Aqueous organic anode I2 battery and preparation method thereof

Abstract

The present invention provides an aqueous organic anode I2 battery and a method for preparing the same. The aqueous organic anode I2 battery comprises an anode, a cathode, and an electrolyte. The anode comprises an anode active material comprising 3,4,9,10-perylenetetracarboxylic diimide, the cathode comprises a cathode active material comprising I2, and the electrolyte is an aqueous electrolyte. The present invention aims to improve the lifespan, energy density, and power density of I2-cathode batteries.

Description

Technical Field

[0001] The present invention belongs to the field of electrochemical energy storage, and in particular relates to an aqueous organic anode I2 battery and a preparation method thereof. Background Art

[0002] In recent years, rechargeable metal halide batteries have attracted great attention in the field of electrochemical energy storage due to their high energy and power density. Solid iodine (I2) has better operability and stability than liquid bromine and gaseous chlorine; and it has a high abundance of 50-60 (g / L ocean ), high theoretical capacity (422mAh g -1 ), high reversibility and I 0 / I + The high theoretical redox potential (1.07 V compared to the standard hydrogen electrode) of the I2-cathode is - / I 0 / I + The solid-liquid conversion can avoid the electrode collapse problem that is common in other intercalation materials. Therefore, I2 stands out as a promising aqueous battery cathode material. Some progress has been made in the development of various aqueous metal I2 batteries, such as FeI2, AlI2 and ZnI2. However, the inevitable dendrite growth and corrosion of the metal anode of these batteries will lead to rapid capacity decay and short circuit; and the leaked iodine anion species form electrochemically inert complexes with the metal anode, which will lead to irreversibility of the I2-cathode and reduce its service life. Therefore, it is necessary to provide I2-cathode batteries with higher lifespan, energy density and power density. Summary of the Invention

[0003] In view of this, one aspect of the present invention provides an aqueous organic anode I2 battery, comprising an anode, a cathode and an electrolyte, wherein the anode contains an anode active substance, the anode active substance includes 3,4,9,10-perylenetetracarboxamide, the cathode contains a cathode active substance, the cathode active substance includes I2, and the electrolyte is an aqueous electrolyte.

[0004] In some embodiments, the electrolyte is a saturated KCl aqueous solution.

[0005] In some embodiments, the mass ratio of the 3,4,9,10-perylenetetracarboxylic acid diimide to I2 is 4:1.

[0006] In some embodiments, the electrolyte is a saturated aqueous solution of KCl and I2.

[0007] Another aspect of the present invention provides a method for preparing the aqueous organic anode I2 battery, comprising the following steps:

[0008] 1) mixing 3,4,9,10-perylenetetracarboxylic acid diimide, carbon black and polyvinylidene fluoride in N-methylpyrrolidone solvent, coating the mixture on a graphite paper substrate, and drying the mixture to obtain an anode;

[0009] 2) grinding and mixing I2 and activated carbon, and preparing the cathode material through hydrothermal reaction;

[0010] 3) mixing carbon black and polyvinylidene fluoride binder with the cathode material of step 2) in N-methylpyrrolidone solvent, coating the mixture on a graphite paper substrate, and drying the mixture to obtain a cathode;

[0011] 4) Assembling the electrolyte, the anode obtained in step 1) and the cathode obtained in step 3) into a battery.

[0012] In some embodiments, the mass ratio of 3,4,9,10-perylenetetracarboxamide diimide, carbon black and polyvinylidene fluoride binder in step 1) is 7:2:1.

[0013] In some embodiments, based on the total mass of the cathode material, the I2 content in the cathode material obtained in step 2) is 47.2%.

[0014] In some embodiments, in step 3), the mass ratio of cathode material, carbon black, and polyvinylidene fluoride is 8:1:1.

[0015] In some embodiments, the average mass loading of the anode obtained in step 1) and the cathode obtained in step 3) is 1.0-1.3 mg cm -2 .

[0016] In some embodiments, the hydrothermal reaction temperature in step 2) is 80° C. and the reaction time is 4 h.

[0017] Compared with the prior art, the aqueous organic anode I2 battery provided by the embodiment of the present invention has an ultra-long life (at 40A g -1 (94.8°C) and extremely high rate tolerance (at 160A g -1 104mAh g -1 ), high energy density (at 50420 Wkg -1 434Wh kg -1 ) and high power density (at 86Wh kg -1 155072W kg -1 ), and far exceeds the I2-cathode aqueous batteries and most K + Ion aqueous battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 CV curves of the PTCDI electrode according to Example 1 of the present invention at different scan rates.

[0019] Figure 2 The reversible K of the PTCDI electrode of Example 1 of the present invention is + Schematic diagram of the redox mechanism of the storage reaction.

[0020] Figure 3 Graph showing the contribution rates of the capacitance process and the diffusion control process of the PTCDI electrode in the three-electrode system at different scan rates according to the first embodiment of the present invention.

[0021] Figure 4 The full battery of Example 1 of the present invention is at 40A g -1 Cycle performance diagram.

[0022] Figure 5 This is a rate performance diagram of the full battery of Example 1 of the present invention at different current densities.

