Solvation Sheath Research Articles

Kinetic and thermodynamic synergy of organic small molecular additives enables constructed stable zinc anode

An organic small molecule additive zinc formate is introduced to construct stable Zn metal interphase by electrochemical kinetic control and thermodynamic adjustment. It partially forms a water-formate concomitant dipole layer at the internal Helmholtz electrical double layers (HEDLs) under the preferential adsorption function of formate on Zn surface, reducing the occurrence of side reactions at phase interface. Meanwhile, free formate in HEDLs regulates the Zn2+ solvation sheath structure to accelerate the de-solvation, transference, and deposition kinetics of Zn2+. Besides, the hydrolysis reaction of zinc formate increases the hydrogen evolution overpotential, inhibiting the thermodynamic tendency of hydrogen evolution. Consequently, it presents stable cycle for more than 2400 h at 5 mA cm−2, as well as an average Coulombic efficiency of 99.8% at 1 A g−1 after 800 cycles in the Zn||VO2 full cell. The interphase engineering strategy zinc anode by organic small molecular brings new possibility towards high-performance aqueous zinc-ion batteries.

Achieving Practical High-Energy-Density Lithium-Metal Batteries by a Dual-Anion Regulated Electrolyte.

Lithium-metal batteries (LMBs) using lithium-metal anodes and high-voltage cathodes have been deemed as one of the most promising high-energy-density battery technology. However, its practical application is largely hindered by the notorious dendrite growth of lithium-metal anodes, the fast structure degradation of the cathode, and insufficient electrode-electrolyte interphase kinetics. Here, a dual-anion regulated electrolyte is developed for LMBs using lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and lithium difluoro(bisoxalato)phosphate (LiDFBOP) as anion regulators. The incorporation of TFSI- in the solvation sheath reduces the desolvation energy of Li+ , and DFBOP- promotes the formation of highly ion-conductive and sustainable inorganic-rich interphases on the electrodes. Significantly enhanced performance is demonstrated on Li||LiNi0.83 Co0.11 Mn0.06 O2 pouch cells, with 84.6% capacity retention after 150 cycles in 6.0 Ah pouch cells and an ultrahigh rate capability up to 5 C in 2.0 Ah pouch cells. Furthermore, a pouch cell with an ultralarge capacity of 39.0 Ah is fabricated and achieves an ultrahigh energy density of 521.3Wh kg-1 . The findings provide a facile electrolyte design strategy for promoting the practical utilization of high-energy-density LMBs.

Regulating the solvation sheath of zinc ions by supramolecular coordination chemistry toward ultrastable zinc anodes

AbstractAqueous zinc‐ion batteries (ZIBs) have attracted extensive interest for the next‐generation batteries, which, however, are facing great challenges due to the poor reversibility of zinc (Zn) anodes and side reactions of water decomposition. Herein, we demonstrated a strategy that the solvation sheath of Zn ions could be facilely regulated by supramolecular coordination chemistry by adding small amounts of cyclodextrins (CDs) and, hence, inhibited the side reactions and side products, widened the electrochemical window, facilitated the homogenous deposition of Zn ions, refined the Zn grains, and enhanced the stability of Zn anodes. Importantly, we demonstrated that compared with α‐ and β‐CD, the γ‐CD showed the best regulation effect of the solvation sheath of Zn ions either at the same molar ratio or at the same mass concentration, which could be ascribed to their difference in supramolecular coordination chemistry and the strongest interaction of γ‐CD with Zn ions. As a result, with γ‐CD, the Zn//Zn symmetric cells showed ultrahigh stability with a cycling lifespan of over 2400 h at a current density of 1 mA/cm2. These results highlight the regulation of solvation sheath by supramolecular coordination chemistry for highly stable Zn anodes and pave a new way to realize high‐performance ZIBs.

Hydrogen-Bonded Organic Framework as Superior Separator with High Lithium Affinity C═N Bond for Low N/P Ratio Lithium Metal Batteries.

