High-performance organic lithium-bromine battery realized by dual-electron redox reaction

Abstract

The invention provides a high-performance organic lithium-bromine battery based on dual-electron redox chemistry. The battery includes a bromide-based cathode, an anode, an organic electrolyte located between the cathode and the anode, the electrolyte using an organic solvent containing a chloride ion additive, and a separator disposed between the cathode and the anode. The chloride ions in the organic electrolyte trigger conversion of the positive charge bromide ions to promote additional electron transfer, so that the capacity reaches at least 600mAh g <-1 >, and the voltage platform is raised to 3.8 V, thereby achieving an energy density of at least 2000Wh kg <-1 >.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. patent application No. 18 / 499,255 filed on November 1, 2023, and the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0002] The present invention relates generally to the field of battery technology and energy storage. More specifically, the present invention relates to a high-performance organic lithium-bromine battery. Background Art

[0003] In the rapidly developing field of applied electronics, rechargeable lithium-ion batteries have always led the technological innovation. However, with the increasing dependence on electronic devices, the issue of battery energy density has become increasingly urgent. The contradiction between the two key factors, voltage and capacity, is difficult to achieve an effective balance and coordination. This difference can be observed in the distinction between intercalation batteries and conversion batteries. Although intercalation batteries have higher voltages, they have limited capacity, while conversion batteries show the opposite. In view of this dilemma, it is urgent to explore new ways to improve the energy density of batteries.

[0004] Intercalation electrodes (such as metal oxides and polyanion salts) can accommodate a limited number of lithium ions. 1-3 In contrast, conversion cells, especially those using halogen species, exhibit significant redox potentials even in the single electron transfer mechanism. 4-7 Halogen electrodes are still in their early stages, indicating that their potential for development is still very broad.

[0005] Unlike improving the reaction kinetics or stability by improving the traditional single-electron conversion mode, utilizing innovative multi-electron conversion chemistry in halogen systems is undoubtedly a major improvement in electrochemical performance. 8-9 This approach is expected to achieve predictable multiplicative improvements in voltage and capacity. For example, by activating the two-electron redox mechanism, significant advantages were shown, including a 138% increase in capacity and a 0.5V increase in voltage, especially a 138% increase in energy density compared to the single-electron mode. 9 While these advances are promising, they also highlight the challenges facing conventional lithium-iodine batteries, as their performance remains insufficient. This phenomenon shows that most of the effective capacity is concentrated at 2.9V and below. Therefore, bromine (Br) is seen as a promising alternative.

[0006] Even in single-electron mode, the redox potential of bromine is significantly higher than 3.4 V. In addition, the low mass of bromine contributes to the high capacity and energy density after excluding gaseous fluorine (F) and chlorine (Cl) species. 10 In theory, using Bro / Br + The two-electron mode of the redox pair can achieve a double capacity and bring an additional high voltage platform (up to 3.8V). However, there are challenges in practical applications, such as the thermodynamic instability of bromide ions in the positive state in existing electrolytes. In addition, in non-flow batteries, elemental bromine is not suitable as an electrode material due to its inherent mobility and volatility. 11-12 .

[0007] Therefore, there is an urgent need to develop bromine redox chemical systems and find suitable electrodes. The present invention is intended to meet this need. Summary of the invention

[0008] In a first aspect, the present invention provides a high-performance organic lithium-bromine battery realized by a two-electron redox reaction. The lithium-bromine battery includes a bromide-based cathode, an anode, an organic electrolyte between the cathode and the anode, the electrolyte using an organic solvent containing a chloride ion additive, and a separator disposed between the bromide cathode and the anode. The chloride ions in the organic electrolyte trigger the conversion of positively charged bromide ions, promoting additional electron transfer, resulting in a capacity of at least 600 mAh g-1. 1 and increase the voltage platform to 3.8V, thereby achieving at least 2000Wh kg -1 energy density.

[0009] According to one embodiment, the anode comprises a lithium sheet, a lithium foil, or graphite.

[0010] According to one embodiment, in a bromide-based battery, the cathode comprises a current collector, active material, one or more conductive particles, and a binder. The current collector is selected from one or more of carbon cloth, carbon paper, graphite paper, titanium foil / mesh, stainless steel, aluminum foil, and nickel foam.

[0011] According to one embodiment, the active material is selected from one or more of methylammonium bromide, methylammonium bromide tribromide, tetrabutylammonium bromide, tetrabutylammonium tribromide, and hexadecyltrimethylammonium bromide.

[0012] According to one embodiment, the one or more conductive particles include Super-P, carbon black, Ketjen black, activated carbon, and the binder includes polyvinylidene fluoride, polytetrafluoroethylene, and carboxymethyl cellulose.

[0013] According to another embodiment, the high-performance organic lithium-bromine battery further includes an organic additive selected from acetonitrile, dimethylsulfamide, tetrahydrofuran, acrylate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, ethylene carbonate, propylene sulfite, methyl propionate, fluoroethylene carbonate, lithium nitrate or a combination thereof.

[0014] According to one embodiment, the chloride ion-containing additive includes lithium chloride, ammonium chloride, calcium chloride, cesium chloride, ferrous chloride, magnesium chloride, potassium chloride, sodium chloride, silver chloride, zinc chloride, or a combination thereof.

[0015] According to one embodiment, the organic electrolyte includes a lithium salt as a solute. The lithium salt includes lithium bis(trifluoromethanesulfonyl)sulfite, lithium trifluoromethanesulfonate, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonylimide), lithium glycol phenyl borate, lithium bis(fluorosulfonyl)phenyl borate, lithium bis(fluorosulfonyl)sulfite, lithium chloride, or a combination thereof.

[0016] According to one embodiment, the membrane comprises a polypropylene film.

[0017] According to one embodiment, the organic lithium-bromine battery exhibits remarkable durability, showing a service life of up to 1000 cycles and a capacity decay rate of only 4.4% per 100 cycles.

[0018] This paper introduces a high-performance solid-state lithium-bromine battery that relies on an active bromine salt cathode and achieves Br through electrolyte customization. - / Br + Two electron transfer chemical reaction of redox pair. Introducing NO3 - Ion Improvement Br - The reversibility of the single electron transfer is even more impressive, as the electronegatively coordinated Cl - The anion activates the Br + The conversion facilitates additional electron transfer. The discharge capacity and energy density are improved by 242% and 259% respectively over the single-electron benchmark.

[0019] The two-step conversion mechanism of the present invention exhibits excellent stability, extending the battery life to 1000 cycles, and the capacity decay rate per 100 cycles is only 4.4%. These performances are close to the state-of-the-art level of existing lithium halogen batteries. The established two-electron redox mechanism is regarded as an excellent example of diversified halogen batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Reference is made hereinafter to the accompanying drawings, which illustrate exemplary, non-limiting and non-exhaustive embodiments of the present invention. In order to understand the features of the present invention described above in more detail, reference may be made to these embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that these drawings only illustrate typical embodiments of the present invention and should not be considered as limiting the scope of the present invention, as the present invention may also include other equally effective embodiments.