[0023] Figure 6 The full battery of Example 1 of the present invention and the disclosed aqueous I2-cathode battery and aqueous rechargeable K + Comparison of rate performance of full battery system (ARKFB).

[0024] Figure 7 1 is a comparison diagram of the discharge voltage plateau of the full battery of Example 1 of the present invention and a previously disclosed battery.

[0025] Figure 8 This is a comparison chart of the Ragoneplots (logarithmic relationship between power density and corresponding energy density) of the full battery of Example 1 of the present invention and the disclosed aqueous I2-cathode battery and ARKFB.

[0026] Figure 9 This is a graph showing the contribution rates of the capacitance process and the diffusion control process of the full battery of Example 1 of the present invention at different scan rates.

[0027] Figure 10 1 is a comparison chart of the self-discharge rates of the full battery of Example 1 of the present invention and the ZnI2 full battery.

[0028] Figure 11 A simple overall schematic diagram of PTCDII2 single cell and cascade cell.

[0029] Figure 12 CV curves of the PTCDII2 cascade battery according to Example 2 of the present invention in a mixed electrolyte at different scan rates.

[0030] Figure 13 This is a graph showing the contribution rates of the capacitance process and the diffusion control process of the PTCDII2 cascade battery of Example 2 of the present invention at different scan rates.

[0031] Figure 14 The PTCDII2 cascade battery of Example 2 of the present invention was subjected to a saturated KCl+I2(aq) mixed electrolyte at 60A g -1 Cyclic performance diagram under (142.2C).

[0032] Figure 15 The initial SEM image of the PTCDI anode of Example 2 of the present invention and the SEM image of the PTCDI anode in a saturated KCl+I2(aq) mixed electrolyte at 40A g -1 (94.8C) SEM image after 9200 cycles.

[0033] Figure 16 This is a cycle performance diagram of the PTCDII2 cascade battery of Example 2 of the present invention in a saturated KCl+I2(aq) mixed electrolyte. The specific capacity is calculated based on the mass loading of I2 in the I2-cathode of Example 2.

[0034] Figure 17 This is a graph showing the cycle performance and rate performance of the PTCDII2 cascade battery of Example 2 of the present invention in a saturated KCl+I2(aq) mixed electrolyte. The specific capacity is calculated based on the mass load of I2 in the I2-cathode of Example 2.

[0035] Figure 18 This is a comparison chart of the operating voltage range between the PTCDII2 cascade battery of Example 2 of the present invention and the disclosed high-voltage aqueous battery.

[0036] Terminology

[0037] Unless otherwise indicated, the following terms and phrases as used herein have the following meanings:

[0038] "wt%" means percentage by mass.

[0039] “Ragone plots” represent the logarithmic relationship between power density and the corresponding energy density.

[0040] "ARKFB" means water-based rechargeable K + Full battery.

[0041] "aq" means aqueous solution.

[0042] "M" stands for molar concentration. DETAILED DESCRIPTION

[0043] In order to make the objects and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and Examples. It should be understood that the effects of the specific embodiments described herein are merely for the purpose of explaining the present invention and are not intended to limit the present invention. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as those generally understood by those skilled in the art in the field of this application. The terms used in this specification in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0044] Synthesis of Chemicals and Materials. All materials were purchased and used without further treatment. Iodine (I2; ≥99.8%, Aladdin, China), potassium chloride (KCl; 99%, Aladdin, China), 3,4,9,10-perylenetetracarboxylic diimide (PTCDI; 95%, Alfa Aesar, America), and activated carbon (AC; XFNANO, China) were purchased from commercial sources.

[0045] Electrochemical characterization. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) tests and electrochemical impedance spectroscopy (EIS) measurements were performed on an electrochemical workstation (CHI760E, Chenhua, China). The electrochemical potential window of the aqueous electrolyte was determined by a three-electrode system (working electrode: KB electrode; counter electrode: platinum electrode; reference electrode: standard Ag / AgCl electrode). Constant current charge / discharge (GCD) measurements were performed in a battery test system (CT3002A, LANHE, China). Field pressure tests were performed during the CV tests to determine the release of H2 and O2 through a pressure sensor (CYYZ11, Starsensor, China). The specific current was calculated based on I2-the mass of I2 in the cathode. Specific capacity C (mAhg -1 ) is calculated as follows:

[0046] C=IΔt / 3.6m

[0047] Where I(A) is the applied current, Δt(s) is the corresponding charge or discharge time, and m(g) is I2 - the mass of I2 in the cathode electrode.

[0048] Example 1

[0049] The aqueous organic anode I2 battery of this embodiment includes an anode, a cathode, and an electrolyte. The anode includes an anode active material, and the cathode includes a cathode active material. The anode active material includes PTCDI, and the cathode active material includes I2. The preparation method is as follows.

[0050] 1) Preparation of PTCDI anode

[0051] PTCDI, Ketjen black (KB), and polyvinylidene fluoride (PVDF) binder were uniformly mixed in an N-methylpyrrolidone (NMP) solvent at a mass ratio of 7:2:1. After stirring for 4 hours, the mixture was coated on a graphite paper (GP) substrate and dried under vacuum at 80°C for 12 hours to obtain an average mass loading of 1.0-1.3 mg cm -2 PTCDI anode.

