Solvation Modulation Enhances Anion-Derived Solid Electrolyte Interphase for Deep Cycling of Aqueous Zinc Metal Batteries

Stable Zn anodes with a high utilization efficiency pose a challenge due to notorious dendrite growth and severe side reactions. Therefore, electrolyte additives are developed to address these issues. However, the additives are always consumed by the electrochemical reactions over cycling, affecting the cycling stability. Here, hexamethylphosphoric triamide (HMPA) is reported as an electrolyte additive for achieving stable cycling of Zn anodes. HMPA reshapes the solvation structures and promotes anion decomposition, leading to the in situ formation of inorganic-rich solid-electrolyte-interphase. More interestingly, this anion decomposition does not involve HMPA, preserving its long-term impact on the electrolyte. Thus, the symmetric cells with HMPA in the electrolyte survive ≈500 h at 10 mA cm⁻² for 10 mAh cm⁻² or ≈200 h at 40 mA cm⁻² for 10 mAh cm⁻² with a Zn utilization rate of 85.6 %. The full cells of Zn||V₂O₅ exhibit a record-high cumulative capacity even under a lean electrolyte condition (E/C ratio=12 μL mAh⁻¹), a limited Zn supply (N/P ratio=1.8) and a high areal capacity (6.6 mAh cm⁻²).     

Localized Anion-Cation Aggregated Aqueous Electrolytes with Accelerated Kinetics for Low-Temperature Zinc Metal Batteries

Aqueous zinc metal batteries hold great promise for large-scale energy storage because of their high safety, rich material resources and low cost. However, the freeze of aqueous electrolytes hinders low-temperature operation of the batteries. Here, aqueous localized anion-cation aggregated electrolytes composed of Zn(BF₄)₂ as the salt and tetrahydrofuran (THF) as the diluent, are developed to improve the low-temperature performance of the Zn anode. THF promotes the inclusion of BF₄⁻ in the solvation sheath of Zn²⁺, facilitating the formation of ZnF₂-rich solid-electrolyte-interphase. THF also affects the hydrogen bonding between neighboring H₂O molecules, effectively lowering the freezing point. Therefore, the full cells of Zn||polyaniline (PANI) exhibit an ultralong cycle life of 8000 cycles with an average Coulombic efficiency of 99.99 % at −40 °C. Impressively, the pouch cells display a high capacity retention of 86.2 % after 500 cycles at −40 °C, which demonstrates the great prospect of such electrolytes in cold regions. This work provides new insights for the design of low-temperature aqueous electrolytes.     

Dynamic Zn/Electrolyte Interphase and Enhanced Cation Transfer of Sol Electrolyte for All-Climate Aqueous Zinc Metal Batteries

Zn metal as one of the promising anodes of aqueous batteries possesses notable advantages, but it faces severe challenges from severe side reactions and notorious dendrite growth. Here, ultrathin nanosheets of α-zirconium phosphate (ZrP) are explored as an electrolyte additive. The nanosheets not only create a dynamic and reversible interphase on Zn but also promote the Zn²⁺ transportation in the electrolyte, especially in the outer Helmholtz plane near ZrP. Benefited from the enhanced kinetics and dynamic interphase, the pouch cells of Zn||LiMn₂O₄ using this electrolyte remarkably improve electrochemical performance under harsh conditions, i.e. Zn powders as the Zn anode, high mass loading, and wide temperatures. The results expand the materials available for this dynamic interphase, provide an insightful understanding of the enhanced charge transfer in the electrolyte, and realize the combination of dynamic interphase and enhanced kinetics for all-climate performance.     

An Amphiphilic Molecule-Regulated Core-Shell-Solvation Electrolyte for Li-Metal Batteries at Ultra-Low Temperature

Lithium metal batteries hold great promise for promoting energy density and operating at low temperatures, yet they still suffer from insufficient Li compatibility and slow kinetic, especially at ultra-low temperatures. Herein, we rationally design and synthesize a new amphiphilic solvent, 1,1,2,2-tetrafluoro-3-methoxypropane, for use in battery electrolytes. The lithiophilic segment is readily to solvate Li⁺ to induce self-assembly of the electrolyte solution to form a peculiar core-shell-solvation structure. Such unique solvation structure not only largely improves the ionic conductivity to allow fast Li⁺ transport and lower the desolvation energy to enable facile desolvation, but also leads to the formation of a highly robust and conductive inorganic SEI. The resulting electrolyte demonstrates high Li efficiency and superior cycling stability from room temperature to −40 °C at high current densities. Meanwhile, anode-free high-voltage cell retains 87 % capacity after 100 cycles.     