[0021] Figure 1A The molecular model of BABr3 is shown. Figure 1B Depicting scanning electron microscope (SEM) images of TBABr3 and its energy dispersive analysis (EDX) mapping data. Figure 1C The cyclic voltammetry (CV) curves of Li||TBABr3 battery in different electrolytes are depicted, with the test range of 2.0–3.8V and the scan rate of 2mV / s. Figure 1D Depict the charge and discharge (GCD) curves of Li||TBABr3 batteries in different electrolytes. Figure 1E CV curves of Li||TBABr3 cells with E2 electrolyte at different scan rates are plotted. Figure 1F Plot the GCD curves of Li||TBABr3 cells with E2 electrolyte at different current densities.

[0022] Figure 2 The energy dispersive spectrometry (EDS) spectrum of TBABr3 is shown.

[0023] Figure 3 Plotting the b-values ​​of the redox peaks for the Li||TBABr3 cell with E2 electrolyte.

[0024] Figure 4 dQ / dV curves plotting the GCD curve of a Li||TBABr3 cell with E2 electrolyte.

[0025] Figure 5 Plotting the energy density of Li||TBABr3 cells with E2 electrolyte at different current densities.

[0026] Fig. 6A Plot the CV curves of Li||TBABr3 cells using different electrolytes in the range of 2.0-4.0V, and Figure 6B Show the corresponding GCD curve. Figure 6C Shown are the CV curves of Li||TBABr3 cells with CE2 electrolyte at different scan ranges. Fig.6D Plotting the GCD curves of Li||TBABr3 cells with CE2 electrolyte over different scan ranges. Fig. 6E Depicts the improvement in capacity and energy density due to two-electron transfer compared to one-electron transfer reactions. Fig. 6F The CV curves of Li||TBABr3 cells with CE2 electrolyte at different scan rates are plotted, and the b-values ​​of the redox peaks are calculated.

[0027] Figure 7 Plotting the b-values ​​of the redox peaks for Li||TBABr3 cells with CE2 electrolyte.

[0028] Fig. 8ALinear sweep voltammetry (LSV) curves of CE2 electrolyte at 10 mV / s are plotted. Figure 8B CV curves of an asymmetric lithium||stainless steel cell at 10 mV / s are plotted. Figure 8C Plotting the current density of 1mA and 1mAh / cm at a specific cycle 2 GCD curves of asymmetric lithium||stainless steel battery under energy density conditions. Fig.8D Depicts the symmetric Li||Li cell at 1 mA current density and 1 mAh / cm 2 Long-term cycling performance under energy density conditions.

[0029] Fig. 9 Plotting the Coulombic efficiency (CE) values ​​of the asymmetric lithium||stainless steel cell with CE2 electrolyte.

[0030] Fig.10 Plotting the current density of 1mA and 1mAh / cm at a specific cycle 2 GCD curves of asymmetric lithium||stainless steel battery under energy density conditions.

[0031] Fig.11 Depicted are electrochemical impedance spectroscopy (EIS) plots of symmetric Li||Li cells with E2 and CE2 electrolytes.

[0032] Fig.12 Shown are the enlarged GCD curves of the symmetric Li||Li cell in the long-term cycling test at the time periods of 194-200 hours and 495-500 hours, respectively.

[0033] Fig.13A The long-term cycling performance at a current density of 1.5 A / g is depicted, and Fig. 13B The corresponding GCD curves for cycle 2 and cycle 1000 are shown. Fig. 13C Describe the rate performance at current densities of 1-4 A / g, and Fig.13D The corresponding discharge curve is displayed. Fig.13E Plotting the dQ / dV curves of Li||TBABr3 cells with CE2 electrolyte. Fig.13F Plotting the generalized pulsed lasing (GITT) curve. Figure 13G The performance comparison between the present invention and reported lithium-ion batteries is shown.

[0034] Fig.14A In situ high-resolution I 3d external X-ray photoelectron spectroscopy (XPS) spectra at selected state-of-charge (SOC) points are depicted. Fig. 14B High-resolution Cl 2p XPS spectra at selected SOC points are depicted. Fig. 14C Depicted are in situ Raman spectra at selected SOC sites. Fig.14DIn situ EIS plots at selected SOC points are plotted. Fig.14E Plot the curves of Ro and Rct values ​​changing with SOC.

[0035] Fig.15 Shown is a CR2032-type battery case with an open quartz glass window for in situ Raman characterization.

[0036] Fig.16A Show from Br - To Br 0 Then to Br + The proposed reaction pathway. Fig. 16B Describe the charging process containing Cl - and Cl-free - The cohesive energy of the system. Fig. 16C and Fig.16D The electron localization function (ELF) and atomic charges of BrCl, BrCl2, and BrCl3 are shown respectively. DETAILED DESCRIPTION

[0037] Despite the potential of static lithium-bromine (SLB) batteries as conversion-based energy storage technologies, their performance has stagnated over the past few decades. Conversion chemistry of bromine has significant potential due to its significant advantages in physicochemical and electrochemical properties, such as low cost, abundant valence states, and high redox potential. However, all documented Li-Br batteries are based on the reversible Br - / Br o The inherent liquid-liquid redox mode and single electron transfer characteristics of these batteries limit their further development.

[0038] Because Br + The instability of cations in organic electrolytes has not been achieved so far. - / Br + Reversible two-electron redox transition at high potential. Br + The forward conversion of 2-Br is thermodynamically unstable and exhibits poor reversibility and limited reaction depth. Therefore, all reported lithium-bromine batteries can only reach 335 mAh g -1 The low capacity of Br2 is about 3.4V (relative to Li+ / Li). In addition, in static batteries, Br2 is not suitable as an electrode material due to its inherent mobility and volatility.

[0039] Therefore, the present invention provides a static lithium-bromine battery (SLB) driven by a novel two-electron redox chemistry, characterized by using a halogen material as an electrochemically active cathode, a Cl-rich - The electrolyte and separator. The introduced NO3 -ions in single electron mode enhance the Br - Reversible efficiency of ions.

[0040] The lithium-bromine battery is designed for energy storage and combines an optimized electrolyte strategy to achieve excellent performance. In order to replace elemental bromine (Br2), bromide is used as the active bromine source, which has better thermal stability than traditional elemental bromine. - / Br + The redox process significantly improves the electrochemical performance, surpassing the traditional Br - / Br3 - / Br 0 The right ability.