[0052] At 5mVs -1 to 45mV s -1 The PTCDI electrode was tested by CV at multiple scan rates. Figure 1 As the scan rate increases, the intensity of the electrode redox peak gradually increases, and the CV curves maintain a similar shape, confirming the excellent high-rate tolerance of the PTCDI electrode.

[0053] PTCDI has a monoclinic phase, and the interplanar spacing of its layers is 0.393 nm, which is larger than the interplanar spacing of graphite (0.335 nm), which is beneficial to K + Diffusion in the PTCDI crystal. Due to the large interplanar distance of PTCDI, PTCDI as the anode active material, K + The intercalation / deintercalation is highly reversible. Figure 2 K + Schematic diagram of the redox mechanism of the reversible storage reaction in PTCDI. The conversion between the carbonyl (-C=O) and enol (-CO) groups at the PTCDI anode is also highly reversible.

[0054] The contribution rates of the capacitance process and the diffusion control process were tested at different scan rates for the PTCDI anode of this embodiment in a three-electrode system. The results are shown in FIG. Figure 3 As shown. At 15mV s -1 At a scan rate of 45 mV s, the contribution rate of PTCDI capacitance control is close to 69.0%. In addition, the proportion of its capacitance control increases with the increase of scan rate, and at 45 mV s -1 It can reach 83.9% when the working current density is high. + The ion transport speed is fast enough. Since the capacitive effect can provide more charge transfer than bulk lattice diffusion, it helps the PTCDI electrode maintain its capacity at high operating current density.

[0055] 2) Preparation of I2- cathode materials

[0056] Equal amounts of solid I2 and AC were ground and mixed, sealed in a hydrothermal reactor, and heated at 80°C for 4 hours. After natural cooling, a porous I2-cathode material was obtained, in which I2 was the cathode active material.

[0057] 3) Preparation of I2- cathode

[0058] The I2-cathode material, KB, and PVDF binder from step 2) were uniformly mixed in an NMP solvent at a mass ratio of 8:1:1. After stirring for 4 hours, the mixture was coated on a GP substrate and dried under vacuum at 40°C for 12 hours. The average mass loading was 1.0-1.3 mg cm -2 I2 - cathode.

[0059] 4) Battery Preparation

[0060] A beaker-type PTCDII2 full cell was assembled using 10 mL of saturated KCl aqueous solution at 25°C as the electrolyte, the PTCDI anode (1 × 1 cm) obtained in step 1) as the anode, and the I2-cathode obtained in step 3) as the cathode (1 × 1 cm). The distance between the two electrodes was approximately 1 cm. Considering I2 (422 mAh g -1 ) and PTCDI (137 mAh g -1 )'s theoretical capacity, using a mass ratio of PTCDI:I2=4:1.

[0061] Compared with the traditional metal I2 battery system, the PTCDII2 full battery shows obvious advantages in fully utilizing the anode. During the charge / discharge process, I - / I 0 / I + The oxidation / reduction reaction occurs at the I2-cathode, while the enolization / recovery of the carbonyl group and the K + The intercalation / deintercalation occurs at the PTCDI anode. Therefore, the chemical equation of the full cell of PTCDII2 in saturated KCl aqueous solution can be described as Equation (1-2).

[0062] cathode:

[0063] anode:

[0064] In GCD mode at 40A g -1 The cycling performance of the PTCDII2 full cell was studied, and the specific capacity was calculated based on the mass of I2 in the I2-cathode. Figure 4 As shown, after 92,000 cycles, at 40 A g -1 Under the conditions of (94.8C), the PTCDII2 full battery of this embodiment achieved 154mAh g -1 After 92,000 cycles, the theoretical specific capacity of the battery (422 mAh g -1 ) and initial specific capacity (363.4 mAh g-1 ) retention percentages were 36.5% and 42.4%, and the decay rates per thousand cycles were 0.7% and 0.6%, respectively.

[0065] This extraordinarily long life and high capacity at high rates are attributed to the - The inertness and large interplanar spacing of the PTCDI anode, along with the large π-conjugated structure of PTCDI, contribute to its excellent stability at high oxidation potentials. Furthermore, the highly reversible olefination of quinone (-C=O) to quinone salt (-COM) facilitates the structural stability of the PTCDI anode during repeated cycling, thus benefiting the cycling performance of the full cell.

[0066] like Figure 5 As shown, the PTCDII2 full cell was studied at 40A g -1 to 160A g -1 The rate performance diagram at different current densities. -1 , 70A g -1 、100A g -1 、130A g -1 and 160A g -1 In the case of PTCDII2 full battery, the battery reaches 323mAh g -1 , 204mAh g -1 , 140mAh g -1 , 116mAh g -1 and 104mAh g -1 It is worth noting that when the current density is increased from 160A g -1 becomes 40A g -1 The full battery of this embodiment achieves 322 mAh g -1 The discharge capacity, which is 99.7% of the initial specific capacity, verifies the excellent rate performance of the full battery.