Lithium dendrite and side reactions are two major challenges for lithium metal anode. Here, the highly lithophilic triazine ring in the hydrogen-bonded organic framework is recommended to accelerate the desolvation process of lithium ions. Among them, the formation of Li-N bonds between lithium ions and the triazine ring in CAM reduces the diffusion energy barrier of Li+ crossing the SEI interface and the desolvation energy barrier of Li+ exiting from the solvent sheath so that the rapid and homogeneous deposition of lithium-ion can be achieved. Meanwhile, the lithium-ion migration coefficient can be as high as 0.70. CAM separator is used to assemble lithium metal batteries with nickel-rich cathodes (NCM 622). When N/P = 8 and 5, the capacity retention rates of Li-NCM 622 full cell are 78.2% and 80.5% after 200 and 110 cycles, respectively, and the Coulomb efficiency can be maintained at 99.5%, showing excellent cycle stability.

Stable Li Metal Anode Enabled by Simultaneous Regulation of Electrolyte Solvation Chemistry and The Solid Electrolyte Interphase

AbstractThe application of Li metal batteries is hindered by the uncontrollable growth of Li dendrites due to the lack of control over Li ion transfer and the formation of solid electrolyte interphase (SEI). Herein, polypropylene (PP) separator modified with acyclic polyaminoborane (PAB, (NH2‐BH2)n) and polyiminoborane (PIB, (NH═BH)n) is developed to regulate electrolyte solvation chemistry and simultaneously facilitate the construction of robust SEI. The mediating effect of PAB and PIB promotes favorable formation of (O)2Li+N to weaken the Li bonds between Li ion and solvent in the electrolyte, which homogenizes Li ion diffusion and reduces the desolvation barrier of Li ions. Additionally, the increase of anions content in the solvation sheath and the reaction between Li metal and PAB and PIB can induce the formation of [LiNBH]n‐enhanced SEI enriched with LiF and Li3N that have Li ion conductivity and mechanical strength to tolerate the volume change of Li metal anode. Therefore, the symmetric cell exhibits a cycling lifetime of over 4000 h.

An efficient electrolyte additive of 1,3,6-hexanetricarbonitrile for high performance aqueous zinc-ion batteries

The growth of Zn dendrites and parasitic side reactions between electrode and electrolyte are major obstacles to the development of rechargeable aqueous zinc-ion batteries. To address these critical issues, the use of nitrile organic compounds as electrolyte additives holds great promise. Herein, for the first time, we prepared a small volume concentration (x) of 1,3,6-Hexanetricarbonitrile (HTCN-x) as additives into zinc trifluoromethanesulphonate (Zn(OTF)2) electrolyte and studied their electrochemical properties in Zn||ZnxV2O5·nH2O (Zn||ZVO) cells. It was found that the strong interaction between H2O and HTCN could significantly reduce the population of solvated H2O outside the solvation sheath, leading to reduced side reactions in the aqueous Zn(OTF)2 electrolyte. Moreover, the HTCN additive also facilitates the formation of strong and stable solid electrolyte interphase (SEI) film on the surface of the Zn anode, which effectively prevents the growth of Zn dendrites and the anode corrosion caused by the electrolyte. As a result, the HTCN-x (x = 0.3) electrolyte enabled the symmetrical Zn||Zn cell to cycle over 950 h at a current of 1 mA cm−2 with a limited capacity of 1 mAh cm−2. When the HTCN-0.3 electrolyte was used in Zn||ZVO cell, the cell delivered a high initial capacity of 355.6 mAh g−1 at 0.1 A g−1 and maintained a high capacity of 330.0 mAh g−1 at 1 A g−1 after 465 cycles.

A Multifunctional Organic Electrolyte Additive for Aqueous Zinc Ion Batteries Based on Polyaniline Cathode.

The practical applications of aqueous zinc ion batteries are hindered by the formation of dendrites on the anode, the narrow electrochemical window of electrolyte, and the instability of the cathode. To address all these challenges simultaneously, a multi-functional electrolyte additive of 1-phenylethylamine hydrochloride (PEA) is developed for aqueous zinc ion batteries based on polyaniline (PANI) cathode. Experiments and theoretical calculations confirm that the PEA additive can regulate the solvation sheath of Zn2+ and form a protective layer on the surface of the Zn metal anode. This broadens the electrochemical stability window of the aqueous electrolyte and enables uniform deposition of Zn. On the cathode side, the Cl- anions from PEA enter the PANI chain during charge and release fewer water molecules surrounding the oxidized PANI, thus suppressing harmful side reactions. When used in a Zn||PANI battery, this cathode/anode compatible electrolyte exhibits excellent rate performance and long cycle life, making it highly attractive for practical applications.