[0041] In one embodiment, the negative electrode may include lithium sheet, lithium foil, and graphite.

[0042] In one embodiment, the halogen-based cathode includes a current collector, an active material, one or more conductive particles, and a binder. The current collector can be carbon cloth, carbon paper, graphite paper, titanium foil / mesh, stainless steel, aluminum foil, or nickel foam. The active material can be methylammonium bromide, methylammonium tribromide, tetrabutylammonium bromide, tetrabutylammonium tribromide, or hexadecyltrimethylammonium bromide. The one or more conductive particles can be Super-P, carbon black, Ketjen black, activated carbon, or a combination thereof. The binder can be polyvinylidene fluoride, polytetrafluoroethylene, or carboxymethyl cellulose.

[0043] Preferably, the active material is tetrabutylammonium tribromide (TBABr3).

[0044] In one embodiment, the halogen-based cathode is a bromide-based cathode.

[0045] In one embodiment, the high performance organic lithium-bromine battery further comprises organic additives, which may be acetonitrile, dimethyl sulfoxide, tetrahydrofuran, acrylic carbonate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, vinyl carbonate, acrylic sulfoxide, methyl propionic ester, fluoroethylene carbonate and lithium nitrate.

[0046] In one embodiment, the chloride ion-enriched electrolyte can be a solution containing an organic lithium salt. The lithium salt includes lithium bis(trifluoromethanesulfonyl)sulfite, lithium trifluoromethanesulfonate, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl imide), lithium ethylene glycol phenyl borate, lithium bis(fluorosulfonyl)phenyl borate, lithium bis(fluorosulfonyl)sulfite, lithium chloride, or a combination thereof.

[0047] In one embodiment, the separator may be a polypropylene film.

[0048] In one embodiment, the electronegative Cl- The anion triggers the Br + , promoting additional electron transfer, thereby achieving a capacity of at least 600 mAh / g and a voltage platform of 3.8 V.

[0049] Preferably, the electronegative Cl - Anions can trigger Br + conversion, promoting additional electron transfer, thereby achieving a capacity of 653mAh / g and a voltage platform of 3.8V.

[0050] In one embodiment, the lithium-bromine battery exhibits a high energy density of at least 2000 Wh / kg (calculated as bromine) and shows excellent cycling stability.

[0051] Preferably, the lithium-bromine battery exhibits 2180Wh kg -1 Br High energy density.

[0052] In addition, the battery exhibits excellent durability, with a service life of up to 1,000 cycles and a capacity decay rate of only 4.4% per 100 cycles.

[0053] Examples

[0054] The examples and embodiments described herein are for illustrative purposes only, and those skilled in the relevant art may make various modifications or changes on this basis, and these modifications or changes are within the spirit and scope of this application. In addition, any invention or element or limitation disclosed in this application or its embodiment may be combined with any other element or limitation disclosed in this application (used alone or in combination) or any other invention or embodiment, and all these combinations are within the scope of the present invention and are not subject to any limitation.

[0055] Example 1

[0056] Materials and Methods

[0057] Tetrabutylamino tribromide (TBABr3, Aladdin, >99%), commercial electrolyte (1.0M LiTFSI in a volume ratio of 1:1 DME and DOL, DoDoChem), lithium chloride (LiCl, Aladdin, 98%), polyvinylidene fluoride (PVDF, Aladdin) binder, carbon black (conductive carbon black EC-600JD, Azko Nobel), N-methylpyrrolidone (NMP; AR grade, Aladdin), lithium foil (Li, Canrd, >99.9%), copper foil (Cu, Canrd, >99.9%), carbon cloth (HCP331, Canrd), carbon foam (Zhengtairong, >99.9%). All substances were used directly without any treatment.

[0058] To obtain the microstructural and elemental data of the samples, a field emission scanning electron microscope (SEM; S-4700, Hitachi) equipped with an energy dispersive spectroscopy (EDS) detector was used. Raman spectra of the samples were recorded using a HoribaLabRam HR Evolution instrument equipped with a 532 nm laser. XPS spectra were analyzed using a Thermo Fisher ESCALAB XI+ instrument.

[0059] Electrochemical characterization

[0060] The prepared TBABr3 electrode was directly used as the cathode, and lithium metal (radius = 10 mm) and Celgard 3050 (thickness = 20 μm) were used as the anode and separator, respectively, and assembled into a CR2032 button cell in an argon-filled glove box. All electrochemical tests were performed at room temperature. In addition, a CR2032 button cell with a quartz window was specially assembled for in situ Raman testing. In the symmetric Li||Li cell configuration, two identical lithium metals were used as the anode and cathode. In the asymmetric Li||Cu cell, lithium metal was used as the anode, while copper metal was used as the cathode. LSV, CV, and EIS tests were performed using a versatile CHI 760E electrochemical workstation.

[0061] Example 2

[0062] Preparation of chloride-saturated electrolyte

[0063] As controls, three commercial electrolytes with different contents of LiNO3 were used, namely E0 (1.0 M LiTFSI dissolved in DME and DOL with a volume ratio of 1:1, without LiNO3), E1 (1.0 M LiTFSI dissolved in DME and DOL with a volume ratio of 1:1, containing 1% LiNO3, and E2 (1.0 M LiTFSI dissolved in DME and DOL with a volume ratio of 1:1, containing 2% LiNO3), while LiCl was used as Cl - Source. In all cases, excess LiCl powder was slowly added to different commercial electrolytes in an argon-protected glove box and then vigorously stirred for 48 hours. The mixture was then left to stand for 72 hours to allow excess LiCl crystals to precipitate. Finally, the supernatant was extracted as the target product. Three chlorine-saturated electrolytes were prepared, labeled CE0, CE1, and CE2, based on the composition differences of the commercial electrolytes used. The applied rolling pressure was approximately 50 MPa, and the thicknesses of the collector and separator were approximately 380 microns and 20 microns, respectively. To ensure that the cathode material under investigation could undergo complete electrochemical conversion, excess electrolyte and lithium metal anode were used. The lithium metal disc had a diameter of 10 mm and a thickness of 300 microns.

[0064] Example 3

[0065] Fabrication of TBABr3 cathode

[0066] The TBABr3 cathode was manufactured by conventional methods. First, the active material (TBABr3 powder), polyvinylidene fluoride and carbon black were mixed in an N-methylpyrrolidone solvent in a mass ratio of 7:2:1. After vigorous stirring for 1 hour, a uniform slurry was obtained, which was then poured on a carbon cloth substrate. Next, the electrode was vacuum-assisted dried at 70°C for 72 hours. The mass loading of the TBABr3 cathode was about 1.5 mg / cm 2 .