[0067] The full battery of this embodiment is compared with the disclosed I2-cathode battery and ARKFB (see Figure 6 and references) were compared with the rate performance, and the results are as follows Figure 6 As shown, the full-cell rate performance level of this embodiment is the highest.

[0068] In addition, the PTCDII2 full battery of this embodiment is compared with the battery of the disclosed literature (see Figure 7 and reference documents) are compared, and the results are as follows Figure 7As shown in the figure, its voltage stability is much better than all the published aqueous rechargeable ZnI2, FeI2, AlI2, H2I2 and most ARKFBs, indicating that the PTCDII2 full battery of this embodiment has good prospects in terms of high energy output.

[0069] Figure 8 The PTCDII2 full battery of this embodiment is compared with the disclosed aqueous I2-cathode battery and ARKFB (see Figure 8 and reference documents) of the Ragone plots. -1 At a power density of , the energy density of the full battery in this embodiment is 434Wh kg -1 . At 155072W kg -1 At the peak power density of 100W, the full battery of this embodiment can also maintain 86Wh kg -1 It can be seen that its energy density and power density far exceed those of the published I2-cathode aqueous batteries and most ARKFBs.

[0070] Figure 9 The contribution rate diagram of the capacitance process and diffusion control process of the full battery of this embodiment at different scan rates is shown in Figure 2. -1 At a scan rate of 100 mV s, the contribution of capacitance control is close to 53.3%. In addition, as the scan rate increases, the contribution of capacitance control of the full battery of this embodiment increases at 30 mV s -1 It reaches 72.1% when the power consumption is 2.537 W / m, which means it has excellent rate performance.

[0071] At 40A g -1 After charging to 2.4 V at 94.8 C, the self-discharge rate of the full cell (PTCDII2) was evaluated. A ZnI2 full cell was constructed in a 1M KCl+1M ZnCl2 mixed electrolyte as a control group and the self-discharge rate was evaluated at 40 A g -1 The self-discharge rate was evaluated after charging to 1.8V (94.8C). Figure 10 As shown in Figure 3, the 0.4V voltage drop of the PTCDII2 full cell takes 78.2 seconds, while the same voltage drop of the ZnI2 full cell takes 27.6 seconds. In other words, the self-discharge rate of the PTCDII2 full cell is reduced to 35.3% compared with the ZnI2 full cell.

[0072] Since the PTCDI anode is - The inherent inertia of - / I 0 / I + The rapid conversion in saturated KCl aqueous solution, so the full battery of this embodiment has an ultra-long life (at 40A g-1 (94.8°C) and extremely high rate tolerance (at 160Ag -1 104mAh g -1 ), high energy density (at 50420W kg -1 434Wh kg -1 ) and high power density (at 86Whkg -1 155072W kg -1 ), and in this respect far exceeds the disclosed I2-cathode aqueous batteries and most disclosed K + Ion aqueous battery.

[0073] Example 2

[0074] The preparation method for the aqueous organic anode I2 battery in this example is the same as that in Example 1, except that in step 4), a beaker-type PTCDII2 full cell is assembled using 10 mL of a saturated KCl+I2 mixed aqueous solution as the electrolyte. The saturated KCl+I2 mixed aqueous solution refers to an aqueous solution in which both KCl and I2 are saturated at 25°C. The preparation method is as follows.

[0075] At 25°C, take 20 mL of saturated KCl aqueous solution (molar concentration of approximately 3.4 mol / L). Then, under magnetic stirring at 400 r / min, add 20 mg of solid iodine to the saturated KCl aqueous solution. Because iodine easily sublimes, the amount of solid iodine here is slightly excessive to ensure that the mixed solution is saturated with KCl and I2. Finally, seal the container and continue magnetic stirring for 2 hours to obtain a saturated KCl + I2 (aq) mixed aqueous solution.

[0076] The PTCDII2 full battery of this embodiment can work stably in a saturated KCl aqueous solution as a single battery, and can also work stably in a saturated KCl+I2(aq) mixed aqueous solution as a cascade battery. The simplified schematic diagram of the single battery and cascade battery is shown in the figure. Figure 11 As shown. The PTCDII2 full cell includes an I - / I 0 I 0 / I + Symmetrical battery [Formula (3-4)] and a PTCDII2 single battery [Formula (5-6)].

[0077] Symmetrical cell: cathode:

[0078] anode:

[0079] Single cell: cathode:

[0080] anode:

[0081] It can be seen that, unlike the strategy of limiting I2 to the cathode to prevent it from entering the electrolyte in metal I2 batteries (in fact, this cannot completely prevent I2 from entering the electrolyte), there is no need to consider the problem of I2 leakage in the PTCDII2 full battery. On the contrary, introducing I2 into the electrolyte is beneficial to the PTCDII2 battery because it will lead to the self-construction of a cascade battery in the KCl+I2(aq) mixed electrolyte. Cascade batteries integrate two or more battery reactions into one battery, avoiding the non-electrochemically active connections required for external integration, improving the utilization of the reaction chamber, and effectively increasing energy output, so they have obvious advantages.

