High-rate long-cycle lead-halogen battery and preparation method thereof

Abstract

The invention belongs to the field of novel energy storage batteries, and discloses a high-rate long-cycle lead-halogen battery and a preparation method thereof. The battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is an electrode containing metal lead; the electrolyte takes soluble lead salt as a solute and water or organic liquid as a solvent; an active material of the positive electrode is selected from any one of the following: (a) a halogen composite material which is formed by loading halogen X2 on a carrier material, and the halogen X2 is Br2 or I2; wherein the carrier material is selected from a carbon material or a ligand framework material; (b) a halogen-containing compound; and (c) a halogen-containing compound composite material, wherein the halogen-containing compound composite material is formed by loading a halogen-containing compound on a carbon material. In the charging and discharging process of the battery, the negative electrode Pb is subjected to oxidation / reduction reaction, Pb < 2 + > in the electrolyte is migrated to the positive electrode to form solid PbX2 with halogen, and the shuttle effect of a multi-halogen intermediate is effectively inhibited. The battery can realize complete charging and discharging in a short time, has excellent rate capability, and has super-long cycle stability under high current density.

Description

A high-rate, long-cycle lead-halogen battery and its preparation method Technical Field

[0001] This invention belongs to the field of novel energy storage batteries, specifically a novel high-rate long-cycle lead-halogen battery and its preparation method. Background Technology

[0002] Lithium-ion batteries have garnered significant attention in the emerging energy storage field due to their superior energy density and portability. However, safety concerns stemming from the traditional flammable organic electrolytes used in lithium-ion batteries, coupled with the rising price of lithium resources, have hindered their further development. Meanwhile, traditional lead-acid batteries, as the mainstream aqueous battery type, while inexpensive and safe, suffer from low energy density (actually only 30-50 Wh / kg) and poor performance at high charge / discharge rates, limiting their application in fast-charging energy storage.

[0003] With advancements in scientific research and technology, aqueous rechargeable metal batteries have gained popularity due to their high safety and low cost. While zinc, aluminum, and magnesium anodes possess high theoretical capacity, they are prone to side reactions such as hydrogen evolution and corrosion in aqueous electrolytes, severely limiting battery cycle life and rate performance. In contrast, lead (Pb) exhibits high chemical stability, a high hydrogen evolution overpotential, and a suitable redox potential, and its mature industrial chain makes it an ideal anode material.

[0004] In the field of cathode materials, bromine / iodine cathodes have attracted much attention due to their high theoretical specific capacity and multi-valence state characteristics. However, traditional metal-iodine / bromine batteries face severe technical bottlenecks: halogens (I₂ / Br₂) have poor intrinsic conductivity and readily form soluble polyhalogen intermediates (such as I₃) during charge and discharge. ⁻ I5 ⁻ These intermediates (such as...) are prone to the "shuttle effect," leading to the loss of active materials and a decrease in coulombic efficiency. More importantly, the shuttle effect and poor conductivity severely deteriorate the battery's kinetic characteristics, resulting in extremely poor rate performance at high current densities and a rapid decline in cycle life, making it difficult to meet the practical needs of high-rate, long-cycle energy storage applications.

[0005] Therefore, there is an urgent need to develop a battery system that can effectively suppress the multihalogen shuttle effect while possessing excellent electron / ion transport capabilities, in order to achieve a novel aqueous energy storage battery that combines high-rate performance and long cycle life. The high-rate, long-cycle lead-halogen battery described in this invention is precisely proposed to solve the above-mentioned problems. Summary of the Invention

[0006] Based on the aforementioned problems, this invention uses two halogens (X2=Br2, I2) or halogen-containing compounds (X=I, Br) as positive electrodes and matches them with a lead-containing negative electrode to construct a high-rate, long-cycle lead-halogen battery with excellent electrochemical performance. This battery can achieve complete charge and discharge in a short time and has excellent rate performance and long-cycle stability.

[0007] To achieve the above objectives, the present invention provides the following technical solution: In one aspect, the present invention provides a high-rate, long-cycle lead-halogen battery, comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode is an electrode containing metallic lead; and the electrolyte uses soluble lead salt as a solute and water or an organic liquid as a solvent.

[0008] The active material of the positive electrode is selected from any of the following: (a) a halogen composite material, wherein the halogen composite material is formed by loading halogen X2 onto a support material, wherein halogen X2 is Br2 or I2; wherein the support material is selected from carbon materials or ligand framework materials; (b) a halogen-containing compound; (c) a halogen-containing compound composite material, wherein the halogen-containing compound composite material is formed by loading a halogen-containing compound onto a carbon material; wherein the positive electrode active material is reduced during the discharge process to form X⁻ (X=I / Br) and Pb. 2 ⁺ Combines to form solid PbX2; during charging, PbX2 is oxidized and decomposed into Pb. 2+ And X2. Taking the adsorption of I2 by different carbon materials as an example, during battery discharge, the metallic lead in the negative electrode loses electrons and the elemental iodine in the positive electrode gains electrons to generate lead iodide at the positive electrode. During charging, lead iodide loses electrons and is converted into elemental iodine and lead ions, while the lead ions are deposited at the negative electrode through the electrolyte.