[0067] Example 4

[0068] Preparation of Li||TBABr3 battery containing LiNO3 electrolyte

[0069] Single Electron Transfer Chemistry

[0070] like Figure 1A As shown in Figure 2, the molecular structure of TBABr3 includes a positively charged tetrabutylammonium (TBA+) cation and a negatively charged tribromide ion (Br3 - ), which are held together by moderately strong ionic bonds. Figure 1B and Figure 2SEM and EDX elemental mapping are shown, revealing the uniform distribution of elemental bromine in TBABr3 powder. Quantitative analysis shows that the mass fraction of bromine in TBABr3 is about 50wt.%. When TBABr3 is used as an electrode, TBA+ cations are shown to act as surfactants, promoting electrolyte wetting and inhibiting the transport of polybromine ions.

[0071] In one embodiment, a complete Li||TBABr3 battery is prepared, including a 2032-type circular battery case, a commercial ether-based electrolyte, a polypropylene separator, and a lithium metal anode. The battery is assembled in three different ether-based electrolytes, and different amounts of LiNO3 are added to adjust the stability and redox conditions of the electrolyte. The first electrolyte (E0) is composed of 1.0M LiTFSI dissolved in a DME / DOL mixed solvent with a volume ratio of 1:1, which does not contain LiNO3. The second electrolyte (E1) is 1.0M LiTFSI dissolved in a DME / DOL mixed solvent with a volume ratio of 1:1, to which 1% LiNO3 is added. The third electrolyte (E2) is 1.0M LiTFSI dissolved in a DME / DOL mixed solvent with a volume ratio of 1:1, to which 2% LiNO3 is added. At this stage, excess lithium and electrolyte are used to ensure sufficient reaction of TBABr3.

[0072] The assembled cells were electrochemically tested to investigate the direct usability and adaptability of the TBABr3 cathode. Figure 1C As shown in Figure 2, the CV curves of the three batteries obtained at a scan rate of 2 mV / s and a scan range of 2–3.8 V exhibit similar electrochemical characteristics. Each battery shows a pair of obvious redox peaks. These redox peaks correspond to Br - / Br3 - Yes, their redox potentials are approximately 3.4V and 3.6V respectively 20 .

[0073] However, the Li||TBABr3 battery using E0 electrolyte exhibited lower Coulombic efficiency and higher voltage polarization, indicating poor reaction reversibility and slow kinetics. Electrochemical evidence showed that the current response was significantly weaker and a cathodic peak appeared at 3.34 V. Therefore, Br3 - The reduction reaction is not completely reversible. In contrast, the Li||TBABr3 cells using E1 and E2 electrolytes with LiNO3 additives optimize the reduction reaction in all aspects, as can be seen from the nearly symmetrical CV curves and the reduction peak at 3.4 V. In addition, the slightly larger peak area in the E2 electrolyte indicates that the completeness of the reduction reaction is improved.

[0074] The above differences are verified by GCD curves. All electrochemical data are obtained based on the bromine content of the TBABr3 cathode. Figure 1D As shown in the figure, when testing the Li||TBABr3 battery using an electrolyte without LiNO3 additive (E0), the charging curve extends to 468mAh / g due to insufficient redox reaction, which is significantly higher than the discharge capacity of 188mAh / g, resulting in a low Coulombic efficiency of 40%. The discharge platform is located at 3.45V, but the capacity utilization is limited, less than 38%. In contrast, the Coulombic efficiency of the Li||TBABr3 battery using E1 electrolyte reached 97%, and the capacity of the electrolyte was 205mAh / g, showing significantly improved redox reversibility. The discharge capacity of the E2 electrolyte was further increased to 224mAh / g, close to the theoretical Br - / Br3 - In addition, both E1 and E2 electrolytes have a plateau at 3.56 V, accounting for 53% of the total capacity. These results indicate that the LiNO3 additive plays a key role in stabilizing the redox activity and enhancing the kinetics.

[0075] The CV curves of Li||TBABr3 cells using E2 electrolyte were recorded at different scan rates to study their electrochemical kinetics in detail. Figure 1E The results show that at a scan rate of 0.1–0.5 mV / s, two sharp peaks are located at 3.42–3.46 V and 3.50–3.51 V, respectively, with narrow half-peak widths. The main coverage area of ​​the peaks in the entire CV curve indicates that the charge transfer process is mainly driven by Br - and Br3 - The reversible redox reaction between them is driven by no obvious side reactions.

[0076] To gain insight into the charge storage mechanism, the b-values ​​of the two peaks were determined using the following equations: i=av b , Where i represents current, v represents scan rate, and a and b represent variables.

[0077] If b = 0.5, it means that the current is controlled by battery-like diffusion behavior; if b = 1, it means that the current is affected by the overall surface control behavior. Figure 1E and Figure 3 As shown, the calculated b-values ​​of the cathodic and anodic peaks are 0.78 and 0.68, respectively, which indicates that the two charge storage mechanisms coexist.

[0078] The superior kinetics reduce the sensitivity of Li||TBABr3 batteries to current changes and improve their rate performance. Figure 1FAs shown in Figure 1, the GCD curves show that the battery achieves capacities of 225, 221, 212, and 196 mAh / g at current densities of 0.5, 1.0, 2.0, and 4.0 A / g, respectively. It can be observed that the capacity retention rate reaches 87% when the current increases eightfold, and the discharge platform is still clearly visible under all conditions. Figure 4 As shown, the dQ / dV curve of the GCD curve of the Li||TBABr3 battery using E2 electrolyte shows paired peaks.

[0079] In addition, the large coverage area of ​​the peak indicates the main contribution of the plateau voltage to the capacity. Therefore, the maximum energy density is calculated to be 717Wh / kg ( Figure 5 ).

[0080] Double Electron Transfer Chemistry

[0081] like Fig. 6A As shown in the figure, the Li||TBABr3 battery using an electrolyte without LiNO3 additive also exhibits weak multi-electron transfer characteristics in a wide voltage range of 2-4V. - / Br3 - In addition to the redox reaction, a weak peak pair at about 3.8 V was also found ( Fig. 6A ), which corresponds to Br + Redox reactions of cations 22 After adding LiNO3 additive, the current response of the new reduction peak is enhanced, indicating that Br + The redox process was improved. However, its absolute current value was significantly lower than that of Br - / Br3 - Yes, this indicates that its reversibility and Coulombic efficiency are low.

[0082] like Figure 6B As shown, the relevant GCD curve does not show Br + The new discharge platform of the restored Br - / Br3 - The 3.7V flat platform is derived from Br + However, only a portion of Br was observed during the discharge phase. + At this time, the discharge capacity reaches 281 mAh / g, close to Br - / Br 0 The upper limit of the single electron transfer mode 23 .

[0083] Example 5

[0084] Preparation of Li||TBABr3 batteries containing CE2 electrolyte

[0085] In this example, Br - / Br + The basic redox mechanism of the + -Formation of Cl2.