Low Concentration Sulfolane-Based Electrolyte for High Voltage Lithium Metal Batteries

Electrolyte engineering is crucial for the commercialization of lithium metal batteries. Here, lithium metal is stabilized in the highly reactive sulfolane-based electrolyte under low concentration (0.25 M) for the first time. Inorganic-polymer hybrid solid electrolyte interphase (SEI) with high ionic conductivity, low bonding with lithium and high flexibility enables dense chunky lithium deposition and high plating/stripping efficiency. Low concentration electrolyte (LCE) also enables excellent cycling stability of LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523)/Li cells at 1 C (90.7 % retention after 500 cycles) and 0.3 C (83.3 % retention after 1000 cycles). With a low N/P ratio (≈2), the capacity retention for NCM523/Li cells can achieve 94.3 % after 100 cycles at 0.3 C. Exploring the LCE is of paramount significance because it provides more possibilities of the lithium salt selections, especially reviving some lithium salts that are excluded before due to their low solubility. More importantly, LCE has the significant advantage of commercialization due to its cost-effectiveness.     

Realizing Textured Zinc Metal Anodes through Regulating Electrodeposition Current for Aqueous Zinc Batteries

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.     

Steric-hindrance Effect Tuned Ion Solvation Enabling High Performance Aqueous Zinc Ion Batteries

Despite many additives have been reported for aqueous zinc ion batteries, steric-hindrance effect of additives and its correlation with Zn²⁺ solvation structure have been rarely reported. Herein, large-sized sucrose biomolecule is selected as a paradigm additive, and steric-hindrance electrolytes (STEs) are developed to investigate the steric-hindrance effect for solvation structure regulation. Sucrose molecules do not participate in Zn²⁺ solvation shell, but significantly homogenize the distribution of solvated Zn²⁺ and enlarge Zn²⁺ solvation shell with weakened Zn²⁺−H₂O interaction due to the steric-hindrance effect. More importantly, STEs afford the water-shielding electric double layer and in situ construct the organic and inorganic hybrid solid electrolyte interface, which effectively boost Zn anode reversibility. Remarkably, Zn//NVO battery presents high capacity of 3.9 mAh ⋅ cm⁻² with long cycling stability for over 650 cycles at lean electrolyte of 4.5 μL ⋅ mg⁻¹ and low N/P ratio of 1.5, and the stable operation at wide temperature (−20 °C~+40 °C).     

Bio-Inspired Trace Hydroxyl-Rich Electrolyte Additives for High-Rate and Stable Zn-Ion Batteries at Low Temperatures

High-rate and stable Zn-ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost-resistant plants, we report trace hydroxyl-rich electrolyte additives that implement a dual remodeling effect for high-performance low-temperature Zn-ion batteries. The additive with high Zn absorbability not only remodels Zn²⁺ primary solvent shell by alternating H₂O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn²⁺ de-solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α-D-glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of −55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm⁻² under −25 °C, with a high cumulative capacity of 5000 mAh cm⁻². A full battery that stably operates for 10000 cycles at −50 °C is also demonstrated.     

Co-Intercalation of Dual Charge Carriers in Metal-Ion-Confining Layered Vanadium Oxide Nanobelts for Aqueous Zinc-Ion Batteries

Vanadium-based oxides with high theoretical specific capacities and open crystal structures are promising cathodes for aqueous zinc-ion batteries (AZIBs). In this work, the confined synthesis can insert metal ions into the interlayer spacing of layered vanadium oxide nanobelts without changing the original morphology. Furthermore, we obtain a series of nanomaterials based on metal-confined nanobelts, and describe the effect of interlayer spacing on the electrochemical performance. The electrochemical properties of the obtained Al_2.65V₆O₁₃ ⋅ 2.07H₂O as cathodes for AZIBs are remarkably improved with a high initial capacity of 571.7 mAh ⋅ g⁻¹ at 1.0 A g⁻¹. Even at a high current density of 5.0 A g⁻¹, the initial capacity can still reach 205.7 mAh g⁻¹, with a high capacity retention of 89.2 % after 2000 cycles. This study demonstrates that nanobelts confined with metal ions can significantly improve energy storage applications, revealing new avenues for enhancing the electrochemical performance of AZIBs.     