[0009] Preferably, in either category (a) or category (c), the carbon material is selected from at least one of graphene, carbon nanotubes, carbon fibers, activated carbon, porous carbon (ZIF-8), mesoporous carbon (CMK-3), and biochar; in category (a), when the carbon material is loaded with halogens, the loading amount of halogens is 30-40 wt%; preferably 30 wt% or 40 wt%.

[0010] In category (a), the ligand framework material is selected from at least one of metal-organic frameworks (MOFs), covalent organic frameworks (COFs), two-dimensional transition metal carbides, nitrides, and carbonitrides (MXene); in category (b) or (c), the halogenated compound is at least one of PbX2 (X=Br, I), triiodine / tetramethyl bromide quaternary ammonium salt (TMAI3 / TMABr3), triiodine / tetraethyl bromide quaternary ammonium salt (TEAI3 / TEABr3), and triiodine / tetrabutyl bromide quaternary ammonium salt (TBAI3 / TBABr3); in category (c), the content of the halogenated compound is 50-70 wt%. Preferably, it is 50 wt%, 60 wt%, or 70 wt%.

[0011] Preferably, the carbon material is at least one of activated carbon (AC), porous carbon (ZIF-8 or ZIF-8 pyrolysis carbon), mesoporous carbon (CMK-3), and biochar; wherein the porous carbon is ZIF-8 or ZIF-8 pyrolysis carbon; and the biochar is biochar alkali (coconut shell), that is, biochar alkali prepared from coconut shell.

[0012] More preferably, the carbon material is activated carbon (AC) or mesoporous carbon (CMK-3); the ligand framework material is MXene.

[0013] The specific processing method for biomass alkaline char (coconut shell) is as follows: The raw coconut shells are washed with deionized water and dried thoroughly in a 105 °C oven for 12 h. Then, the dried coconut shells are ball-milled at 800 r / min for 8 h to pulverize them. A 50% KOH solution is prepared, and 10 g of dried coconut shell powder is mixed with 20 g of the 50% KOH solution at an impregnation ratio of 1:2. The mixture is thoroughly stirred to ensure the coconut shells are completely impregnated by the alkali solution. The resulting paste is allowed to stand at room temperature for 24 h for impregnation, and then dried at 105 °C to obtain a dry solid mixed with an activator. The obtained dry solid is activated in a tube furnace, heated to 800 °C at a rate of 5 °C / min, and held at that temperature for 3 h. The activated solid is repeatedly soaked and rinsed with 0.1 M dilute hydrochloric acid until pH=7, then repeatedly rinsed with deionized water until no chloride ions are detected by silver nitrate test, and finally placed in an oven at 105 °C for thorough drying to obtain biomass alkali char (coconut shell).

[0014] The specific processing method for ZIF-8 pyrolysis carbon is as follows: First, 1.53 g of Zn(NO3)2·6H2O and 3.72 g of 2-methylimidazole were dissolved in 70 mL of methanol, and the solution was formed by magnetic stirring for 15 min. Then, Zn(NO3)2·6H2O was added dropwise to the 2-methylimidazole solution while stirring, and the mixture was stirred for another 1 h at room temperature and then allowed to stand for 12 h. The resulting white ZIF-8 crystals were centrifuged, washed several times with deionized water and methanol to obtain the precipitate, and finally dried at 60 °C for 12 h. The ZIF-8 crystals prepared according to the above method were heated to 900 °C at a heating rate of 5 °C / min under a N2 atmosphere and held for 4 h to obtain ZIF-8 pyrolysis carbon.

[0015] Preferably, the negative electrode is a metal lead foil, an electrode containing metal lead powder, or a metal lead alloy.

[0016] Preferably, the soluble lead salt is one or more of lead perchlorate, lead acetate, lead salicylate, lead citrate, lead nitrate, lead fluorosilicate, or lead tetrafluoroborate; its concentration is 0.01~10 mol / L, preferably 0.5~3 mol / L.

[0017] Preferably, the solvent is one or more selected from water, acetonitrile, ethylene glycol, ethylene carbonate, and dimethyl ether.

[0018] More preferably, the concentration of the soluble lead salt is 1 mol / L.

[0019] Preferably, the diaphragm is permeable to lead ions, and is preferably filter paper or glass fiber.

[0020] Preferably, the positive electrode is prepared as follows: the active material, conductive agent and binder of the above positive electrode are mixed in a mortar and ground, and dispersed in a solvent to form a slurry, which is then uniformly coated on the current collector and dried to obtain the final product.