[0086] Br + The uneven electron density tends to bind to more electronegative anions, which is believed to activate the reversible Br + Therefore, the present invention further introduces saturated Cl in the form of LiCl into the E2 electrolyte (1.0M LiTFSI dissolved in DME / DOL=1:1, and 2% LiNO3 is added). - Anion.

[0087] like Figure 6C As shown, using Cl - The CV curves of the Li||TBABr3 battery with the modified E2 electrolyte (called CE2) at a scan rate of 2 mV / s showed significant redox peaks at 3.42 / 3.55 V and 3.68 / 3.85 V in the range of 2–4 V, corresponding to the Br - and Br + Reversible redox reaction. It is worth noting that Br + The current response during the oxidation and reduction phases is significantly enhanced, even exceeding that of Br - This observation suggests that in CE2 electrolyte, Br + The reversible reaction was fully activated, showing high stability and integrity, which was a significant improvement compared to the original electrolyte mentioned above. There was no sudden increase in current at the cut-off voltage, indicating that CE2 maintained good stability within the specified voltage range.

[0088] The entire reaction follows a strict two-step charge transfer process, and no additional redox features are identified on the CV curve. When the cutoff voltage is adjusted to 3.8 V, the transition interval between the two reactions, the CV curve shows a two-step electrochemical feature, in which Br + The redox reaction of Cl occurs in the main stage. These results confirm that - The anion participates in the Br at the beginning of the reaction + of the body and plays a dual activating and stabilizing role.

[0089] In the GCD curve ( Fig.6D ), the characteristics of two electron transfers become more obvious. In addition to Br at 3.4 V -In addition to the excitation platform, a series of new charge and discharge platforms appeared at 3.4V and 4.2V. These platforms correspond to the Br at the cut-off voltage point of 3.92V. + Redox process 24 The discharge capacity reached an unprecedented 568 mAh g -1 , where the newly emerged 3.8 V platform contributes nearly half of the capacity. As expected, no electrochemical features indicating additional reactions were found in the GCD curves. At the 3.8 V cutoff voltage, two paired platform appeared. However, due to the Br + Due to the incomplete redox reaction, the length of the high voltage platform was shortened, which is consistent with the above CV results. At 3.6 V, only one discharge platform was detected, located at 3.5 V, with a capacity of 236 mAh g -1 , because the current reaction has not yet entered the second stage. This new redox chemistry significantly improves the electrochemical performance, including capacity, voltage, and energy density. Quantitative analysis shows that the capacity and energy density of the new two-electron mode are 242% and 259% of those of the traditional single-electron mode, respectively. Fig. 6E ).

[0090] Example 6

[0091] Reversible Br + Kinetics of redox reactions

[0092] CV curves were established in the voltage range of 2–4 V at a scan rate of 1–9 mV / s. Fig. 6F As shown in Figure 2, under all conditions, the two symmetrical redox peaks remain consistent without significant fluctuations. As the scan rate increases, the current response of the peaks also increases accordingly. It is worth noting that the Br + The two high voltage peaks of the redox reaction are always larger. In this process, the voltages of the two reduction peaks shifted to a higher direction, from 3.44V / 3.70V at 1mV / s to 3.37V / 3.62V at 9mV / s, resulting in minimum voltage hysteresis of 0.07V and 0.08V, respectively. In addition, for Br + For the oxygen reduction reaction, despite a nine-fold increase in scan rate, the voltage polarization only slightly increased from 0.13 V (3.70 V / 3.83 V) to 0.33 V (3.62 V / 3.95 V), indicating excellent oxygen reduction kinetics in the conversion battery system.

[0093] refer to Fig. 6F and Figure 7 , for Br + The b values ​​of the two peaks of the oxygen reduction reaction were evaluated. The calculated results showed that the b value of the cathode peak was 0.76 and the b value of the anodic peak was 0.68. This indicates that Br+ The oxygen reduction process is both surface-controlled and diffusion-controlled and is more sensitive to electrochemical cells.

[0094] Example 7

[0095] Lithium Metal Anode Compatibility Analysis

[0096] Although TBABr3 performs well in CE2 electrolyte, its compatibility with the negative electrode still needs to be ensured for a comprehensive battery evaluation. The electrochemical stability of the electrolyte as well as the reversibility and redox kinetics of the lithium anode in this electrolyte were further analyzed. To determine the stable voltage range of CE2, an asymmetric lithium||stainless steel cell was tested using LSV testing at a scan rate of 10mV / s, with the stainless steel plate as the working electrode. Fig. 8A As shown, the sudden change of the response current begins to appear at 4.05 V, while no decomposition signal is detected before that, thus confirming the redox stability of the battery. Subsequently, the CV method was used to evaluate the reversibility of lithium deposition / stripping in CE2 electrolyte, in which the stainless steel plate was used as the working electrode. Figure 8B CV curves showing the deposition of lithium during the cathodic scan phase and the dissolution behavior during the anodic scan phase. The deposition / dissolution onset potential (-0.05 V relative to 0.00 V) only produced a polarization voltage of 0.05 V, demonstrating the excellent redox kinetics of the lithium anode.

[0097] Subsequently, the Coulombic efficiency was recorded at a current density of 1 mA and 1 mAh cm-2 in galvanostatic mode to evaluate its cycling stability and reversibility. Fig. 9 As shown in Figure 2, the Coulombic efficiency of the first cycle is 84%, which increases rapidly to 98% after 6 cycles and then remains stable. Figure 8C and Fig.10 As shown, the related GCD curves show that the voltage polarization of lithium deposition / stripping is almost symmetrical (28mV vs. 30mV) and remains stable within 100 cycles. In addition, when closed-loop cycling is performed, the GCD curve remains stable without fluctuations due to redox stability issues.

[0098] Example 8

[0099] Cl - Effects of ions on charge transfer processes

[0100] The EIS graphs of symmetric Li||Li cells using CE2 and E2 electrolytes are shown. The charge transfer resistance (R ct ) is 149.6Ω, which is lower than 158.7Ω of E2, indicating that the introduced Cl - ions effectively reduce the Li +diffusion resistance, bringing positive effects ( Fig.11 ). In addition, the mass transfer process in the electrode-electrolyte region is also improved, and the ohmic resistance (R o ) from 5.3Ω to 4.4Ω.

[0101] The introduced electrochemically insulating LiCl phase contributes to the improved redox stability because it regulates the electrodeposition of Li ions on the Li surface, thereby suppressing the growth of dendrites. This phenomenon is confirmed by long-term plating / stripping tests on symmetric Li||Li cells. Fig.8D and Fig.12 When using CE2 electrolyte, at 1 mA current and 1 mAh cm -2 The voltage-time curve recorded under capacity remained stable, and no short-circuit signal was observed for up to 500 hours.

