硝酸锂（LiNO3）作为电解液添加剂的研究起源于锂硫电池领域，其核心参数的迭代情况

… additive to the electrolyte solution, suppressing the shuttle phenomena in Li-sulfur batteries. … of LiNO 3 in electrolyte solutions and with electrodes relevant to Li-S cells. EQCM UV-Vis …

… this is because this electrolyte has the highest conductivity… electrolyte of Li-S cells are known to be related to effects centred on the lithium anode, the short-term influence of this additive …

Abstract Lithium nitrate (LiNO3) has been reported as a novel additive to improve the cycling performance of Li/S batteries because LiNO3 suppresses the polysulfide shuttling problem. However, several studies indicate that LiNO3 instead decreases the battery performance due to the formation of irreversible products at the cathode. In this study, we investigated the role of LiNO3 in irreversible product formation. To elucidate the effect of LiNO3, electrolytes with an excess concentration of LiNO3 were employed in the Li/S cell for discharge and cyclic voltammetry tests. In the discharge test, a distortion of the discharge profile near the end of the discharge was clearly observed for the Li/S battery using a 0.8 M LiNO3 electrolyte. The third plateau (distortion) representing the irreversible reaction was significantly more pronounced when a poor cathode that was not subjected to heat-treatment was used. In addition, cyclic voltammetry tests showed an extra cathodic peak at 1.5 V corresponding to the irreversible reaction. It was confirmed that the irreversible product can be partially recovered to high-order polysulfides and elemental S8 by applying a potential of over 2.9 V. Finally, to provide a more detailed explanation, we carried out a computational simulation of the irreversible reaction. The simulation indicated that the reaction was related to the formation of crystallized lithium sulfide, and the simulation results successfully reproduced the third plateau (distortion) in the discharge profile.

… 3 in lithiated Nafion polymer and added an electrolyte co-solvent (1,1,2,… Li||S full cells with this SEI achieved a long lifespan of 250 cycles, far exceeding cells with a routine SEI. The Li||S …

… liquid additives to stabilise lithium metal surfaces in Li–S batteries. We also compare the cycling performance of cells with and without both the ionic liquid and LiNO 3 additives. Li–S …

… into the important role of LiNO 3 for the protection of lithium anodes, which will be beneficial for the further development of new electrolyte additives for high-performance Li-S batteries. …

… research studies on LiNO 3 as an additive in Li–S batteries, we find that there are other … better understand Li–S batteries. The important effects of LiNO 3 in a Li–S battery system should …

… The design of practical Li single bond S batteries requires more research on the parameters of electrolyte additives under high‑sulfur-loading conditions. After gradient increasing the …

Lithium–sulfur (Li–S) batteries, with theoretical energy densities exceeding 2600 Wh kg−1, are poised to revolutionize energy storage. However, their practical viability hinges on resolving two critical challenges: uncontrolled lithium dendrite growth at the anode and polysulfide shuttling at the sulfur cathode. Here, a compound additive integrating lithium nitrate (LiNO3), sodium saccharin (SAC), and octaphenyl polyoxyethylene (OP‐10) is proposed to construct an electrolyte for Li–S battery. With the compound additive added, the as‐prepared electrolyte is capable of evolving a robust solid electrolyte interphase (SEI) with refined morphology while suppressing polysulfide reactivity. The synergistic effects of this additive enable Li|Li symmetric cells to achieve unprecedented cycling stability (>1400 h at 1 mA cm−2 and 3 mAh cm−2) and Li–S full cells with high sulfur loading (4.12 mg cm−2) to retain 2.72 mAh cm−2 after 150 cycles. This work underscores the importance of dual‐electrode stabilization in electrolyte design, offering a scalable strategy for high‐energy‐density Li–S batteries and related systems plagued by dendrites and shuttle effects. This study highlights the effectiveness of synergistic electrolyte engineering in suppressing lithium dendrites and polysulfide shuttling, providing new insights for the development of high‐performance Li–S batteries and other energy storage systems facing similar challenges.