[0082] At 3mV s -1 , 6mV s -1 , 10mV s -1 , 12mV s -1 , and 15mV s -1 The CV curve of the PTCDII2 cascade battery prepared in this example was tested at a scan rate to evaluate its kinetic behavior. Figure 12 As shown, the five CV curves exhibit similar shapes, confirming that the tandem battery has excellent high-rate tolerance.

[0083] Figure 13 The contribution rate diagram of the capacitance process and diffusion control process at different scan rates of the PTCDII2 cascade battery of Example 2 is shown in FIG. The PTCDII2 cascade battery of this example shows a higher capacitance contribution at high scan rates, which means that it has excellent rate performance.

[0084] Figure 14 For this embodiment, the PTCDII2 cascade battery is -1 The cycling performance diagram at a higher current density of 60 A g -1 It achieved 105,000 cycles, showing excellent cycle stability.

[0085] Figure 15 The initial SEM image of the PTCDI anode of this embodiment and the SEM image of the PTCDI anode in a saturated KCl+I2(aq) mixed electrolyte at 40A g -1 (94.8C) SEM image after 9200 cycles. It can be seen that after 9200 cycles, the morphology and particle size of the PTCDI anode are almost the same as those of the original anode, further verifying the effect of PTCDI on I -Intrinsic advantages of immunity and excellent structural stability.

[0086] Figure 16 The figure shows the cycling performance of the PTCDII2 cascade battery of this embodiment in a saturated KCl+I2(aq) mixed electrolyte. The specific capacity is calculated based on the mass loading of I2 in the I2-cathode. After 6000 cycles, the battery is charged at 40A g -1 In this case, the PTCDII2 cascade battery of this embodiment provides 625mAh g -1 High discharge capacity.

[0087] Figure 17 The cycle performance and rate performance of the PTCDII2 cascade battery of Example 2 of the present invention in a saturated KCl+I2(aq) mixed electrolyte are shown in FIG. The specific capacity is calculated based on the mass load of I2 in the I2-cathode of Example 2. At a current density of 40A g -1 , 70A g -1 、100A g -1 、130A g -1 and 160A g -1 The discharge capacity of the cascade battery is 574 mAh g -1 , 500mAh g -1 , 376mAh g -1 , 285mAh g -1 and 264mAh g -1 It is worth noting that when the current density is increased from 160A g -1 becomes 40A g -1 When the PTCDII2 cascade battery of the embodiment of the present invention provides 572mAh g -1 The discharge capacity is the initial 40Ag -1 99.7% of the time, indicating superb rate performance.

[0088] Figure 18 The PTCDII2 cascade battery of the second embodiment of the present invention and the disclosed high-voltage aqueous battery (see Figure 18 The working voltage range comparison chart between the two (and references). It can be seen that the working voltage range of the cascade battery of this embodiment is quite large. Unlike the disclosed I2-cathode single cell, this embodiment successfully constructed a PTCDII2 cascade battery in a saturated KCl+I2(aq) mixed electrolyte, proving the feasibility of the cascade battery in the I2-battery and making full use of the I2 leaked from the I2-cathode as I in the electrolyte. - / I 0 I 0 / I + Symmetrical batteries can output more energy.

[0089] In this example, a saturated KCl+I2(aq) mixed aqueous solution was used as the electrolyte to evolve the PTCDII2 battery into a cascade form, allowing the battery voltage to further reach 2.5V without the need for water-based salts or polymer additives. By replacing the metal anode with an organic compound, a new approach was provided for the research of high-performance I2-cathode aqueous batteries. In addition, the concept of the PTCDII2 cascade battery not only enriches the family of high-performance aqueous halogen batteries, but also paves a new path for the construction of high-performance battery systems based on sulfur electrodes.

[0090] Finally, it should be noted that the above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

[0091] The publicly available batteries used in the control test are as follows:

[0092] The positive electrode of the Ref.3 battery is I2 / PAC, the negative electrode is zinc sheet, and the electrolyte is a mixed aqueous solution of ZnCl2, LiCl, and ACN (molar ratio of 19:19:8). Its preparation method refers to Zou, Y. et al. A four-electron Zn-I2 aqueous battery enabled by reversible I - / I2 / I + conversion. Nat. Commun. 12, 170 (2021).

[0093] The positive electrode of Ref.5 battery is Ti3C2I2 (obtained by etching MXenes with CuI), the negative electrode is zinc sheet, and the electrolyte is a mixed solution of 2MZnCl2 and 1M KCl. Its preparation method is based on the literature Li, X. et al. Activating the I 0 / I + redox couple in an aqueous I2-Zn battery to achieve a high voltage plateau.EnergyEnviron.Sci.14, 407-413(2021).

[0094] Ref.6 positive electrode is I2-Nb2CT x(obtained by electroplating), the negative electrode is zinc sheet, the electrolyte is 1M ZnSO4, and its preparation method refers to the literature Li, X. et al. Enhanced redox kinetics and duration of aqueous I2 / I - conversion chemistry by MXene confinement.Adv.Mater.33,2006897(2021).