[0102] Example 9

[0103] Electrochemical performance of Li||TBABr3 batteries using CE2 electrolyte

[0104] After confirming the stable voltage window of CE2 and its excellent compatibility with lithium metal anode, the electrochemical performance of all-lithium||TBABr3 cells using innovative two-electron transfer chemistry was comprehensively evaluated. Fig.13A Demonstrating Li||TBABr3 battery at 2Ag -1 The long-term cycling capability under high temperature and low humidity is excellent. After 1000 cycles, the capacity decay rate is only 4.4% per 100 cycles, showing excellent reversible operation capability.

[0105] like Fig. 13B As shown in the figure, even after 1000 cycles, the Li||TBABr3 battery continued to show two obvious discharge plateaus, indicating that it maintained a strict two-electron transfer mode in the initial cycle. In addition, no electrochemical features originating from side reactions were observed, demonstrating the long-term stability of this two-electron chemical reaction. Therefore, it is speculated that the capacity decay observed during the cycle may be due to the inevitable shuttle effect leading to the continuous loss of active materials rather than the degradation of the new redox mode. The fast kinetic characteristics enable the battery to exhibit excellent rate performance. For example, at low current density (1A g -1 ), the battery discharge capacity reached 653mAh g -1 Br , close to the theoretical limit of two-electron redox reactions 24 Therefore, the energy density reaches 2180Wh kg -1 Br .

[0106] In addition, if Fig. 13CAs shown, the battery has a higher performance at 4A g compared to other conversion equivalents. -1 The capacity retention rate under 3.8V is more than 68%, showing the low sensitivity of capacity to current change. Moreover, at all rates, there are two stable platforms in the relevant discharge curves, and their triggering voltage and time do not decrease significantly with the increase of current. The capacity contribution of the 3.8V platform is always greater than that of the 3.5V platform ( Fig.13D ), and no additional side reactions were observed. The above electrochemical differences can be intuitively observed through the dQ / dV curve obtained by mathematically processing the discharge curve.

[0107] refer to Fig.13E , all dQ / dV curves show two obvious peaks, located at about 3.46V and 3.72V, which is consistent with the previous CV curves. These peaks appear in the discharge platform region, where the voltage slowly decreases in a small dV range, and the sharpness of the peak is determined by the flatness of the platform. The absolute value of the dQ / dV of the 3.72V peak is usually higher than that of the dQ / dV of the 3.46V peak, indicating that the fresh Br under high voltage + The reversible redox reaction has better stability and its kinetic performance is better than other Br - Anions 25 .

[0108] The galvanic intermittent titration technique (GITT) was used to verify whether there was kinetic limitation in the charging process. Fig.13F As shown, the pseudo-equilibrium curve shows two clear platform regions in the two-stage oxygen reduction process, where the curve thickness is small, indicating that the high-voltage platform has excellent kinetic performance and discharge voltage 26 The newly developed two-electron oxygen reduction chemical system not only meets the demand for high voltage output, but also provides large-capacity battery performance, making the full TBABr3 battery show excellent electrochemical performance.

[0109] To demonstrate this advantage intuitively, the battery is compared with well-known lithium intercalation batteries and lithium conversion batteries in terms of voltage platform and capacity. Figure 13G As shown, the existing Li||TBABr3 battery shows overwhelming advantages over the conventional lithium-halogen (Br or I) single electron transfer mechanism battery. The voltage platform as high as 3.8V is beyond the range of most conversion systems, such as lithium-sulfur, lithium-selenium and lithium-tellurium systems. 8,27,28 , and even exceeds the performance of some established intercalation cathode materials such as LiFePO4 and LiCo x O y New redox chemistry boosts capacity of lithium-bromine conversion battery to 653 mAh g -1, significantly improving its performance from the previous low level, showing good potential for practical applications.

[0110] Example 10

[0111] Characterization of redox mechanisms

[0112] In this example, multiple experimental characterizations were performed, including XPS, in situ Raman spectroscopy, and EIS. XPS spectroscopy was used to track the evolution of the chemical valence states of Br and Cl at different states of charge on the TBABr3 electrode. Fig.14A As shown in Figure 2, as the charging process proceeds, the high-resolution Br 3d spectrum shows a significant blue shift, indicating that the valence state of Br has increased. In the fully discharged state, only the characteristic signals of Br- anions can be fitted at 68.9 eV and 69.8 eV, while the weak Cl signal appearing in the high-resolution Cl 2p spectrum may originate from surface adsorption or residues ( Fig. 14B When the charging voltage is 3.6V, polybromide (Br n - , n≥3) and the peaks of Br2 element fitting are mainly 68.2, 68.7, 69.6 and 70.2 eV, corresponding to Br - In the first stage of the oxidation reaction 29-30 At this time, the chlorine signal increased significantly, and the fitted peaks were 198.8 and 200.2 eV, corresponding to the Cl- anion. When the voltage was 3.95 V, fitted peaks at 71.8 and 73.1 eV also appeared, which were attributed to Br + ions, suggesting a second electron transfer process. In addition, the 201.9 eV peak in the Cl 2p spectrum may be caused by Br + -Cl - x The redox products of the complex are excited.

[0113] In order to monitor the evolution of redox products in real time and identify reversible changes throughout the charge-discharge cycle, a special cell housing with an open quartz glass window was used to monitor the redox product evolution in real time at 100–700 cm -1 In situ Raman spectroscopy was recorded in the range Fig. 14C and Fig.15 When the voltage reaches 3.6 V, a new region at 260–290 cm -1 The intensity of the Raman peak increases as the charging process proceeds. In the subsequent discharge stage, the signal decays as the voltage decreases until it disappears completely at 3.5V. This reversible signal depicts the Br + -Cl - x The synchronous generation and decomposition of species are consistent with the results of XPS analysis.

[0114] In situ EIS technique was used to determine the kinetic differences between the two redox steps. Fig.14D The EIS spectra obtained at specific voltage points during the charging stage are shown. The mid-frequency region of the spectrum is semicircular, while the low-frequency region is linear. Due to the excellent wettability of the electrolyte and electrodes, the ohmic resistance (Ro) is always kept at a low level of 6.5 to 8.2Ω. As the voltage increases, R ct Two clear trends emerge: In the 2.0–3.2V range, R ct increases (8.2Ω at 2V and 8.3Ω at 3.2V); while in the 3.6–3.9V range, R ct The R is decreased (7.7Ω at 3.6V and 6.5Ω at 3.92V). This obvious phenomenon is due to the different charge transfer mechanisms in the two-step process. A sudden voltage point is observed at 3.6V; at this time, R ct It dropped sharply from 8.3Ω to 7.7Ω, which is consistent with Br + With Cl - The formation voltage is consistent with that of Fig.14E ). Subsequently, the charge transfer barrier gradually decreases, resulting in faster kinetics. During the charging process, Cl - The pre-enrichment of anions on the cathode side of TBABr3 may play a role in this phenomenon.