Lithium sulfur (Li/S) batteries suffer from "shuttle" reactions as soluble polysulfide species continuously migrate to and from the Li-metal anode. As a consequence, the loss of active material and reactions at the surface of Li limit practical applications of Li/S batteries. LiNO3 has been proposed as an electrolyte additive to address the "shuttle" reactions, due to its ability to aid in the formation of stable solid electrolyte interphase (SEI) at the Li-metal, limiting polysulfide shuttling. However, LiNO3 is continuously consumed during cycling, in particular at low current rates, thus the Li/S battery cycle-life is limited by its concentration in the electrolyte. In this work we propose the use of an ionic liquid (Py1,4TFSI) as an additive to enable longer cycle-life of Li/S batteries. By tuning the IL concentration, we demonstrate an enhanced stability of the SEI and lower flammability of the solutions, i.e. higher safety of the battery. The Li/S cell built at high sulfur mass loading (4 mg cm-2) using the IL-based electrolyte demonstrated a stable capacity of 600 mAh g-1 for more than double of cycles of a cell using LiNO3 additive.

… , affecting Li/S battery performance. ► Discharge mechanism of Li/S battery is explained from … functions of LiNO 3 in rechargeable Li/S batteries by using a high sulfur loading cathode. …

… these parasitic reactions, different additives are used in the liquid electrolyte. Lithium nitrate (LiNO 3 ) is nowadays a common such electrolyte additive in Li–S batteries, often used in …

… In this study, we focused on improving the self-discharge behavior of Li/S batteries by reducing … In order to study the effect of LiNO 3 electrolyte additive on the self-discharge of the Li/S-…

It is generally understood that the reduction of nitrate on the metallic Li surface aids in the formation of a solid-electrolyte interphase. LiNO3 is, therefore, frequently used as an electrolyte additive to help suppress the polysulfide redox shuttle in lithium-sulfur (Li-S) batteries. Although LiNO3 enables cycling of cells with considerably improved Coulombic efficiency and cyclic performance, the self-discharge behavior has largely been neglected. We present in this work a basic but systematic study to assess self-discharge of Li-S batteries with electrolytes possessing LiNO3. Comparative electrochemical tests and interfacial analysis reveal that the redox shuttle is fast enough to cause cells to self-discharge at a relatively rapid rate with limited concentration of the LiNO3 additive. Despite the capacity loss of a full-charged cell under rest for one day can be controlled to 2% with LiNO3 concentration as high as 0.5 M, the development of a practically viable Li-S technology looks like a daunting challenge. Further increasing LiNO3 would potentially cause more irreversible reduction of LiNO3 on the cathode during the first discharge. Therefore, a possible pathway for a long shelf life and low self-discharge is offered as well by the synergic protection of the separator and stabilization of the Li anode surface. The cell using a nanosized Al2O3-coated microporous membrane and a LiNO3-possessing electrolyte exhibits an extremely suppressed self-discharge, providing an alternative perspective for the practical use of Li-S batteries.

… of cathode binders with modified electrolytes in lithium–sulfur batteries. We compared the … strongly facilitated the decomposition of the electrolyte additive LiNO 3 at potentials lower than …

… In order to further understand the function of LiNO 3 in the Li–S batteries, in the present work … This finding will be very helpful for further development of the rechargeable Li–S batteries. …

… This work reveals that good reversibility of the Li/S batteries with a LiNO 3 -contained electrolyte can be established between elemental sulfur and insoluble Li 2 S 2 through a …

… concentration of the electrochemically active species, we can take the peak current in this case as an indicator of the concentration… from the coulombic efficiency on galvanostatic cycling. …

… and improve the coulombic efficiency of the Li–S battery was the addition of … Li–S batteries. To better understand how it functions, we prepared electrolytes with different concentrations …

… cycling performance with the coulombic efficiency above 95% … The Li/S battery with the LiNO 3 modified electrolyte shows … and dissolution in different concentration of LiNO 3 modified …