[0095] The positive electrode of Ref.14 is I2 / ACF (solution adsorption method, similar to Ref.3), the negative electrode is zinc sheet, and the electrolyte is 1M ZnSO4. Its preparation method refers to Pan, H. et al. Controlling solid-liquid conversion reactions for a highly reversible aqueous zinc-iodine battery. ACS Energy Lett. 2, 2674-2680 (2017).

[0096] The positive electrode of Ref.16 is I2 / N-HPC (the two are solid-phase mixed and heated to 130 degrees Celsius), the negative electrode is iron sheet, and the electrolyte is 1M FeSO4. The preparation method refers to Bai, C., Jin, H., Gong, Z., Liu, X. & Yuan, ZA high-poweraqueous rechargeable Fe-I2 battery. Energy Stor. Mater. 28, 247-254 (2020).

[0097] The positive electrode of Ref.17 is I2@ZIF-8-C (the two are solid-phase mixed and heated to 120 degrees Celsius), the negative electrode is aluminum sheet, and the electrolyte is 9M LiTFSI+1M AlCl3. The preparation method refers to Yang, S. et al. High-rate aqueous aluminum-ton batteries enabled by confined iodine conversion chemistry. Small Methods 5, 2100611 (2021).

[0098] The negative electrode of Ref.18 is a zinc sheet, the cathode contains 0.5M ZnSO4, 1M LiI and 0.1M I2, and the anode contains 0.5MZnSO4 and 0.5M Li2SO4. Its preparation method refers to Yang, H. et al. A metal-organic framework as a multifunctional ionic sieve membrane for long-life aqueous zinc-iodide batteries. Adv. Mater. 32, 2004240 (2020).

[0099] The positive electrode of Ref.19 is iodine / nitrogen doped porous carbon (I2–NPC-900), the negative electrode is zinc sheet, and the electrolyte is 1M ZnSO4. The preparation method refers to Yu, D., Kumar, A., Tuan Anh, N., Nazir, MT&Yasin, G. High-voltage and ultrastable aqueous zinc-iodine battery enabled by N-doped carbon materials: Revealing the contributions of nitrogen configurations. ACSSustain. Chem. Eng. 8, 13769-13776 (2020).

[0100] The positive electrode of Ref.20 is Co[Co 1 / 4 Fe 3 / 4 (CN)6] / I2. The negative electrode is a zinc sheet. The electrolyte is 0.4g acrylamide added to 3mL of 2M ZnSO4 solution. The preparation method is based on the reference Ma, L. et al. Electrocatalytic iodine reduction reaction enabled by aqueous zinc-iodine battery with improved power and energy densities. Angew. Chem. Int. Ed. 60, 3791-3798 (2021).

[0101] The positive electrode of Ref.21 is ZC-mK2CO3@I2, the negative electrode is zinc sheet, and the electrolyte is 2M Zn(CF3SO3)2 containing 0.1M ZnI2 as an additive. Its preparation method refers to Chen, C. et al. High-energy density aqueouszinc-iodine batteries with ultra-long cycle life enabled by the ZnI2additive. ACS Sustain. Chem. Eng. 9, 13268-13276 (2021).

[0102] Ref.36 used bipyridine phenazine (DPPZ) and indium ferrocyanide (InHCF) as anode and cathode, respectively, and used a mixed solution containing 0.05M H2SO4 and 1M KCl (pH = 1) as electrolyte. The preparation method of the solution was based on the reference Qiao, J. et al. Long-life aqueous H + / K + dual-cation batteries based on dipyridophenazine / / hexacyanoferrate electrodes. ACS Appl. Energy Mater. 4, 4903-4909 (2021).

[0103] Ref.37 uses environmentally friendly 1,4,5,8-naphthalenetetracarboxylic dianhydride-derived polyimide (PNTCDA) as the anode, Berlin green (FeHCF) as the cathode, and the electrolyte is a saturated potassium nitrate solution. The preparation method refers to Wang, M., Wang, H., Zhang, H. & Li, X. Aqueous K-ion battery incorporating environment-friendly organic compound and berlin green. J. Energy Chem. 48, 14-20 (2020).

[0104] Ref.38 uses KTi2(PO4)3 / C crystalline nanoparticles as the anode material, ferrocyanide as the cathode, and 21MKCF3SO3 as the electrolyte. Its preparation method is based on the literature Li, Y. et al. An ultra-long life aqueous full K-ion battery. J. Mater. Chem. A 9, 2822-2829 (2021).

[0105] Ref.39 uses Prussian blue potassium (KPB) as the bipolar material, and the electrolyte is 1.0M KCl aqueous solution. The preparation method refers to Lu, K., Zhang, H., Gao, S., Cheng, Y. & Ma, H. High rate and stable symmetric potassium ion batteries fabricated with flexible electrodes and solid-state electrodes. Nanoscale 10, 20754-20760 (2018).

[0106] Ref.40 positive electrode is δ-K 0.5 V2O5 (KVO), the negative electrode is PTCDI, the electrolyte: a 22M KCF3SO3, the preparation method of which refers to Liang, G. et al. Reconstructing vanadium oxide with anisotropic pathways for a durable and fast aqueous K-ion battery. ACS Nano 15, 17717-17728 (2021).