A Polarized Gel Electrolyte for Wide-Temperature Flexible Zinc-Air Batteries

The development of flexible zinc-air batteries (FZABs) has attracted broad attention in the field of wearable electronic devices. Gel electrolyte is one of the most important components in FZABs, which is urgent to be optimized to match with Zn anode and adapt to severe climates. In this work, a polarized gel electrolyte of polyacrylamide-sodium citric (PAM-SC) is designed for FZABs, in which the SC molecules contain large amount of polarized −COO⁻ functional groups. The polarized −COO⁻ groups can form an electrical field between gel electrolyte and Zn anode to suppress Zn dendrite growth. Besides, the −COO⁻ groups in PAM-SC can fix H₂O molecules, which prevents water from freezing and evaporating. The polarized PAM-SC hydrogel delivers a high ionic conductivity of 324.68 mS cm⁻¹ and water retention of 96.85 % after being exposed for 96 h. FZABs with the PAM-SC gel electrolyte exhibit long cycling life of 700 cycles at −40 °C, showing the application prospect under extreme conditions.     

水系锌离子电池电解液添加剂的研究进展

电解液添加剂能有效缓解锌金属阳极的不可控枝晶生长和固有副反应,大幅提升锌金属阳极的循环稳定性和可逆性,对水系锌离子电池的发展和商业化应用具有重要意义。本文通过对近期水系锌离子电池电解液添加剂的研究进展进行了系统总结和分析,简要介绍了锌金属阳极目前面临的主要挑战及其相关机理,重点阐述了电解液添加剂对锌金属阳极界面的作用机制,包括改变溶剂化结构、调节沉积方式、构筑界面保护层。此外,还对不同类型电解液添加剂进行了分类讨论,包括离子添加剂、无机添加剂和有机添加剂。最后,我们进一步对电解液添加剂策略在提升水系锌离子电池电化学性能中存在的科学问题和未来的研究方向进行了总结与展望。     

电解液对水系可充电池MnO2正极电化学性能的影响

研究了水系电解液中Li⁺、Zn²⁺和Mn²⁺阳离子对具有不同晶型结构和形貌的MnO₂正极电化学性能的影响,探讨其储能机理。结果表明,在不含Mn(II)离子的水溶液中,MnO₂电极所表现的电化学性能趋同,容量低,衰减快。含有Zn²⁺离子的水溶液中,MnO₂电极因二价锌离子的嵌入-脱出,容量明显提升,但衰减严重。当溶液中同时含有Zn²⁺、Mn²⁺离子时,基于Mn²⁺和Zn²⁺离子之间的协同作用和Mn²⁺离子氧化/还原反应过程的作用,有效抑制MnO₂颗粒的聚集和结构塌陷,削弱碱式硫酸锌杂质不利的影响,保持了锌离子在MnO₂电极中嵌入-脱出的高容量特性(200 mAh·g^-1,电流密度：100 mA·g^-1),及良好的循环稳定性。     

ZnF2-Riched Inorganic/Organic Hybrid SEI: in situ-Chemical Construction and Performance-Improving Mechanism for Aqueous Zinc-ion Batteries

Uncontrolled dendrites growth and serious parasitic reactions in aqueous electrolytes, greatly hinder the practical application of aqueous zinc-ion battery. On the basis of in situ-chemical construction and performance-improving mechanism, multifunctional fluoroethylene carbonate (FEC) is introduced into aqueous electrolyte to construct a high-quality and ZnF₂-riched inorganic/organic hybrid SEI (ZHS) layer on Zn metal anode (ZMA) surface. Notably, FEC additive can regulate the solvated structure of Zn²⁺ to reduce H₂O molecules reactivity. Additionally, the ZHS layer with strong Zn²⁺ affinity can avoid dendrites formation and hinder the direct contact between the electrolyte and anode. Therefore, the dendrites growth, Zn corrosion, and H₂ evolution reaction on ZMA in FEC-included ZnSO₄ electrolyte are highly suppressed. Thus, ZMA in such electrolyte realize a long cycle life over 1000 h and deliver a stable coulombic efficiency of 99.1 % after 500 cycles.     