Li metal thickness has been considered a key factor in determining the electrochemical performance of Li metal anodes. The use of thin Li metal anodes is a prerequisite for increasing the energy density of Li secondary batteries intended for emerging large-scale electrical applications, such as electric vehicles and energy storage systems. To utilize thin (20 μm thick) Li metal anodes in Li metal secondary batteries, we investigated the synergistic effect of a functional additive (Li nitrate, LiNO3) and a dual-salt electrolyte (DSE) system composed of Li bis(fluorosulfonyl)imide (LiTFSI) and Li bis(oxalate)borate (LiBOB). By controlling the amount of LiNO3 in DSE, we found that DSE containing 0.05 M LiNO3 (DSE-0.05 M LiNO3) significantly improved the electrochemical performance of Li metal anodes. DSE-0.05 M LiNO3 increased the cycling performance by 146.3% [under the conditions of a 1C rate (2.0 mA cm-2), DSE alone maintained 80% of the initial discharge capacity up to the 205th cycle, whereas DSE-0.05 M LiNO3 maintained 80% up to the 300th cycle] and increased the rate capability by 128.2% compared with DSE alone [the rate capability of DSE-0.05 M LiNO3 = 50.4 mAh g-1, and DSE = 39.3 mAh g-1 under 7C rate conditions (14.0 mA cm-2)]. After analyzing the Li metal surface using scanning electron microscopy and X-ray photoelectron spectroscopy, we were able to infer that the stabilized solid electrolyte interphase layer formed by the combination of LiNO3 and the dual salt resulted in a uniform Li deposition during repeated Li plating/stripping processes.

… an effective additive and genuinely beneficial for enhancing electrochemical performance of Li-S … perspective for the design of high-energy-density Li-S batteries beyond LiNO3 additive. …

… Lithium–sulfur (Li–S) batteries have attracted many attentions in the energy storage … the formation of robust solid electrolyte interface (SEI) film composed of LiNO 3 -derived compounds …

Lithium metal batteries (LMBs) have been regarded as one of the most promising alternatives in the post‐lithium battery era due to their high energy density, which meets the needs of light‐weight electronic devices and long‐range electric vehicles. However, technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs. However, lithium nitrate (LiNO 3 ) is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges. To date, considerable research efforts have been devoted toward understanding the roles of LiNO 3 in regulating the surface properties of Li anodes and toward the development of many effective strategies. These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically. To fill this gap, we discuss the recent advances in fundamental and technological research on LiNO 3 and its derivatives for improving the performances of LMBs, particularly for Li–sulfur (S), Li–oxygen (O), and Li–Li‐containing transition‐metal oxide (LTMO) batteries, as well as LiNO 3 ‐containing recipes for precursors in battery materials and interphase fabrication. This review pays attention to the effects of LiNO 3 in lithium‐based batteries, aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.

Lithium–sulfur (Li–S) batteries are promising candidates for next‐generation energy storage systems, but practical use is limited by polysulfide (PS) shuttling and Li metal anode instability. Lithium nitrate (LiNO3) is widely used to mitigate these issues; however, its interfacial effects across the anode, electrolyte, and cathode during operation are not fully understood. Here, operando optical microscopy with a custom side‐by‐side cell enables simultaneous monitoring of the Li anode, liquid electrolyte, and sulfur cathode in a single field of view under conditions with and without LiNO3. In the absence of LiNO3, the Li surface undergoes rough stripping and fragmented, non‐coalescent deposition, accompanied by PS‐induced corrosion and accumulation of parasitic byproducts at the anode‐electrolyte interface. Redness Intensity (RI), introduced to quantify electrolyte‐phase PS dynamics, indicates sustained transport toward the anode and delayed conversion to elemental sulfur. By contrast, LiNO3 induces uniform Li stripping and the growth of aggregated, interconnected deposits, while mitigating PS crossover and promoting efficient sulfur crystallization at the cathode. Complementary SEM‐EDS, UV–vis, XPS, TXM, and CT analyses corroborate these observations. By elucidating the multifunctional role of LiNO3, this study clarifies the interfacial dynamics that govern Li–S battery performance.image

… Lithium nitrate (LiNO 3 ) serves as a highly effective electrolyte additive for lithium metal anodes (LMAs), promoting the formation of a Li 3 N-rich solid electrolyte interphase (SEI) that …

