degrees C), and 93.6 % after 1300 cycles at 1C (-20 degrees C). This work provides an efficient strategy to design practical olivine cathode at the material level for fast charging and all-climate LIBs.

Metal selenides are considered as one of the most promising anode materials for Na-ion batteries owing to high specific capacity and relatively higher electronic conductivity compared with metal sulfides or oxides. However, such anodes still suffer from huge volume change upon repeated Na+ insertion/extraction processes and simultaneously undergo severe shuttle effect of polyselenides, thus leading to poor electrochemical performance. Herein, a facile chemical-blowing and selenization strategy to fabricate 3D interconnected hybrids built from metal selenides (MSe, M = Mn, Co, Cr, Fe, In, Ni, Zn) nanoparticles encapsulated in in situ formed N-doped carbon foams (NCFs) is reported. Such hybrids not only provide ultrasmall active nanobuilding blocks (≈15 nm), but also efficiently anchor them inside the conductive NCFs, thus enabling both high-efficiency utilization of active components and high structural stability. On the other hand, Cu-driven replacement reaction is utilized for efficiently inhibiting the shuttle effect of polyselenides in ether-based electrolyte. Benefiting from the combined merits of the unique MSe@NCFs and the utilization of the conversion of metal selenides to copper selenides, the as-obtained hybrids (MnSe as an example) exhibit superior rate capability (386.6 mAh g-1 up to 8 A g-1 ) and excellent cycling stability (347.7 mAh g-1 at 4.0 A g-1 after 1200 cycles).

The uncontrolled growth of dendrites and serious sidereactions,such as hydrogen evolution and corrosion, significantly hinder theindustrial application and development of aqueous zinc-ion batteries(ZIBs). This article presents ovalbumin (OVA) as a multifunctionalelectrolyte additive for aqueous ZIBs. Experimental characterizationsand theoretical calculations reveal that the OVA additive can replacethe solvated sheath of recombinant hydrated Zn2+ throughthe coordination water, preferentially adsorb on the surface of theZn anode, and construct a high-quality self-healing protective film.Notably, the OVA-based protective film with strong Zn2+ affinity will promote uniform Zn deposition and inhibit side reactions.As a result, Zn||Zn symmetrical batteries in ZnSO4 electrolytescontaining OVA achieve a cycle life exceeding 2200 h. Zn||Cu batteriesand Zn||MnO2 (2 A g(-1)) full batteriesshow excellent cycling stability for 2500 cycles, demonstrating promisingapplication prospects. This study provides insights into utilizingnatural protein molecules to modulate the kinetics of Zn2+ diffusion and enhance the stability of the anode interface.

Antimony (Sb) has been considered an attractive anode material for sodium-ion batteries (SIBs) because of its high theoretical capacity (660 mAh g(-1)), abundant resources, and relatively safe working potential (similar to 0.8 V). However, such an anode still suffers from huge volume change and repeated formation/destruction of a solid electrolyte interface (SEI) at the interface upon sodiation/de-sodiation, thus leading to poor electrochemical performance. To address these issues, we design and construct a unique hybrid nanostructure built from hollow/porous Sb nanocubes embedded in interconnected nitrogen-doped carbon frameworks. Such a hybrid combines the merits of internal void engineering for the Sb anode and threedimensional (3D) continuous conductive protection layer where the former can efficiently accommodate the structural strain upon sodiation and de-sodiation processes, while the latter not only prevents the direct contact of an electrolyte and active component but also provides a high-efficiency electron/ion transport system, consequently leading to higher structure/interface stability and better sodium storage capability. When evaluated as an anode for SIBs, such a hybrid delivers reversible capacities of 588.8 mAh g(-1) at 0.05 A g(-1) and 359.4 mAh g(-1) at 2 A g(-1), as well as retains a specific capacity of 347.8 mAh g(-1) after 200 cycles at 1 A g(-1). Our work provides a simple and effective strategy to construct a unique 3D interconnected hybrid architecture with a simultaneously improved structure and interface stability for the alloying-based anode.

Electrochemical energy storage has experienced unprecedented advancements in recent years and extensive discussions and reviews on the progress of multivalent metal-ion batteries have been made mainly from the aspect of electrode materials, but relatively little work comprehensively discusses and provides an outlook on the development of electrolytes in these systems. Under this circumstance, this Review will initially introduce different types of electrolytes in current multivalent metal-ion batteries and explain the basic ion conduction mechanisms, preparation methods, and pros and cons. On this basis, we will discuss in detail the research and development of electrolytes for multivalent metal-ion batteries in recent years, and finally, critical challenges and prospects for the application of electrolytes in multivalent metal-ion batteries will be put forward.

The vast superiority in resource sustainability and volumetric energy density enables metallic zinc (Zn) to construct cost-effective and environment-benign battery systems for the energy storage. However, the problems of Zn dendrites and poor Coulombic efficiency (CE) during cell's whole life cycle stump its advancement as a rechargeable battery choice. The solution is to modulate the Zn2+ desolvation prior to electro-reduction and subsequent deposition. Herein, a transferred protection tactic via a bifunctional sulfonated covalent polymer interlayer is proposed to regulate the Zn2+ desolvation, which affects the formation of solid-electrolyte interphase, and guides its plating along with preferable (002) crystal plane. Thus, the high initial CE of 96.3% and the long-term average CE of 99.8% for 310 cycles are achieved in Zn||Cu cells and 570-h circulation is also realized at 2 mA cm(-2)/10 mAh cm(-2) in Zn||Zn cells. Besides, Zn||hydrated vanadium oxide-based full batteries with the low-concentration organic electrolytes are also demonstrated with the high specific capacity of 173.8 mAh g(-1) at 0.5 A g(-1) and 64% capacity retention over 305 cycles and oriented Zn deposition.