[0021] The conductive agent is conductive carbon black, activated carbon, porous carbon, acetylene black (BP-2000), Ketjen black (KB), Vulcan XC-72, super carbon black (Super P), or carbon nanotubes; the binder is polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), sodium alginate (SA), or styrene-butadiene rubber (SBR); the solvent is N-methylpyrrolidone (NMP) or water; the current collector is titanium foil, stainless steel foil, non-woven fabric, or carbon paper; the mass ratio of the active material of the positive electrode to the conductive agent and binder is (4.5-8):(1-4.5):1, preferably 8:1:1 or 7:2:1.

[0022] More preferably, the conductive agent is Super P; more preferably, the current collector is titanium foil with a thickness of 30 µm.

[0023] On the other hand, the present invention provides a method for preparing the high-rate, long-cycle lead-halogen battery described above, specifically as follows: At room temperature, the following components are placed in sequence: negative electrode shell, negative electrode, separator, positive electrode, gasket, spring sheet, and positive electrode shell. 50 μL of the electrolyte is added between the negative and positive electrodes to completely wet the separator, thus transporting ions. Finally, the battery is sealed to obtain a rechargeable rocking chair-type aqueous lead-ion button battery. Alternatively, if a pouch battery is to be installed, the following components are stacked in sequence: pouch positive electrode side, positive electrode, separator, electrolyte, lead negative electrode, and pouch negative electrode side. 50 μL of the electrolyte is added to the separator between the positive and negative electrodes to completely wet the separator. The battery is then encapsulated to obtain a rechargeable rocking chair-type aqueous lead-ion pouch battery.

[0024] This invention uses a lead-containing electrode as the negative electrode, and combines it with a specific positive electrode active material and an aqueous lead-containing electrolyte with high ionic conductivity and safety factor to construct a rechargeable lead-iodine / bromine battery system for the first time.

[0025] Compared to metals such as Zn, Al, and Mg, Pb metal not only possesses advantages such as higher hydrogen evolution overpotential and higher chemical stability, but also benefits from a mature lead-acid battery industry chain, well-developed Pb metal production technology, low cost, and easy availability, making it highly suitable as the negative electrode for rechargeable aqueous metal batteries. The stable deposition / precipitation of lead as the negative electrode allows the rechargeable lead-iodine / bromine battery system described in this invention to achieve complete charge-discharge in a short time. Furthermore, the rate performance, cycle stability, and safety of this battery system are far superior to conventional metal-iodine / bromine batteries; in other words, using Pb as the negative electrode is one of the strong guarantees for realizing rechargeable lead-iodine / bromine batteries.

[0026] Compared with existing technologies, the beneficial effects of this invention are as follows: The positive electrode material of the rechargeable lead-iodine / bromine battery described in this invention has broad applicability, namely, it includes halogen-adsorbing positive electrode materials made of carbon materials with different shapes / pore sizes, halogen-adsorbing positive electrode materials made of different ligand framework materials (MOF, COF, MXene, etc.), and positive electrode materials made of different halogen-containing compounds (PbX2, TMAX3, TEAX3, TBAX3, X=I / Br) or composites. All of the above-mentioned positive electrode materials can be matched with Pb-containing negative electrodes to achieve complete charge-discharge and stable cycling in a short time. This is due to the reaction mechanism of the battery described in this invention. Taking the adsorption of I2 by different carbon materials as an example, during discharge, the negative electrode containing metallic lead loses electrons and transforms into lead ions, which react with iodine anions at the positive electrode to generate lead iodide. During charging, lead iodide loses electrons and transforms into elemental iodine and lead ions, while the lead ions are deposited at the negative electrode through the electrolyte.

[0027] This study innovatively inhibited the polyhalogen intermediate (I3). - / Br3 - I5 - / Br5 - The shuttle effect of soluble species (such as lead-acid and iodine / bromine) effectively overcomes the bottleneck problems of capacity decay and shortened cycle life caused by polyhalogen shuttle in other metal-iodine / bromine battery systems. Based on the above reaction mechanism, the rechargeable aqueous lead-acid / iodine / bromine battery of this invention can achieve more than 90% of the theoretical energy density, while traditional lead-acid batteries can only achieve 30%-40% of the theoretical energy density. Therefore, the aqueous lead-ion battery of this invention will also provide a new direction for the transformation of lead-acid batteries. Attached Figure Description

[0028] Figure 1 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 1 at a current density of 100 mA / g.

[0029] Figure 2 is a cyclic voltammetry curve of the rechargeable aqueous lead-iodine battery of Example 1 at a scan rate of 0.1 mV / s.

[0030] Figure 3 shows the rate performance of the rechargeable aqueous lead-iodine battery of Example 1 at different current densities.

[0031] Figure 4 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 1 at a current density of 8000 mA / g.

[0032] Figure 5 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 2 at a current density of 100 mA / g.