[0115] Example 11

[0116] Conversion mechanism in two-electron transfer reactions

[0117] In this example, density functional theory (DFT) calculations were performed. DFT calculations were performed using the Vienna Ab Initio Simulation Package (VASP) 13-14 The electron exchange and correlation are described by the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional. 15 The van der Waals correction is described using the semi-empirical Grimme parameter DFT-D3 correction 16 A 2x 2x 1 TBABr3 supercell was constructed and a plane wave basis set calculation was performed with a cutoff energy of 500 eV. The vacuum spacing in the Z direction was set to exceed The maximum residual energy and force of the cutoff are 1×10 -5 eV and The charge distribution of atoms in BrCl, BrCl2 and BrCl3 was calculated by Bader analysis program. 17-18All molecular structures were visualized using the VESTA software package. 19 To measure the stability of different systems, the cohesive energy (EC) was calculated by DFT: Where m and n are the number of Br and Cl atoms respectively; E sys 、E Br 、E Cl and E sub E represents the energy of the system, the energy of separating Br atoms, the energy of separating Cl atoms, and the energy of the TBABr3 matrix. C The larger the value, the higher the thermodynamic stability of the corresponding system.

[0118] refer to Fig.16A The experimental results suggest a new method from Br - To Br 0 Then to Br + At the same time, the presence or absence of Cl - Cohesive energy curve of the reaction when participating Fig. 16B ). The results showed that Cl - ions promote Br3 by lowering the energy barrier - To Br2 and Br + The energy differences of the transitions are 0.93 and 1.48 eV, respectively. Subsequently, three potential redox products were proposed and studied: BrCl, BrCl2, and BrCl3. The results showed that the binding energy of BrCl2 reached 1.85 eV, which is higher than that of BrCl (1.23 eV) and BrCl3 (1.68 eV), indicating that BrCl2 has higher thermodynamic stability.

[0119] In addition, the electron localization function (ELF) calculations were performed for different redox products containing Br, and the results showed that the coupling strength between Cl and Br in BrCl2 was stronger than that in other products ( Fig. 16C ). Specifically, Fig.16D The atomic charge data in the results show that the charges of Br in BrCl, BrCl2, and BrCl3 are 0.4, -0.1, and 0.18e, respectively. The opposite atomic charges between Br and Cl in BrCl2 are consistent with the strong coupling strength observed in the ELF. In other words, the results of the comprehensive analysis of ELF, binding energy, and atomic charge show that the final redox product prefers BrCl2 rather than BrCl or BrCl3.

[0120] In summary, this invention highlights a significant advance in the field of energy storage through the strategic use of electrolytes. - The additives enhance the Br- The redox efficiency of the conversion was further increased by introducing saturated Cl - Realized Br + These breakthroughs have made Br-based - / Br + A high-performance solid-liquid battery with two-electron transfer chemistry is realized.

[0121] Excellent results were achieved using an improved CE2 electrolyte combined with a lithium metal anode. The discharge capacity was increased to 653 mAh g by using a new electron transporter. -1 Br , the output platform voltage jumped to 3.8V, and the energy density reached about 2180Whkg -1 Br .

[0122] In addition, the battery exhibits excellent durability, with a service life of up to 1,000 cycles and a capacity decay rate of only 4.4% per 100 cycles.

[0123] definition

[0124] Throughout this specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising" will be understood to imply the inclusion of the stated integer or groups of integers, but not the exclusion of any other integer or groups of integers. It should also be noted that in this disclosure and particularly in the claims and / or paragraphs, terms such as "comprises", "comprised", "comprising", etc. may have the meanings ascribed to them in U.S. patent law; for example, they allow for elements not expressly recited, but exclude elements that are found in the prior art or that affect the basic or novel characteristics of the invention.

[0125] Furthermore, throughout the present specification and claims, unless the context requires otherwise, the word "include" or variations such as "includes" or "including", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

[0126] As used herein and not otherwise defined, the terms "substantially," "essentially," "roughly," and "approximately" are used to describe and take into account minor variations. When used in conjunction with an event or circumstance, the terms may encompass situations where the event or circumstance clearly occurs as well as situations where the event or circumstance closely approximates to occurring. For example, when used in conjunction with a numerical value, the terms may encompass a range of variation of less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%.

[0127] References in this specification to "one embodiment," "an embodiment," "an exemplary embodiment," etc. indicate that the described embodiment may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases do not necessarily refer to the same embodiment. Furthermore, when a particular feature, structure, or characteristic is described in conjunction with an embodiment, it should be understood that it is within the knowledge of a person skilled in the art to affect this feature, structure, or characteristic in conjunction with other embodiments, whether or not explicitly described.

[0128] Other definitions of selected terms used herein can be found in the detailed description of the present invention and are applicable to the entire text. Unless otherwise defined, all other technical terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention belongs.