Low-cost sodium superionic conductor (NASICON) solid electrolytes featuring high ionic conductivity and high safety characteristics are regarded as one of the best choices to replace liquid electrolytes in energy-intensive lithium (Li)-metal batteries. However, the conventional NASICON electrolytes prepared by pressureless sintering generally exhibit low density and poor fracture toughness, largely limiting their wide practical application. In this work, borosilicate glass (BG) as the second phase was added to Li-1.4 Al0.4Ti1.6(PO4)(3) (LATP) during the sintering process and a strong and tough ceramic electrolyte. The results showed that after BG was added, the fracture strength of the obtained ceramic electrolytes reached 74 MPa, which was 2.38 times that of pure LATP. The activation energy showed a reduction of 14.3% to 0.3 eV compared with pure LATP, and the relative density reached 97.17%, attaining a high level under pressureless sintering conditions. In addition, the all-solid-state batteries with LiFePO4 (LFP) as the cathode and Li metal as the anode exhibited good cycling stability after surface modification and a discharge specific capacity of 154.5 mA.h-g(-1) at 25 degrees C and 0.1 C. After 100 cycles, the Coulombic efficiency was close to 100%. This method provides a feasible avenue for preparing ceramic electrolytes with high mechanical strength and high ionic conductivity.

设计了一种含仲胺基团的苝酰亚胺衍生物N,N-二(2-乙基乙二胺基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4,9,10-苝酰亚胺(B-PDI-1),并采用紫外吸收光谱与荧光光谱研究了B-PDI-1在四氢呋喃(THF)/H2O混合溶剂中的光物理性质;通过扫描电镜(SEM)与X射线粉末衍射(XRD)表征B-PDI-1在THF/H2 O中所形成的聚集体形态结构;利用循环伏安法(CV)与Guassion模拟运算研究了其变色机理;使用电化学工作站测定了聚集体的J-V曲线与瞬态光响应,并评估了它的光伏性能.结果表明,B-PDI-1在THF/H2 O二元溶剂体系自组装过程中由红色变为蓝色,其紫外吸收光谱则出现了红移现象,在THF含量fTHF=10％时达到了最大值35.4 nm,随着THF/H2 O二元溶剂体系中THF含量减少,荧光强度将会逐渐降低,但始终存在着微弱的荧光,意味着B-PDI-1具有J型聚集的特征;B-PDI-1在不同THF/H2 O比例的混合溶液中都能形成具有明确形貌的聚集体,在不同THF含量的溶液中分别获得了螺旋带状、长斜四边形、棒状、类球形以及长直纳米带等纳米结构;随着该组装体系中THF含量发生变化,分子堆积方式也将改变,分子间的微扰作用集中体现在HOMO能级的提高,由于不同聚集体能带的差异导致了颜色的变化,且在fTHF=10％时B-PDI-1的光波转化效率达到最大值(0.43％).

It is crucial to tune the morphology of aggregates to obtain functional photoelectric properties in perylene bisimide (PBI). The associated properties can be controlled by appropriate molecular design and by tuning the self-assembly conditions. However, many studies only focused on the modification with easily-protonated groups at the bay positions of perylene bisimide, which greatly limited their potential applications. In this work, four PBI derivates bearing tertiary amine groups at the imide positions were synthesized and their self-assembly with different concentrations of hydrochloric acid were performed. The final morphology and the properties of the aggregates were tuned by modifying the charge interaction in addition to π-π stacking and hydrophobic interactions. The evolution of the specific morphology with the acidity of the self-assembly conditions was discussed and the molecular structure was optimized. The photophysical properties of the aggregates were characterized by UV–visible and fluorescence spectroscopy. The shapes of the spectra varied with the molecular structures and the acid concentration. Moreover, the emission spectra of the aggregates experienced a large Stokes shift. The color of the aggregates formed from the three derivates (MDI-PBI, EDI-PBI, and AEP-PBI) changed from red to blue upon protonation. These derivatives may have potential applications in organic photoelectric functional devices where a strict morphology or size is needed. The protonation-dependent morphology, the color change, and the large Stokes shift makes the aggregates potential candidate for fluorescent probes or pH sensors.

In this work, perylene bisimide derivatives (PBI-1 and PBI-2) with tertiary amine groups were designed and synthesized. To control the final morphologies and properties of their aggregates, seven kinds of organic acids were used to alter the self-assembly environment. The influence of organic acids on the morphology of the aggregates was investigated. Photophysical properties of the aggregates were markedly affected by the kind and concentration of the organic acid. The thermal and gas sensitivities of the PBI-1 aggregates were studied with the use of UV–visible spectroscopy and digital imaging. The shift of the UV–visible spectra varied with time, temperature, acid type and acid concentration. Furthermore, PBI-1 aggregates showed a red-to-blue color change after addition of seven organic acids, whereas the color of the PBI-2 aggregates remained red. These changes of morphologies, photophysical properties and their thermal and gas sensitivities make these aggregates potentially useful in the fields of optoelectronics or sensors.