Exceptional Li‐Rich Mn‐Based Cathodes Enabled by Robust Interphase and Modulated Solvation Microstructures Via Anion Synergistic Strategy

AbstractCoupling Li‐rich Mn‐based oxide (LRMO) cathodes with lithium metal anodes is crucial to enabl high‐energy batteries. However, capacity decline of LRMO caused generally by unexpected parasitic reactions needs to be solved. Herein, an anion synergistic strategy is developed to manipulate the solvation structure to boost the electrochemical performance of high‐voltage lithium batteries. Multi‐salt electrolytes containing TFSI−, DFOB−, and DFBOP− anions are formulated via facilitating a distinctive aggregate, Li+‐(DFBOP−)0.10(DFOB−)0.49(TFSI−)0.51EC0.63EMC2.49DEC0.77, which can reduce the penetration of other anions into the first solvation sheath and strengthen the interaction between Li+ ions and solvent molecules simultaneously. The solvation structure is studied by molecular dynamics (MD) and its feature is found to be able to enhance the transport kinetics of Li+ effectively and favor the formation of an inorganic‐rich interphase. Corrosion of the Al collector is retarded effectively by a cathode−electrolyte interphase (CEI) constructed by the decomposition of DFBOP−, thereby enhancing the cyclability. In addition, Li||LRMO cell can retain its 85% initial capacity after 650 cycles at 1 C. This study provides a guideline to formulate high‐voltage electrolytes with excellent kinetics by regulating the microstructures of solvation and interphases via anion formulation engineering.

Optimizing NaF‐Rich Solid Electrolyte Interphase for Stabilizing Sodium Metal Batteries by Electrolyte Additive

AbstractNaF‐rich electrode–electrolyte interphases play crucial roles in determining the cycling stability of sodium metal batteries (SMBs) because of their electronic insulation and mechanical stability. In this work, perfluorobenzene (PFB) is proposed as the additive to contribute the formation of NaF‐rich solid electrolyte interphases (SEI). PFB at the periphery of the solvation layer can pull out a part of the EC with the lowest solvation energy by Van der Waals forces, thus allowing more to participate in the Na+ solvation layer and form an anion‐aggregated solvation sheath, thus promoting the decomposition of to produce NaF. In addition, PFB has a higher highest occupied molecular orbital and lower lowest unoccupied molecular orbital energy level, which also preferentially decomposes to produce NaF at both electrodes. Benefiting from the intensified NaF ratio in SEI, the Na||Na symmetric cells with such an electrolyte achieves a superior cycling life over 350 h at 1 mA cm−2, and the Na||Na3V2(PO4)2O2F batteries also realize ultrahigh cycling performance with 88.8% capacity retention after 500 cycles.

Cell-nucleus structured electrolyte for low-temperature aqueous zinc batteries

Rechargeable aqueous zinc (Zn) batteries hold great promise for large-scale energy storage, but their implementation is plagued by poor Zn reversibility and unsatisfactory low-temperature performance. Herein, we design a cell-nucleus structured electrolyte by introducing low-polarity 1,2-dimethoxyethane (DME) into dilute 1 M zinc trifluoromethanesulfonate (Zn(OTf)2) aqueous solution, which features an OTf−-rich Zn2+-primary solvation sheath (PSS, inner nucleus) and the DME-modulated Zn2+-outer solvation sheath (outer layer). We find that DME additives with a low dosage do not participate in the Zn2+-PSS but reinforce the Zn-OTf− coordination, which guarantees good reaction kinetics under ultralow temperatures. Moreover, DME breaks the original H-bonding network of H2O, depressing the freezing point of electrolyte to −52.4 °C. Such a cell-nucleus-solvation structure suppresses the H2O-induced side reactions and forms an anion-derived solid electrolyte interphase on Zn and can be readily extended to 1,2-diethoxyethane. The as-designed electrolyte enables the Zn electrode deep cycling stability over 3500 h with a high depth-of-discharge of 51.3% and endows the Zn||V2O5 full battery with stable cycling over 1000 cycles at −40 °C. This work would inspire the solvation structure design for low-temperature aqueous batteries.