[0033] Figure 6 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 2 at a current density of 8000 mA / g.

[0034] Figure 7 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 3 at a current density of 100 mA / g.

[0035] Figure 8 is a cyclic voltammetry curve of the rechargeable aqueous lead-iodine battery of Example 3 at a scan rate of 0.1 mV / s.

[0036] Figure 9 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 3 at a current density of 5000 mA / g.

[0037] Figure 10 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 4 at a current density of 100 mA / g.

[0038] Figure 11 is a cyclic voltammetry curve of the rechargeable aqueous lead-iodine battery of Example 5 at a scan rate of 0.1 mV / s.

[0039] Figure 12 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 5 at a current density of 100 mA / g.

[0040] Figure 13 is a charge-discharge curve of the rechargeable aqueous lead-bromine battery of Example 6 at a current density of 100 mA / g.

[0041] Figure 14 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 7 at a current density of 100 mA / g.

[0042] Figure 15 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 8 at a current density of 100 mA / g.

[0043] Figure 16 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 9 at a current density of 100 mA / g.

[0044] Figure 17 is a cyclic voltammetry curve of the rechargeable aqueous lead-iodine battery of Example 9 at a scan rate of 0.1 mV / s.

[0045] Figure 18 is a charge-discharge curve of the rechargeable aqueous lead-bromine battery of Example 10 at a current density of 100 mA / g.

[0046] Figure 19 is a cyclic voltammetry curve of the rechargeable aqueous lead-bromine battery of Example 10 at a scan rate of 0.1 mV / s.

[0047] Figure 20 is a charge-discharge curve of the rechargeable aqueous lead-bromine battery of Example 11 at a current density of 100 mA / g.

[0048] Figure 21 is a charge-discharge curve of the rechargeable aqueous lead-bromine battery of Example 12 at a current density of 100 mA / g.

[0049] Figure 22 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 13 at a current density of 100 mA / g.

[0050] Figure 23 is a cyclic voltammetry curve of the rechargeable aqueous lead-iodine battery of Example 13 at a scan rate of 0.1 mV / s.

[0051] Figure 24 shows the rate performance of the rechargeable aqueous lead-iodine battery of Example 13 at different current densities.

[0052] Figure 25 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 13 at a current density of 2000 mA / g.

[0053] Figure 26 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 14 at a current density of 100 mA / g.

[0054] Figure 27 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 14 at a current density of 1000 mA / g.

[0055] Figure 28 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 15 at a current density of 100 mA / g.

[0056] Figure 29 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 15 at a current density of 1000 mA / g.

[0057] Figure 30 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 16 at a current density of 100 mA / g.

[0058] Figure 31 shows the rate performance of the rechargeable aqueous lead-iodine battery of Example 16 at different current densities.

[0059] Figure 32 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 16 at a current density of 5000 mA / g.

[0060] Figure 33 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 17 at a current density of 100 mA / g.

[0061] Figure 34 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 17 at a current density of 100 mA / g.

[0062] Figure 35 is a cyclic voltammetry curve of the rechargeable aqueous lead-bromine battery of Example 18 at a scan rate of 0.1 mV / s.

[0063] Figure 36 is a charge-discharge curve of the rechargeable aqueous lead-bromine battery of Example 18 at a current density of 100 mA / g.

[0064] Figure 37 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 19 at a current density of 100 mA / g.

[0065] Figure 38 is a cyclic voltammetry curve of the rechargeable aqueous lead-iodine battery of Example 19 at a scan rate of 0.1 mV / s.

[0066] Figure 39 shows the rate performance of the rechargeable aqueous lead-iodine battery of Example 19 at different current densities.

[0067] Figure 40 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 19 at a current density of 2000 mA / g.

[0068] Figure 41 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 20 at a current density of 100 mA / g.

[0069] Figure 42 shows the long-cycle performance of the rechargeable aqueous lead-iodine battery of Example 20 at a current density of 5000 mA / g.

[0070] Figure 43 is a charge-discharge curve of the rechargeable aqueous lead-iodine battery of Example 21 at a current density of 100 mA / g.

[0071] Figure 44 is a charge-discharge curve of the rechargeable organic lead-iodine battery of Example 22 at a current density of 100 mA / g. Detailed Implementation

[0072] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features described therein can be combined with each other.

[0073] The carbon materials involved in the embodiments of this invention are labeled as A, B, C, and D, wherein carbon material A is activated carbon; carbon material B is mesoporous carbon (CMK-3); carbon material C is biomass alkaline carbon (coconut shell); and carbon material D is ZIF-8 pyrolysis carbon.