Proton-Reservoir Hydrogel Electrolyte for Long-Term Cycling Zn/PANI Batteries in Wide Temperature Range

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 −SO₃⁻H⁺ 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.     

Reforming the Uniformity of Solid Electrolyte Interphase by Nanoscale Structure Regulation for Stable Lithium Metal Batteries

The stability of high-energy-density lithium metal batteries depends on the uniformity of solid electrolyte interphase (SEI) on lithium metal anodes. Rationally improving SEI uniformity is hindered by poorly understanding the effect of structure and components of SEI on its uniformity. Herein, a bilayer structure of SEI formed by isosorbide dinitrate (ISDN) additives in localized high-concentration electrolytes was demonstrated to improve SEI uniformity. In the bilayer SEI, LiN_xO_y generated by ISDN occupies top layer and LiF dominates bottom layer next to anode. The uniformity of lithium deposition is remarkably improved with the bilayer SEI, mitigating the consumption rate of active lithium and electrolytes. The cycle life of lithium metal batteries with bilayer SEI is three times as that with common anion-derived SEI under practical conditions. A prototype lithium metal pouch cell of 430 Wh kg⁻¹ undergoes 173 cycles. This work demonstrates the effect of a reasonable structure of SEI on reforming SEI uniformity.     

Eutectic-Based Polymer Electrolyte with the Enhanced Lithium Salt Dissociation for High-Performance Lithium Metal Batteries

The deployment of lithium metal anode in solid-state batteries with polymer electrolytes has been recognized as a promising approach to achieving high-energy-density technologies. However, the practical application of the polymer electrolytes is currently constrained by various challenges, including low ionic conductivity, inadequate electrochemical window, and poor interface stability. To address these issues, a novel eutectic-based polymer electrolyte consisting of succinonitrile (SN) and poly (ethylene glycol) methyl ether acrylate (PEGMEA) is developed. The research results demonstrate that the interactions between SN and PEGMEA promote the dissociation of the lithium difluoro(oxalato) borate (LiDFOB) salt and increase the concentration of free Li⁺. The well-designed eutectic-based PAN_1.2-SPE (PEGMEA: SN=1: 1.2 mass ratio) exhibits high ionic conductivity of 1.30 mS cm⁻¹ at 30 °C and superior interface stability with Li anode. The Li/Li symmetric cell based on PAN_1.2-SPE enables long-term plating/stripping at 0.3 and 0.5 mA cm⁻², and the Li/LiFePO₄ cell achieves superior long-term cycling stability (capacity retention of 80.3 % after 1500 cycles). Moreover, Li/LiFePO₄ and Li/LiNi_0.6Co_0.2Mn_0.2O₂ pouch cells employing PAN_1.2-SPE demonstrate excellent cycling and safety characteristics. This study presents a new pathway for designing high-performance polymer electrolytes and promotes the practical application of high-stable lithium metal batteries.     

Anion-modulated Ion Conductor with Chain Conformational Transformation for stabilizing Interfacial Phase of High-Voltage Lithium Metal Batteries

In solid-state lithium metal batteries (SSLMBs), the inhomogeneous electrolyte-electrode interphase layer aggravates the interfacial stability, leading to discontinuous interfacial ion/charge transport and continuous degradation of the electrolyte. Herein, we constructed an anion-modulated ionic conductor (AMIC) that enables in situ construction of electrolyte/electrode interphases for high-voltage SSLMBs by exploiting conformational transitions under multiple interactions between polymer and lithium salt anions. Anions modulate the decomposition behavior of supramolecular poly (vinylene carbonate) (PVC) at the electrode interface by changing the spatial conformation of the polymer chains, which further enhances ion transport and stabilizes the interfacial morphology. In addition, the AMIC weakens the “Li⁺-solvation” and increases Li⁺ vehicle sites, thereby enhancing the lithium-ion transport number (t_Li⁺=~0.67). Consequently, Li || LiNi_0.8Co_0.1Mn_0.1O₂ cell maintains about 85 % capacity retention and Coulombic efficiency >99.8 % in 200 cycles at a charge cut-off voltage of 4.5 V. This study provides a new understanding of lithium salt anions regulating polymer chain segment behavior in the solid-state polymer electrolyte (SPE) and highlights the importance of the ion environment in the construction of interfacial phases and ionic conduction.