Stable Non‐flammable Phosphate Electrolyte for Lithium Metal Batteries via Solvation Regulation by the Additive

AbstractThe application of lithium metal batteries (LMBs) is impeded by safety concerns. Employing non‐flammable electrolytes can improve battery reliability while the cost and performance deterioration limit their popularization. Herein, a high‐performance non‐flammable electrolyte is designed, 1.5 m LiTFSI in propylene carbonate (PC)/triethyl phosphate (TEP) (4:1 by vol.) with 4‐nitrophenyl trifluoroacetate (TFANP) as the additive, which can facilitate the construction of LiF‐rich solid electrolyte interphase (SEI) on Li anode surface and cathode electrolyte interphase (CEI) on cathode surface through its prioritized decomposition. In TFANP‐containing electrolyte, the decreased TEP coordination number in the solvation sheath relieves the adverse effect of active TEP on both the SEI and CEI for suppressing the growth of Li dendrites and reducing the continuous electrolyte consumption. Thus, the Li||LiNi0.6Co0.2Mn0.2O2 battery with such an electrolyte can deliver 132 mAh g−1 after 150 cycles with high coulombic efficiency (99.5%) and superior rate performance (110 mAh g−1 at 5 C, 1 C = 200 mA g−1). This work provides a new additive insight on non‐flammable electrolyte for reliable LMBs.

A Dual‐Functional Organic Electrolyte Additive with Regulating Suitable Overpotential for Building Highly Reversible Aqueous Zinc Ion Batteries

AbstractAqueous zinc ion batteries (AZIBs) with high safety, low cost, and eco‐friendliness advantages show great potential in large‐scale energy storage systems. However, their practical application is hindered by low Columbic efficiency and unstable zinc anode resulting from the side reactions and deterioration of zinc dendrites. Herein, tripropylene glycol (TG) is chosen as a dual‐functional organic electrolyte additive to improve the reversibility of AZIBs significantly. Importantly, ab initio molecular dynamics theoretical simulations and experiments such as in situ electrochemical impedance spectroscopy, and synchrotron radiation‐based in situ Fourier transform infrared spectroscopy confirm that TG participates in the solvation sheath of Zn2+, regulating overpotential and inhibiting side reactions; meanwhile, TG inhibits the deterioration of dendrites and modifies the direction of zinc deposition by constructing an adsorbed layer on the zinc anode. Consequently, a Zn‐MnO2 full cell with TG electrolyte exhibited a specific capacity of 124.48 mAh g‐1 after 1000 cycles at a current density of 4 A g‐1. This quantitative regulation for suitable solvation sheath and adsorbed layer on zinc anode, and its easy scalability of the process can be of immediate benefit for the dendrite‐free, high‐performance, and low‐cost energy storage systems.

Hydrated solvation suppression of zinc ions for highly reversible zinc anodes

Low-cost and high-safety aqueous zinc batteries are promising for large-scale energy storage applications. However, the actual performance of aqueous zinc batteries is hampered by the irreversibility of the zinc metal anode originating from the dendrite growth and side reactions, which are associated closely with the hydrated solvation sheath of Zn2+ ions in aqueous electrolytes. Here, dimethylacetamide is employed as a water dragger agent in low-concentration ZnSO4 electrolytes to reshape the solvation structure of Zn2+ ions. Theoretical calculations and experimental investigations reveal that a low fractional addition of dimethylacetamide in aqueous ZnSO4 electrolytes performs strong interactions with water molecules and Zn2+ ions, which inhibits hydrated Zn2+–H2O solvation, facilitates Zn2+-SO42- association and captures free water molecules via H-bonds formation. The coulombic efficiency of Zn plating/stripping is improved from 94.3% to 98.1% and can be stabilized at 99.5% over 200 cycles with the hybrid electrolyte. The cycle lifespan of the Zn symmetric cell is prolonged over 1000 h at 1 mA cm−2 and over 450 h at 5 mA cm−2 with the dimethylacetamide -hybrid electrolyte, which are over fourfold higher than that of the pristine ZnSO4 electrolyte. Moreover, when the designed electrolyte is incorporated in full cells, the Zn-MnO2 cell exhibits an improved rate performance and an excellent long-term cyclability with a capacity-retention rate of 81% over 2,000 cycles at 1 A g−1. This work provides a feasible strategy for the development of highly stable aqueous zinc batteries.