[0074] In this invention, the carbon materials are graphene, carbon nanotubes, carbon fibers, activated carbon, porous carbon (ZIF-8), and mesoporous carbon (CMK-3), some of which are shown in Table 1; Table 1: Reagent Name, Specification, Manufacturer, Activated Carbon (1800 m³) 2 g -1 Fuzhou Yihuan Carbon Co., Ltd. Mesoporous carbon >800 m 2 g -1 Xianfeng Nanomaterials Technology Co., Ltd. Super Carbon Black AR Taiyuan Lizhiyuan Technology Co., Ltd. In this invention, the conductive agent is conductive carbon black, activated carbon, porous carbon, BP-2000, Ketjen black (KB), Vulcan XC-72, super carbon black (Super P), or carbon nanotubes, some of which are listed in Table 1; the binder is polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), sodium alginate (SA), or styrene-butadiene rubber (SBR), some of which are listed in Table 2. Table 2: Reagent Name, Specification, Manufacturer: Polyvinylidene fluoride (PVDF), Yantai Jiayineng New Material Technology Co., Ltd., Sodium carboxymethyl cellulose (SMC), Cyber ​​Electrochemical Materials Co., Ltd., Sodium alginate (SA), Tianjin Damao Chemical Reagent Factory, Styrene-butadiene rubber (SBR), Cyber ​​Electrochemical Materials Co., Ltd. Other raw materials, some of whose sources are shown in Table 3; Table 3: Reagent Name, Specification, Manufacturer, Tetramethylammonium iodide 98%, Tianjin Xiens Biochemical Technology Co., Ltd., Tetraethylammonium iodide 98%, Tianjin Xiens Biochemical Technology Co., Ltd., Tetrabutylammonium iodide 98%, Tianjin Xiens Biochemical Technology Co., Ltd., Tetrabutylammonium bromide 98%, Tianjin Xiens Biochemical Technology Co., Ltd. Table Example 1 A rechargeable aqueous lead-iodine battery and its preparation and application, including the following steps: (1) Preparation of positive electrode active material: 0.3 g of I2 is placed in an agate mortar and ground into powder. Then, it is placed in a clean, opaque glass bottle and 60 mL of deionized water is added. After stirring for 2 h, 0.7 g of carbon material A (C A The mixture was stirred for 12 hours. After the reaction was complete, it was centrifuged three times with deionized water. Finally, it was dried in a forced-air oven at 60 °C for 10 hours to obtain I. 30% @C A powder.

[0075] Preparation of the positive electrode: First, I 30% @C A Super P (SP) and CMC binder are placed in an agate mortar at a mass ratio of 8:1:1 and ground for 15 min to mix evenly. Then, deionized water is added appropriately and ground for 5 min to make a paste-like active material. This paste is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air drying oven and dried at 60 °C for 10 h to obtain the positive electrode sheet.

[0076] (2) Preparation of electrolyte: First, prepare a clean, dry empty bottle and mark the position of 10 mL solution. Then, at room temperature, pour 4.601 g of Pb(ClO4)2·3H2O solid into the empty bottle and add deionized water to the mark. Finally, shake thoroughly until the lead salt is completely dissolved, and prepare 10 mL of 1 mol·L⁻¹ electrolyte. -1 Pb(ClO4)2-H2O electrolyte.

[0077] (3) Preparation of negative electrode: The negative electrode can be lead foil (Pb foil), lead alloy or lead powder. In this example, lead foil is used, and the lead foil with a thickness of 50 µm is cut into a circular piece with a diameter of 16 mm and used directly as the negative electrode.

[0078] (4) Battery assembly: The negative electrode shell, negative electrode, separator, electrolyte, positive electrode, gasket, spring sheet, and positive electrode shell are stacked in sequence. 50 μL of electrolyte is dropped onto the separator between the positive and negative electrodes to wet the separator. The separator is then pressed and sealed using a small hydraulic button battery sealing machine to obtain the rechargeable rocking chair type aqueous lead-ion button battery described in this embodiment, which is a rechargeable aqueous lead-iodine battery.

[0079] (5) Battery performance testing: The lead-iodine batteries assembled according to the above steps, at room temperature, in the voltage range of 0.2~1.1V, were tested using a blue battery testing system at 100 mA·g. -1 The battery was subjected to constant current charge-discharge tests at a specific current density; at room temperature, the battery was subjected to 0.1 mV·s tests using a CHI760E electrochemical workstation. -1 Cyclic voltammetry tests were performed at voltage ranges of 0.2–1.0 V, at values ​​of 200, 500, 800, 1000, 2000, 5000, 8000, and 10000 mA·g. -1 Rate performance of the battery was tested at current density; within the voltage range of 0.2–1.1 V, the Blue Battery testing system was used at 8000 mA·g. -1 The battery was subjected to long-cycle testing at current density. The test results are shown in Figures 1-4.