[0107] Ref.42 is a coin-type half-cell (CR2032), using PTCDI electrode as the working electrode and K metal as the counter electrode and reference electrode. The preparation method refers to Bai, Y. et al. Perylenetetracarboxylic diimide as a high-rate anode for potassium-ion batteries. J. Mater. Chem. A 7, 24454-24461 (2019).

[0108] Ref.43 The positive electrode is MoS2 / graphene; the negative electrode is zinc sheet, and the electrolyte is 3M Zn(CF3SO3)2. The preparation method refers to Li, S. et al. Sandwich-like heterostructures of MoS2 / graphene with enlarged interlayer spacing and enhanced hydrophilicity as high-performance cathodes for aqueous zinc-ion batteries. Adv. Mater. 33, 2007480 (2021).

[0109] Ref.44 mainly cites the reference Chao, D. & Fan, HJ Intercalation pseudocapacitive behavior powers aqueous batteries. Chem 5, 1359-1361 (2019), which interprets the capacitance effect.

[0110] Ref.45 mainly cites the reference Chao, D. et al. Array of nanosheets render ultrafast and high-capacity Na-ion storage by tunable pseudocapacitance. Nat. Commun. 7, 12122 (2016) for the interpretation of capacitance effect.

[0111] Ref.46 uses polyiodine-doped polyaniline (PANI-I2) as the ZIB cathode, the negative electrode is zinc sheet; the electrolyte is 2MZnSO4. Its preparation method refers to Zeng, X. et al. Anchoring polyiodide to conductive polymers as cathode for high-performance aqueous zinc-iodine batteries. ACSS Sustain. Chem. Eng. 8, 14280-14285 (2020).

[0112] Ref.47 uses activated carbon (AC) as the cathode material, low-cost glass fiber as the separator, and Pt / C as the simulated H2 anode. The electrolyte is a 1 M KI neutral electrolyte solution supplemented with 1.2 M KH2PO4 and K2HPO4. The preparation method is based on the reference Zhu, Z., Meng, Y., Cui, Y. & Chen, W. An ultrastable aqueous iodine-hydrogen gas battery. Adv. Funct. Mater. 31, 2101024 (2021).

[0113] Ref.48 uses PTCDI electrode as the working electrode, Na metal as the counter electrode and reference electrode, and the electrolyte (Solvonic, 99%) used is 1M NaFSI (sodium bis(fluorosulfonyl)imide) in a 1:1 (v / v) mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC). The preparation method is based on the literature Liebl, S. et al. Perylenetetracarboxylicdiimide as diffusion-less electrode material for high-rate organic Na-ion batteries. Chem. Eur. J. 26, 17559-17566 (2020).

[0114] Ref.49 uses potassium manganese hexacyanoferrate K1.82Mn[Fe(CN)6]0.96·0.47H2O as cathode, PTCDI as anode, and 21M KCF3SO3 as electrolyte. Its preparation method refers to Ge, J., Fan, L., Rao, AM, Zhou, J.&Lu, B. Surface-substituted prussian blue analogue cathode for sustainable potassium-ion batteries. Nat. Sustain. 5, 225-234 (2022).

[0115] The positive electrode of Ref.50 is an activated carbon cloth / polymer-iodine (ACC / PVP–I2) composite material, and the negative electrode is a lithium sheet; the electrolyte is 1M LiN(CF3SO2)2 (LiTFSI). Its preparation method refers to the reference Meng, Z. et al. Ultra-stable binder-free rechargeable Li / I2 batteries enabled by "betadine" chemical interaction. Chem. Commun. 54, 12337-12340 (2018).

[0116] Ref.51 uses Fe2[(2,3,9,10,16,17,23,24-octahydroxyphthalocyanine)Cu]MOF composited with I2(Fe2–O8–PcCu / I2) as the cathode, the electrolyte is 1M NaClO4 in ethylene carbonate and diethyl carbonate (EC / DEC) (volume ratio of 1:1), and Nafoil is used as the counter electrode / reference electrode. The preparation method refers to Wang, F. et al. Fully conjugatedphthalocyanine copper metal-organic frameworks for sodium-iodine batteries with long-time-cycling durability. Adv. Mater. 32, 1905361 (2020).

[0117] Ref.52 uses an independent I2 / C composite cathode and a metal K anode. The electrolyte is 0.5M potassium hexafluorophosphate (KPF6) dissolved in ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1:1). Its preparation method is referenced in the literature.

[0118] Lu, K. et al. Rechargeable potassium-ion batteries enabled by potassium-iodine conversion chemistry. Energy Stor. Mater. 16, 1-5 (2019).

[0119] Ref.53 uses I2-graphene composite as cathode, lithium as anode, and 0.2M LiNO3 as electrolyte. Its preparation method refers to Sun, C. et al. Ti3C2T x MXene interface layer driving ultra-stable lithium-iodine batteries with both high iodine content and mass loading.ACS Nano 14, 1176-1184 (2020). The Ref.54 battery uses an ACC / I2 cathode and a magnesium anode. Its preparation method refers to Tian, ​​H. et al. High power rechargeable magnesium / iodine battery chemistry. Nat. Commun. 8, 14083 (2017).