[0129] References: The disclosures of the following references are incorporated by reference 1. Lu, Y. and Chen, J., Prospects of organic electrode materials in practical lithium batteries, Nature Reviews Chemistry 4, 127-142, doi:10.1038 / s41570-020-0160-9(2020). 2. Zhuo, Z. et al., Cycling mechanism of Li2MnO3: commonality between oxygen redox reactions in Li–CO2 batteries and cathode materials, Joule 5, 975–997 (2021). 3. Lee, J. et al., Unleashing the potential of disordered cationic oxides in rechargeable lithium batteries, Science 343, 519-522, doi: 10.1126 / science.1246432 (2014). 4. Zhu, G. et al., Rechargeable Na / Cl2 and Li / Cl2 batteries, Nature 596, 525-530, doi:10.1038 / s41586-021-03757-z (2021). 5. Li, X. et al., Achieving a high voltage platform by activating the I0 / I+ redox couple in aqueous I2–Zn batteries, Energy &Environmental Science(2018). 6. Gao, L. et al., High-performance aqueous zinc-bromine static battery, iScience 23, 101348, doi: 10.1016 / j.isci.2020.101348 (2020). 7. Yoo, S. J., et al., Fundamentally solving the bromine storage problem via reversible solid-state confinement: Designing high-performance dual-redox electrochemical capacitors in porous carbon electrodes, J Am Chem Soc 139, 9985–9993, doi: 10.1021 / jacs.7b04603 (2017). 8. Zou, Y. et al., Four-electron Zn-I2 aqueous battery via reversible I- / I2 / I+ conversion, Nature Communications 12, 1-11. 9. Li, XL et al., High-performance iodide ion conversion cells based on two-electron redox chemistry, Angewandte Chemie-International Edition 61, e202113576, doi: ARTNe20211357610.1002 / anie.202113576 (2022). 10. Manthiram, A., Yu, X. W., and Wang, S. F., Lithium battery chemistry enabled by solid-state electrolytes, Nature Reviews Materials 2, 1-16, doi: ARTN 1610310.1038 / natrevmats.2016.103 (2017). 11. Biswas, S. et al., Simplified zinc-bromine battery for low-cost electrochemical energy storage, Energy & Environmental Science 10, 114-120, doi:10.1039 / c6ee02782b(2017). 12. Li, X. et al., using Ti3C2T X Halogen redox chemistry of Zn-Br in MXene-confined aqueous systems, ACS Nano 15, 1718-1726, doi:10.1021 / acsnano.0c09380(2021). 13. Kresse G, Furthmüller J., Efficiency of ab initio total energy calculations of metals and semiconductors using plane wave basis sets, Computational materials science 1996, 6(1): 15-50. 14. Kresse G, Furthmüller J., An efficient iterative scheme for ab initio total energy calculation based on a plane wave basis set, Physical review B 1996,54(16):11169. 15. Perdew JP, Burke K, Ernzerhof M., Simplified generalized gradient approximation method, Physical review letters 1996, 77(18):3865. 16. Grimme S., Semiempirical GGA-type density functional with long-range dispersion correction, Journal of computational chemistry 2006, 27(15): 1787-1799. 17. Henkelman G, Arnaldsson A, Jónsson H. A fast and reliable Bader decomposition algorithm for charge density. Computational Materials Science 2006, 36(3): 354-360. 18.Yu M, Trinkle DR., An accurate and efficient Bader charge integration algorithm, The Journal of chemical physics 2011, 134(6): 064111. 19. Momma K, Izumi F., A three-dimensional visualization system for electronic and structural analysis, Journal of Applied crystallography 2008, 41(3): 653-658. 20. Xi, XL et al., High energy density non-aqueous lithium-bromine batteries with carbon-coated membranes, Journal of Energy Chemistry 26, 639-646, doi: 10.1016 / j.jechem.2017.04.013 (2017). 21. Yang, Q. et al., Activation of C-coordinated iron in ferricyanide for zinc hybrid ion batteries, achieving 10,000 Cycle life and excellent rate performance, Adv Mater 31, e1901521, doi:10.1002 / adma.201901521(2019). 22. Yang, C. et al., Aqueous lithium-ion batteries based on halogen conversion-intercalation chemistry in graphite, Nature 569, 245-250 (2019). 23. Popat, Y. et al., Carbon materials as cathodes for bromine-based flow batteries, Chempluschem 87, e202100441,doi:ARTN e20210044110.1002 / cplu.202100441(2022). 24. Xu, Y., Xie, C., Li, T. & Li, X., A high energy density double electron transfer bromine-based flow battery, ACS Energy Letters 7, 1034-1039 (2022). 25. Ji, B.F., Zhang, F., Song, X.H. & Tang, Y.B., A novel potassium-based dual-ion battery, Advanced Materials 29, 1700519, doi: ARTN 170051910.1002 / adma.201700519 (2017). 26. Li, X. et al., Elimination of polysulfides via solid-phase lithium-sulfur conversion to achieve high-energy-density sulfur cathode in carbonate electrolytes, Nat Commun 9, 4509, doi: 10.1038 / s41467-018-06877-9 (2018). 27. 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Claims

1. A high performance organic lithium-bromine battery realized by two-electron redox chemistry, characterized in that: The organic lithium-bromine battery comprises: a bromide-based cathode; an anode; an organic electrolyte disposed in the space between the bromide-based cathode and the anode, the organic electrolyte comprising an organic solvent containing a chloride ion additive; and a separator disposed between the bromide-based cathode and the anode, The chloride ions in the organic electrolyte trigger the conversion of positively charged bromide ions, promoting additional electron transfer, resulting in a capacity of at least 600 mAhg -1 , and raise the voltage platform to 3.8V, thereby achieving an energy density of at least 2000Wh kg-1.

2. A high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 1, wherein the anode comprises a lithium sheet, a lithium foil or graphite.

3. A high performance organic lithium-bromine battery enabled by two-electron redox chemistry according to claim 1, wherein the bromide-based cathode comprises a current collector, active material, one or more conductive particles, and a binder.

4. A high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 3, wherein the current collector is selected from one or more of carbon cloth, carbon paper, graphite paper, titanium foil, titanium mesh, steel, stainless steel, aluminum foil or nickel foam.

5. The high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 3, wherein the active material is selected from methylammonium bromide, methylammonium bromide tribromide, tetrabutylammonium bromide, tetrabutylammonium bromide tribromide, hexadecyltrimethylammonium bromide or a combination thereof.

6. The high performance organic lithium-bromine battery enabled by two-electron redox chemistry of claim 3, wherein the one or more conductive particles comprise Super-P, carbon black, Ketjen black, activated carbon, or a combination thereof.

7. The high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 3, wherein the binder comprises polyvinylidene fluoride, polytetrafluoroethylene or carboxymethyl cellulose or a combination thereof.

8. The high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 1, wherein the organic lithium-bromine battery further comprises an organic additive selected from acetonitrile, dimethylsulfamide, tetrahydrofuran, acrylate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, ethylene carbonate, propylene sulfite, methyl propionate, fluoroethylene carbonate, lithium nitrate or a combination thereof.

9. The high performance organic lithium-bromine battery realized by two-electron redox chemistry of claim 1, wherein the chloride-containing additive comprises lithium chloride, ammonium chloride, calcium chloride, cesium chloride, ferrous chloride, magnesium chloride, potassium chloride, sodium chloride, silver chloride, zinc chloride or a combination thereof.

10. The high performance organic lithium-bromine battery enabled by two-electron redox chemistry of claim 1, wherein the organic electrolyte comprises a lithium salt as a solute.

11. A high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 10, wherein the lithium salt comprises lithium bis(trifluoromethanesulfonyl)sulfite, lithium trifluoromethanesulfonate, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonylimide), lithium ethylene glycol phenyl borate, lithium bis(fluorosulfonyl)phenyl borate, lithium bis(fluorosulfonyl)sulfite, lithium chloride or a combination thereof.

12. The high performance organic lithium-bromine battery enabled by two-electron redox chemistry of claim 1, wherein the separator comprises a polypropylene film.

13. The high performance organic lithium-bromine battery realized by two-electron redox chemistry according to claim 1, wherein the organic lithium-bromine battery exhibits a service life of up to 1000 cycles and a capacity decay rate of only 4.4% per 100 cycles.

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