[0080] Example 2 uses I 40% @C A Lead foil is used as the negative electrode, with the positive electrode being the active material and the negative electrode being the lead foil. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0081] The I mentioned 40% @C A The specific synthesis method of the cathode material is as follows: 0.4 g of I2 is placed in an agate mortar and ground into powder. The powder is then placed in a clean, opaque glass bottle, and 60 mL of deionized water is added. After stirring for 2 hours, 0.6 g of C is added. A Continue stirring for 12 hours. After the reaction is complete, centrifuge three times with deionized water. Finally, dry in a forced-air oven at 60 °C for 10 hours to obtain I. 40% @C A powder.

[0082] The positive electrode sheet is prepared according to the method in Example 1.

[0083] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 5.

[0084] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a voltage range of 0.2–1.1 V and tested at 8000 mA·g. -1 The long-cycle test was performed. The test results are shown in Figure 6.

[0085] Example 3 uses I 30% @C B Lead foil is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0086] The I mentioned 30% @C B The specific synthesis method of the cathode material is as follows: 0.3 g of I2 is placed in an agate mortar and ground into powder. The powder is then placed in a clean, opaque glass bottle, and 60 mL of deionized water is added. After stirring for 2 hours, 0.7 g of carbon material B (C) is added. B The mixture was stirred for 12 hours. After the reaction was complete, it was centrifuged three times with deionized water. Finally, it was dried in a forced-air oven at 60 °C for 10 hours to obtain I. 30% @C B powder.

[0087] The positive electrode sheet is prepared according to the method in Example 1.

[0088] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 7.

[0089] The assembled button cell was subjected to a voltage test of 0.1 mV·s within a voltage range of 0.2–1.1 V. -1 Cyclic voltammetry tests were performed. The test results are shown in Figure 8.

[0090] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a voltage range of 0.2–1.1 V and tested at 5000 mA·g. -1 The long-cycle test was performed. The test results are shown in Figure 9.

[0091] Example 4 with I 30% @C CLead foil is used as the negative electrode, with the positive electrode being the active material and the negative electrode being the lead foil. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0092] The I mentioned 30% @C C C in cathode materials C The specific processing method for biomass alkaline char is as follows: Raw coconut shells are washed with deionized water and dried thoroughly in a 105 °C oven for 12 h. The dried coconut shells are then ball-milled at 800 r / min for 8 h to pulverize them. A 50% KOH solution is prepared, and 10 g of dried coconut shell powder is mixed with 20 g of the 50% KOH solution at an impregnation ratio of 1:2. The mixture is thoroughly stirred to ensure the coconut shells are completely impregnated with the alkali solution. The resulting paste is allowed to stand at room temperature for 24 h for impregnation, and then dried at 105 °C to obtain a dry solid mixed with an activator. The obtained dry solid is activated in a tube furnace, heated to 800 °C at a rate of 5 °C / min, and held at that temperature for 3 h. The activated solid was repeatedly soaked and rinsed in 0.1 M dilute hydrochloric acid until pH=7, then repeatedly rinsed with deionized water until no chloride ions were detected by silver nitrate test. Finally, it was thoroughly dried in an oven at 105 °C to obtain biomass alkali char C. C .

[0093] The I mentioned 30% @C C The specific synthesis method of the cathode material is as follows: 0.3 g of I2 is placed in an agate mortar and ground into powder. The powder is then placed in a clean, opaque glass bottle, and 60 mL of deionized water is added. After stirring for 2 hours, 0.7 g of carbon material C (C2) is added. C The mixture was stirred for 12 hours. After the reaction was complete, it was centrifuged three times with deionized water. Finally, it was dried in a forced-air oven at 60 °C for 10 hours to obtain I. 30% @C C powder.

[0094] The positive electrode sheet is prepared according to the method in Example 1.

[0095] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 10.

[0096] Example 5 uses I 30% @C D Lead foil is used as the negative electrode, with the positive electrode being the active material and the negative electrode being the lead foil. 1 mol L -1Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0097] The I mentioned 30% @C D C in cathode materials D The specific processing method for ZIF-8 pyrolysis carbon is as follows: First, 1.53 g of Zn(NO3)2·6H2O and 3.72 g of 2-methylimidazole were dissolved in 70 mL of methanol, and the solution was formed by magnetic stirring for 15 min. Then, Zn(NO3)2·6H2O was added dropwise to the 2-methylimidazole solution under stirring, and stirring was continued for 1 h at room temperature, followed by standing for 12 h. The resulting white ZIF-8 crystals were centrifuged, washed several times with deionized water and methanol to obtain the precipitate, and finally dried at 60 °C for 12 h. The ZIF-8 crystals prepared according to the above method were heated to 900 °C at a heating rate of 5 °C / min under a N2 atmosphere and held for 4 h to obtain black carbon material C. D .

[0098] The I mentioned 30% @C D The specific synthesis method of the cathode material is as follows: 0.3 g of I2 is placed in an agate mortar and ground into powder. The powder is then placed in a clean, opaque glass bottle, and 60 mL of deionized water is added. After stirring for 2 hours, 0.7 g of carbon material D (C) is added. D The mixture was stirred for 12 hours. After the reaction was complete, it was centrifuged three times with deionized water. Finally, it was dried in a forced-air oven at 60 °C for 10 hours to obtain I. 30% @C D powder.