Spontaneous Desaturation of the Solvation Sheath for High-Performance Anti-Freezing Zinc-Ion Gel-Electrolyte.

In recent years, gel-electrolyte becomes pivotal in preventing hydrogen evolution, reducing dendrite growth, and protecting the zinc metal anode for zinc-ion batteries. Herein, a polyvinyl alcohol-based water-organic hybrid gel electrolyte with Agar and dimethyl sulfoxide is designed to construct the spontaneous desaturation of the solvation sheath for reducing hydrogen evolution and dendrite growth at room temperature and even low temperature. According to experimental characterization and theoretical calculations, the well binding between multihydroxy polymer and H2 O is achieved in the hybrid desaturated gel-electrolyte to regulate the inner and outer sheath. The ionic conductivity of hybrid gel-electrolyte reaches 7.4 mS cm-1 even at -20°C with only 0.5m zinc trifluoromethanesulfonate (Zn(OTf)2 ). The Zn symmetric cells cycle over 1200h under 26 and -20°C with improved mechanical properties and electrochemical performance. The asymmetric Zn || Cu cell with hybrid gel electrolyte reaches ≈99.02% efficiency after 250 cycles. The capacity of full cell is maintained at around 74 mAh g-1 with almost unchanged retention rate from 50 to 300 cycles at -20°C. This work provides an effective strategy for desaturated solvation to reach anti-freezing and high-density Zn energy storage devices.

Regulating solvation sheath by introducing multifunctional fluoride boronic esters for highly efficient magnesium stripping/plating

Rechargeable magnesium batteries (RMBs) are considered a highly promising energy storage system. However, the lack of low-cost and highly effective electrolytes severely hinders the development of RMBs. Herein, a tris(2,2,2-trifluoroethyl) borate (B(Otfe)3) co-solvent is introduced into the magnesium-aluminum-chloride complex electrolyte. The electrophilic B(Otfe)3 as an electron pair acceptor can react with the passivation layer to avoid the electrolytic conditioning process. The B(Otfe)3-modified solvation structure with low desolvation energy increases the concentration of active cation, effectively improving the ionic conductivity and area current density. Meanwhile, the B(Otfe)3-modified solvation ions with lower LUMO energy induce the formation of the B-F/B-O-containing and MgF2-containing solid electrolyte interphase (SEI), reducing the interfacial transfer impedance. The prepared B(Otfe)3/MgCl2/AlCl3 (BMA) electrolyte exhibits excellent electrochemical performance with low overpotential (∼122 mV), high average coulombic efficiency (CE) (∼98.2%) and long-term cycling stability (1000 h). Moreover, the BMA electrolyte shows good compatibility with Mo6S8 and CuS cathodes. The Mg|CuS full cell keeps a high specific capacity of 231 mAh g−1 after 80 cycles at 56 mA g−1, and the Mg|Mo6S8 cell operates 1000 cycles with an average CE of nearly 100%. This work provides an effective way to simultaneously improve the electrolyte solvation sheath and SEI structure for stable magnesium batteries.

Electrolyte solvation chemistry to construct an anion-tuned interphase for stable high-temperature lithium metal batteries

Lithium metal batteries are regarded as promising alternative next-generation energy storage systems. However, the unstable anode interphase results in dendrite growth and irreversible lithium consumption with low Coulombic efficiency (CE). Herein, we rationally design a Li+ coordination structure via electrolyte solvation chemistry. Nitrate anions are aggregated in the solvation sheath, even at low concentration in a solvent with moderate solvation ability, which promotes Li+ desolvation and constructs a nitrate anion-tuned interphase. Meanwhile, a high-donor-number solvent is introduced as an additive to strongly coordinate with Li+, which accelerates the ion-transfer kinetics and rate performance. This not only results in micro-sized lithium deposition and a high CE of 99.5% over 3500 ​h, but also enables superior anode stability even under 50% depth plating/stripping and with a lean electrolyte of 3 ​g ​Ah−1 at 50 ​°C. A lithium–sulfur battery exhibits a prolonged lifespan of 2000 cycles with an average CE of 100%. A full battery using 1x excess lithium exhibits a high capacity near 1600 ​mAh ​gS−1 for 100 cycles without capacity loss. Moreover, a 0.55 ​Ah pouch cell delivers a reversible energy density of 423 ​Wh ​kg−1 based on these electrodes and electrolyte.