Continuous lithium (Li) depletion shadows the increase in energy density and safety properties promised by zero-excess lithium metal batteries (ZELMBs). Guiding the Li deposits toward more homogeneous and denser lithium morphology results in improved electrochemical performance. Herein, a lithium nitrate (LiNO3 ) enriched separator that improves the morphology of the Li deposits and facilitates the formation of an inorganic-rich solid-electrolyte interphase (SEI) resulting in an extended cycle life in Li||Li-cells as well as an increase of the Coulombic efficiency in Cu||Li-cells is reported. Using a LiNi0.6 Co0.2 Mn0.2 O2 positive electrode in NCM622||Cu-cells, a carbonate-based electrolyte, and a LiNO3 enriched separator, an extension of the cycle life by more than 50 cycles with a moderate capacity fading compared to the unmodified separator is obtained. The relative constant level of LiNO3 in the electrolyte, maintained by the LiNO3 enriched separator throughout the cycling process stems at the origin of the improved performance. Ion chromatography measurements carried out at different cycles support the proposed mechanism of a slow and constant release of LiNO3 from the separator. The results indicate that the strategy of using a LiNO3 enriched separator instead of LiNO3 as a sacrificial electrolyte additive can improve the performance of ZELMBs further by maintaining a compact and thus stable SEI layer on Li deposits.

… Dead Li is electrically non-active, which is associated with Li consumption and an increase in internal resistance, resulting in reduced Coulombic efficiency (CE) and capacity decay of …

… Therefore, the combined strategy for a Li-metal anode with a stable structure and robust … electrolyte with a 3D composite Li-metal anode was rationally designed for high-performance …

To be commercially viable, the electrolyte for lithium metal batteries (LMBs) must enable both long cycle life and fast charging characteristics under extreme conditions (high cathode loading, low negative/positive ratio, and low electrolyte/cathode ratio). While LiFSI‐based electrolytes typically provide LMBs with extended cycle life, they often fall short in terms of kinetics. This study, for the first time, demonstrates that the LiNO3‐based electrolyte can simultaneously achieve excellent reversibility and rapid kinetics in LMBs, outperforming state‐of‐the‐art LiFSI‐based electrolytes. Notably, LiNi0.8Co0.1Mn0.1O2 (NCM811) || Li batteries exhibit 80% capacity retention after 430 cycles, along with outstanding rate performance (2.35 mAh cm⁻2 at 12 mA cm−2) under practical conditions (20 mg cm−2 NCM811, 50 µm Li foil, and 5.6 mL Ah⁻¹ electrolyte). The rapid kinetics can be attributed to the efficient transport of lithium ions through both the bulk electrolyte and the electrode/electrolyte interphases. The work highlights the significance of low‐cost LiNO3 salt and presents an alternative pathway to achieving superior performance for lithium metal batteries under extreme conditions.

… electrolytes that are not only more compatible with Li metal … : Figure S5), where coulombic efficiencies for LF30–TEP are … LF30 or LF30–TEP–LiNO3 electrolytes. Also notable here is that…

Manipulating the solvation environment of lithium ions (Li+) in liquid electrolytes is crucial for achieving a stable solid electrolyte interphase (SEI) layer on lithium metal anodes. In this work, we report a method to regulate the Li+ solvation environment in ester-based electrolytes by incorporating lithium nitrate (LiNO3) nanoparticles as an additive. The dipole-dipole interactions at the LiNO3 particle/electrolyte interface result in ordered aggregation of solvent molecules on the surface of LiNO3 particles, forming a molecular confinement layer that drives the formation of a weak Li+ solvation environment. This enables Li+ to bind more readily with anions, facilitates rapid Li+ conduction, and promotes an inorganic-rich SEI. Electrochemical tests show that such changes induced by LiNO3 nanoparticles significantly enhance the Coulombic efficiency, reduce lithium nucleation overpotential, suppress lithium dendrite growth, and extend the cycle life of anode-free cells. Besides, with 6000 ppm of H2O in the electrolyte, cells achieve stable cycling for over 200 cycles with a capacity retention of 71.21%. These findings provide insights into solvent/ion regulation at solid/liquid interfaces in advanced electrolytes.