[0099] The positive electrode sheet is prepared according to the method in Example 1.

[0100] The assembled button cell was subjected to a voltage test of 0.1 mV·s within a voltage range of 0.2–1.1 V. -1 Cyclic voltammetry tests were performed. The test results are shown in Figure 11.

[0101] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 12.

[0102] Example 6 uses Br2@MXene as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-bromine battery was assembled according to the method in Example 1.

[0103] The specific preparation method of the MXene material is as follows: 1 g of NH4F powder is placed in 20 mL of 9 M HCl solution and stirred thoroughly to form an F-containing... - An acidic solution was prepared. Then, 1 g of Ti3AlC2 powder was slowly added to the above solution, and the mixture was heated (60 °C) and stirred for 48 h. The solution was then washed with deionized water until neutral (pH=7), and ultrasonically dispersed for 10 min / time. The mixture was then vacuum dried at 60 °C for 12 h to obtain the etched MXene powder.

[0104] The specific synthesis method of the Br2@MXene cathode material is as follows: 1.35 g of KBr is placed in an opaque glass bottle, 60 mL of bromine water (containing 3% bromine) is added, and the mixture is stirred evenly to obtain a yellow solution. 0.35 g of MXene is added, and the mixture is stirred for 3 h. After the reaction is completed, the mixture is centrifuged 3 times with deionized water. Finally, the mixture is dried at low temperature in a forced-air oven for 6 h to obtain Br2@MXene powder.

[0105] Preparation of positive electrode: First, Br2@MXene, Super P (SP) and CMC binder are placed in an agate mortar at a mass ratio of 8:1:1 and ground for 15 min to mix evenly. Then, deionized water is added appropriately and ground for 5 min to make a paste-like active material. This paste is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode is placed in an opaque cardboard box and allowed to air dry naturally to obtain the positive electrode.

[0106] The rechargeable aqueous lead-bromine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.5 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 13.

[0107] Example 7 uses TMAI3 as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0108] Preparation of TMAI3 cathode material: 0.332 g of KI and 0.5076 g of I2 were added to 10 mL of deionized water to prepare I3. - Solution A (KI:I2 = 1:1) is prepared by dissolving 0.308 g of tetramethylammonium iodide in 2 mL of ethanol solution (solution B) and stirring thoroughly. Then, solution B is added dropwise to solution A to obtain a dark green precipitate. Finally, the precipitate is washed three times with water and dried in a forced-air oven at 60°C for 10 h to obtain TMAI3 dark green powder.

[0109] Preparation of the positive electrode sheet: First, the positive electrode active material TMAI3, Super P and CMC binder are placed in an agate mortar and ground for 5 min and mixed evenly in a mass ratio of 7:2:1. Then, an appropriate amount of deionized water is added and ground for 20 min to make a slurry active material. This slurry is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air drying oven and dried at 60℃ for 10 h to obtain the positive electrode sheet.

[0110] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 14.

[0111] Example 8 uses TEAl3 as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0112] Preparation of TEAI3 cathode material: 0.332 g of KI and 0.5076 g of I2 were added to 10 mL of deionized water to prepare I3. - Solution A (KI:I2 = 1:1) is prepared by dissolving 0.514 g of tetraethylammonium iodide in 2 mL of ethanol solution (solution B) and stirring until homogeneous. Then, solution B is added dropwise to solution A to obtain a reddish-brown precipitate. The precipitate is washed three times with water and dried in a forced-air oven at 60 °C for 10 h to obtain TEAI3 reddish-brown powder.

[0113] Preparation of the positive electrode sheet: First, the positive electrode active materials TEAI3, Super P and CMC binder are placed in an agate mortar at a mass ratio of 7:2:1 and ground for 5 min and mixed evenly. Then, an appropriate amount of deionized water is added and ground for 20 min to make a paste-like active material. This paste is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air drying oven and dried at 60℃ for 10 h to obtain the positive electrode sheet.

[0114] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 15.

[0115] Example 9 uses TBAI3 as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0116] Preparation of TBAI3 cathode material: 0.332 g of KI and 0.5076 g of I2 were added to 10 mL of deionized water to prepare I3. - Solution A (KI:I2 = 1:1) is prepared by dissolving 0.739 g of tetrabutylammonium iodide in 2 mL of ethanol solution (solution B) and stirring until homogeneous. Solution B is then added dropwise to solution A to obtain a black precipitate. Finally, the precipitate is washed three times with water and dried in a forced-air oven at 60℃ for 10 h to obtain TBAI3 black powder.

