Nitrate additives for lithium batteries:Mechanisms,applications,and prospects

Lithium-metal batteries(LMBs)are considered as one of the most promising energy storage devices due to the high energy density and low reduction potential of the Li-metal anode.However,the growth of lithium dendrites results in accumulated dead Li and safety issues,limiting the practical application of LMBs.LiNO_(3)is a well-known additive in lithium-sulfur batteries to regulate the solid-electrolyte interphase(SEI),effectively suppressing the redox shuttle of polysulfides.Recently,other nitrates have been investigated in various electrolyte and battery systems,yielding improved SEI stability and cycling performance.In this review,we provide an overview of various nitrates,including LiNO_(3)for lithium batteries,focusing on their mechanisms and performance.We first discuss the effect of nitrate anions on SEI formation,as well as the cathode-electrolyte interphase(CEI).The solvation behavior regulated by nitrates is also extensively explored.Some strategies to improve the solubility of LiNO_(3)in ester-based electrolytes are then summarized,followed by a discussion of recent progress in the application of nitrates in different systems.Finally,further research directions are presented,along with challenges.This review provides a comprehensive understanding of nitrates and affords new and interesting ideas for the design of better electrolytes and battery systems.

Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries

An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.

Regulating dissolution chemistry of nitrates in carbonate electrolyte for high-stable lithium metal batteries

Lithium metal batteries(LMBs)have received increasing attention due to the high energy density.However,the practical application of LMBs is limited due to the incompatibility of ester electrolytes.Transition metal(TM)nitrates have been reported as effective additives in ester electrolyte to improve the stability of lithium anode.Unfortunately,the nitrates are restricted to use due to their poor solubility.We find that the nitrates containing crystal water have high solubility in ester electrolytes.Considering that most TM nitrates contain crystal water and the crystal water can be used as a perfect solubilizer of nitrates,thus,the method is of universality and facile without introducing any solubilizing agent.Herein,In(NO_(3))_(3.6)H_(2)O is chosen as one typical case with increased solubility up to 0.2 M compared with In(NO_(3))_(3)which hardly dissolves in ester electrolyte.The additive promotes the rapid and stable formation of the solid electrolyte interface(SEI),which effectively inhibits the lithium dendrites formation.Moreover,the induced cathode electrolyte interface(CEI)maintains the structural stability of Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811).As a result,the electrochemical performance of Li|NCM811 cell is obviously improved.Our study provides a new idea for dissolving nitrates in ester electrolytes and discloses the synergistic function of TM-ions.

Experimental and modeling investigations on the unexpected hydrogen sulfide rebound in a sewer receiving nitrate addition: Mechanism and solution

Biogenic hydrogen sulfide is an odorous, toxic and corrosive gas released from sewage in sewers. To control sulfide generation and emission, nitrate is extensively applied in sewer systems for decades. However, the unexpected sulfide rebound after nitrate addition is being questioned in recent studies. Possible reasons for the sulfide rebounds have been studied,but the mechanism is still unclear, so the countermeasure is not yet proposed. In this study, a lab-scale sewer system was developed for investigating the unexpected sulfide rebounds via the traditional strategy of nitrate addition during 195-days of operation. It was observed that the sulfide pollution was even severe in a sewer receiving nitrate addition. The mechanism for the sulfide rebound can be differentiated into short-term and long-term effects based on the dominant contribution. The accumulation of intermediate elemental sulfur in biofilm resulted in a rapid sulfide rebound via the high-rate sulfur reduction after the depletion of nitrate in a short period. The presence of nitrate in sewer promoted the microorganism proliferation in biofilm, increased the biofilm thickness, re-shaped the microbial community and enhanced biological denitrification and sulfur production, which further weakened the effect of nitrate on sulfide control during the long-term operation. An optimized biofilminitiated sewer process model demonstrated that neither the intermittent nitrate addition nor the continuous nitrate addition was a sustainable strategy for the sulfide control. To minimize the negative impact from sulfide rebounds, a(bi)monthly routine maintenance(e.g., hydraulic flushing with nitrate spike) to remove the proliferative microorganism in biofilm is necessary.