Low-temperature environments significantly affect the performance of lithium metal batteries, primarily due to the freezing of commercial electrolytes that induced increased energy barriers for lithium-ion migration and desolvation, unstable solid electrolyte interphases (SEI), and lithium dendrite growth. In this work, an electrolyte was developed with lithium nitrate as an additive and lithium bis(trifluoromethanesulfonyl)imide and lithium hexafluorophosphate as the main lithium salts. Li+-NO3- coordination weakens Li+-solvent binding, enabling anion penetration into solvation shells. This multianion-dominated structure promotes Li+ diffusion/desolvation kinetics while enabling inorganic-rich SEI formation and homogeneous Li deposition. Consequently, Li||Li cells exhibit exceptional stability across -30 to 25 °C with over 2000 h cycle life. Li||NCM811 cells demonstrate outstanding rate capability at 25 °C, retaining 94.7% capacity at 2 C and 85.1% at 5 C over 1000 cycles. Notably, under cryogenic conditions at 0.2 C and -30 °C, the cell achieves 92.4% capacity retention after 400 cycles.

… Despite the superior properties of Li metal, the uncontrollable Li dendrite growth … Li metal anode perform a low coulombic efficiency, leading to the poor cycle performance of the Li metal …

… Li metal anode has been plagued by constant Li dendrite growth and low Coulombic efficiency (… -voltage Li metal battery with carbonate electrolytes. As a result, due to the dissolution of …

The development of safe and high-performance Li-metal anodes is crucial to meet the demanded increase in energy density of batteries. However, severe reactivity of Li metal with typical electrolytes and dendrite formation leads to a poor cycle life and safety concerns. Therefore, it is essential to develop electrolytes that passivate the reactivity toward Li metal and suppress dendrite formation. Carbonate electrolytes display severe reactivity toward Li metal; however, they are preferred above the more volatile ether-based electrolytes. Here, a carbonate electrolyte gel polymer approach is combined with LiNO3 as an additive to stabilize Li-metal plating. This electrolyte design strategy is systematically monitored by operando neutron depth profiling (NDP) to follow the evolution of the plated Li-metal density and the inactive lithium in the solid electrolyte interface (SEI) during cycling. Individually, the application of the LiNO3 electrolyte additive and the gel polymer approach are shown to be effective. Moreover, when used in conjunction, the effects are complementary in increasing the plated Li density, reducing inactive Li species, and reducing the overpotentials. The LiNO3 additive leads to more compact plating; however, it results in a significant buildup of inactive Li species in a double-layer SEI structure, which challenges the cell performance over longer cycling. In contrast, the gel polymer strongly suppresses the buildup of inactive Li species by immobilizing the carbonate electrolyte species; however, the plating is less dense and occurs with a significant overpotential. Combining the LiNO3 additive with the gel polymer approach results in a thin and homogeneous SEI with a high conductivity through the presence of Li3N and a limited buildup of inactive Li species over cycling. Through this approach, even high plating capacities, reaching 7 mAh/cm2, can be maintained at a high efficiency. The rational design strategy, empowered by monitoring the Li-density evolution, demonstrates the possibilities of achieving stable operation of Li metal in carbonate-based electrolytes.

Lithium metal batteries (LMBs) are expected to upgrade their energy density to meet the growing battery market demand; however, intractable lithium dendrites and prominent electrode-electrolyte interface problems have been the stumbling block to their practical applications. Electrolytes play a crucial role in LMBs and are directly involved in the establishment of the electrode-electrolyte interface. In particular, low-concentration electrolytes (LCEs) can significantly save electrolyte costs, but the interface issue is more noteworthy. Here, multifunctional acetamide (N-methyl-N-(trimethylsilyl)-trifluoroacetamide, MTA) and lithium nitrate (LiNO3) additives were introduced together to enhance the performance of LMBs in LCEs. The MTA additive effectively removes the trace water and corrosive HF from the electrolyte, thus suppressing lithium salt decomposition and enhancing the stability of LCEs. Moreover, the MTA additive can construct an inorganic-rich interphase layer on the cathode/anode surface to protect the electrode. Especially, MTA can cooperate with LiNO3 additive to suppress lithium dendrites and reduce interfacial impedance, thus effectively enhancing lithium metal anode stability. Benefiting from the introduction of MTA and LiNO3 additives in the LCEs, the Li||NMC811 metal battery still has a capacity of 110 mA h g-1 after 500 cycles at room temperature, while the reference batteries have failed. The rate capacity and high temperature (50 °C) performance of the Li||NCM811 batteries have also been significantly improved. Significantly, this research explores a cost-effective method of using multifunctional additives to enhance LMBs' stability in LCEs.