[0120] Ref.55 uses PVP-I2 as cathode and Al as negative electrode. The electrolyte is made by mixing AlCl3 and 1-ethyl-3-methylimidazolium chloride (EMIC) in a molar ratio of 1.3:1. The preparation method is based on the reference Tian, ​​H., Zhang, S., Meng, Z., He, W. & Han, W.-Q. Rechargeable aluminum / iodine battery redox chemistry in ionicliquid electrolyte. ACS Energy Lett. 2, 1170-1176 (2017).

[0121] Ref.56 is an I2 cathode encapsulated with conductive carbon (I2@C-50), the negative electrode is a zinc sheet, and the electrolyte is 2M Zn(CF3SO3)2. The preparation method refers to Li, W., Wang, K. & Jiang, KA high energy efficiency and long life aqueous Zn-I2 battery. J. Mater. Chem. A 8, 3785-3794 (2020).

[0122] Ref.57 uses carbon black composite material as cathode, metal zinc foil or copper foil as anode, and 1.5MKI prepared with ethylene glycol as electrolyte. The preparation method refers to Li, H., Li, M., Zhou, X. & Li, TA novel rechargeable iodide ion battery with zinc and copper anodes. J. Power Sources 449, 227511 (2020).

[0123] Ref.58 uses NiHCF as the working electrode, Pt counter electrode, Ag / AgCl reference electrode, and 1M KNO3 or 1M NaNO3 as the electrolyte. Its preparation method refers to Wessells, CD, Peddada, SV, Huggins, RA & Cui, Y. Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries. Nano Lett. 11, 5421-5425 (2011).

[0124] Ref.59 is Ti(SO4)2, and its preparation method refers to Xu, Y., Xie, C., Li, T. & Li, XA high energy density bromine-based flow battery with two-electron transfer. ACS Energy Lett. 7, 1034-1039 (2022).

[0125] Ref.60 anode is magnesium foil, cathode is PTO (or S or P14AQ), electrolyte is 0.5mol kg-1 Mg(CB 11 H 12 )2, its preparation method refers to Dong, H. et al. High-power Mg batteries enabled by heterogeneous enolization redox chemistry and weakly coordinating electrolytes. Nat. Energy 5, 1043-1050 (2020).

[0126] Ref.61 cathode: S, anode: PbO2, electrolyte: 0.5M Pb(NO3)2, preparation method reference Xu, C. et al. Synergistic dual conversion reactions assisting Pb-S electrochemistry for energy storage. P. Nati. Acad. Sci. USA. 119, e2118675119 (2022).

Claims

1. An aqueous organic anode I2 battery comprising an anode, a cathode and an electrolyte, characterized in that: The anode includes an anode active material, the anode active material includes 3,4,9,10-perylenetetracarboxylic acid diimide, the cathode includes a cathode active material, the cathode active material includes I2, and the electrolyte is an aqueous electrolyte.

2. The aqueous organic anode I2 battery according to claim 1, wherein The electrolyte is a saturated KCl aqueous solution at 25°C.

3. The aqueous organic anode I2 battery according to claim 2, wherein The mass ratio of the 3,4,9,10-perylenetetracarboxylic acid diimide to I2 is 4:

1.

4. The aqueous organic anode I2 battery according to claim 1, wherein The electrolyte is a saturated aqueous solution of KCl and I2 at 25°C.

5. A method for preparing an aqueous organic anode I2 battery according to any one of claims 1 to 4, characterized in that: The following steps are involved: 1) mixing 3,4,9,10-perylenetetracarboxylic acid diimide, carbon black and polyvinylidene fluoride in N-methylpyrrolidone solvent, coating the mixture on a graphite paper substrate, and drying the mixture to obtain an anode; 2) grinding and mixing I2 and activated carbon, and preparing the cathode material through hydrothermal reaction; 3) mixing carbon black and polyvinylidene fluoride with the cathode material obtained in step 2) in an N-methylpyrrolidone solvent, coating the mixture on a graphite paper substrate, and drying the mixture to obtain a cathode; 4) Assembling the electrolyte, the anode obtained in step 1) and the cathode obtained in step 3) into a battery.

6. The method for preparing an aqueous organic anode I2 battery according to claim 5, wherein The mass ratio of 3,4,9,10-perylenetetracarboxylic acid diimide, carbon black and polyvinylidene fluoride in step 1) is 7:2:

1.

7. The method for preparing an aqueous organic anode I2 battery according to claim 5, wherein: Calculated based on the total mass of the cathode material, the I2 content in the cathode material obtained in step 2) is 47.2%.

8. The method for preparing an aqueous organic anode I2 battery according to claim 5, wherein In step 2), the hydrothermal reaction temperature is 80° C. and the reaction time is 4 h.

9. The method for preparing an aqueous organic anode I2 battery according to claim 5, wherein In step 3), the mass ratio of cathode material, carbon black and polyvinylidene fluoride is 8:1:

1.

10. The method for preparing an aqueous organic anode I2 battery according to claim 5, wherein: The average mass loading of the anode obtained in step 1) and the cathode obtained in step 3) is 1.0-1.3 mg cm -2 .

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