Erythritol-strengthen electrolytes effectively improve the electrochemical stability window of aqueous symmetric supercapacitor

Due to the advantages of high safety, high conductivity and low cost, the supercapacitor with aqueous electrolytes exhibits the great prospects in the future energy storage market. However, the narrow electrochemical stability window (ESW) of electric double-layer supercapacitor leads to its low energy density, which seriously limits its application. Herein, we demonstrate erythritol (Et) additive could efficaciously decrease the water molecules in the solvation sheath and break the hydrogen bond network of aqueous electrolytes, which resulting in expanded ESW. Especially, symmetric supercapacitor based on 37.9% Et additive to 1 M LiTFSI electrolyte expands ESW from 1.8 to 2.1 V, and the energy density increased to 13.3 Wh kg−1 with high specific capacitance of 86.6F g−1 and the capacitance retention rate of 73.8% after 10,000 cycles. Therefore, this study affords an efficient strategy to achieve high energy density aqueous supercapacitor.

Regulating the Inner Helmholtz Plane with a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn-Ion Batteries.

The performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution reactions (HER) and Zn dendrites both originate from abundant free H2 O and random Zn deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py-to-H2 O volume ratio), for regulating molecule distribution inside IHP. Density functional theory (DFT) calculations and molecular dynamics (MD) simulation verify that incorporated Py additive could tailor Zn2+ solvation sheath and exclude H2 O molecules from IHP effectively, which is in favor of preventing H2 O decomposition. Consequently, even at extreme conditions such as high depth of discharge (DOD) of 80 %, the symmetric cell based on Py additive can sustain approximately 500 h long-term stability. This efficient strategy with high DN additives furnishes a promising direction for designing novel electrolytes and promoting the practical application of AZIBs, despite inevitably introducing trace organic additives.

Dual Role of Bis(borate) Additive in Electrode/Electrolyte Interface Layer Construction for High-Voltage NCM 523 Cathode

Increasing the working voltage of a layered oxide cathode is an efficient way to lift the energy density of lithium-ion batteries. However, uncontrollable side reactions and excessive electrolyte decomposition take place at high voltage. Bulk cathode structure degradation and formation of a high working voltage induce excessive growth of the solid-electrolyte interface (SEI) layer and overconsumption of the electrolyte. Construction of a high-voltage stable SEI layer is crucial to enhance the electrochemical performance. In this work, trimethylene borate (TMEB) as a borate ester additive is used to improve the cycled stability of NCM523 cells at 4.5 V charging-cutoff voltage. On one hand, TMEB can be preferentially decomposed during cycling and participate in the film formation process on the surfaces of both anode and cathode. On the other hand, TMEB can tune the solvation sheath by expelling the carbonate solvent molecules out of the solvation sheath to suppress decomposition of the electrolyte. The cells cycled with the 0.5 wt % TMEB-containing electrolyte exhibit improved cycling stability after 200 cycles with the capacity retention of 90.9% indicating TMEB to be an effective additive to improve the lithium-ion batteries at higher charging-cutoff voltage.

Regulating the Inner Helmholtz Plane with a High Donor Additive for Efficient Anode Reversibility in Aqueous Zn‐Ion Batteries

AbstractThe performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution reactions (HER) and Zn dendrites both originate from abundant free H2O and random Zn deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py‐to‐H2O volume ratio), for regulating molecule distribution inside IHP. Density functional theory (DFT) calculations and molecular dynamics (MD) simulation verify that incorporated Py additive could tailor Zn2+ solvation sheath and exclude H2O molecules from IHP effectively, which is in favor of preventing H2O decomposition. Consequently, even at extreme conditions such as high depth of discharge (DOD) of 80 %, the symmetric cell based on Py additive can sustain approximately 500 h long‐term stability. This efficient strategy with high DN additives furnishes a promising direction for designing novel electrolytes and promoting the practical application of AZIBs, despite inevitably introducing trace organic additives.