[0117] Preparation of the positive electrode sheet: First, place the positive electrode active material TBAI3, Super P and CMC binder in an agate mortar at a mass ratio of 7:2:1 and grind for 5 min and mix evenly. Then, add an appropriate amount of deionized water and grind for 20 min to make a slurry active material. Coat the slurry evenly on a titanium foil with a thickness of 30 µm. Finally, place the coated electrode sheet in a forced-air drying oven and dry at 60℃ for 10 h to obtain the positive electrode sheet.

[0118] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 16.

[0119] The assembled button cell was subjected to a voltage test of 0.1 mV·s within a voltage range of 0.2–1.1 V. -1 Cyclic voltammetry tests were performed. The test results are shown in Figure 17.

[0120] Example 10 uses TBABr3 as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-bromine battery was assembled according to the method in Example 1.

[0121] Preparation of TBABr3 cathode material: 0.675 g of KBr was placed in 30 mL of bromine water (containing 3% bromine) to prepare Br3. - Solution A (KBr:Br2=1:1) is prepared by dissolving 1.8 g of tetrabutylammonium bromide in 2 mL of ethanol solution (solution B) and stirring until homogeneous. Then, solution B is added dropwise to solution A. The resulting orange-yellow precipitate is washed three times with water and then dried in a forced-air oven at 60 ℃ for 10 h to obtain TBABr3 yellow powder.

[0122] Preparation of the positive electrode sheet: First, the positive electrode active material TBABr3, Super P and CMC binder are placed in an agate mortar at a mass ratio of 7:2:1 and ground for 5 min and mixed evenly. Then, an appropriate amount of deionized water is added and ground for 20 min to make a slurry active material. This slurry is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air drying oven and dried at 60℃ for 10 h to obtain the positive electrode sheet.

[0123] The rechargeable aqueous lead-bromine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.5 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 18.

[0124] The assembled button cell was subjected to a voltage test of 0.1 mV·s within a voltage range of 0.2–1.5 V. -1 Cyclic voltammetry tests were performed. The test results are shown in Figure 19.

[0125] Example 11 uses PbBr2@SP as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-bromine battery was assembled according to the method in Example 1.

[0126] Preparation of cathode material: Weigh 6.62 g Pb(NO3)2 and 7.14 g KBr and put them into 40 mL of deionized water and stir evenly. Then add 1.83 g Super P to the Pb(NO3)2 solution, sonicate and stir evenly. Then slowly add KBr solution to Pb(NO3)2 solution. After the addition is complete, age for 12 h, wash with deionized water 3 times, and finally put it into a forced-air drying oven at 80 ℃ for 12 h to obtain PbBr2@SP black powder.

[0127] Preparation of the positive electrode sheet: First, the positive electrode active material PbBr2@SP, Super P and PVDF binder are placed in an agate mortar at a mass ratio of 8:1:1 and ground for 15 min and mixed evenly. Then, an appropriate amount of NMP is added and ground for 10 min to make a paste-like active material. This paste is then uniformly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a vacuum oven and dried at 60 °C for 10 h to obtain the positive electrode sheet.

[0128] The rechargeable aqueous lead-bromine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.5 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 20.

[0129] Example 12 uses PbBr2@C ASP-541 is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-bromine battery was assembled according to the method in Example 1.

[0130] Preparation of cathode materials: PbBr2, C A Super P was weighed at a mass ratio of 5:4:1 and placed into a ball mill. The ball milling conditions were 400 r / min for 8 h. After ball milling, the material was scraped onto weighing paper to obtain PbBr2@CA&SP-541.

[0131] Preparation of the positive electrode: The positive electrode active material PbBr2@C A &SP-541, SA and SBR adhesives are calculated according to a mass ratio of 9:0.5:0.5. First, a certain mass of PbBr2@C is weighed. A &SP-541 and SA were ground in an agate mortar for 15 min and mixed evenly. Then, a certain mass of SBR and an appropriate amount of deionized water were added and ground for 60 min to make a slurry active material. This slurry was then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode was placed in a forced-air oven and dried at 60 °C for 10 h to obtain the positive electrode.

[0132] The rechargeable aqueous lead-bromine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.5 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 21.

[0133] Example 13 uses PbI2@C A SP-541 is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0134] Preparation of cathode materials: PbI2, C A Super P was weighed at a mass ratio of 5:4:1 and placed into a ball mill. The ball milling conditions were 400 r / min for 8 h. After ball milling, the material was scraped onto weighing paper to obtain PbI2@C. A &SP-541.

[0135] Preparation of the positive electrode: The positive electrode active material PbI2@C A &SP-541, SA and SBR adhesives are calculated according to a mass ratio of 9:0.5:0.5. First, a certain mass of PbI2@C is weighed. A&SP-541 and SA are ground in an agate mortar for 15 min and mixed evenly. Then, a certain mass of SBR and an appropriate amount of deionized water are added and ground for 60 min to make a slurry active material. This slurry is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air oven and dried at 60 °C for 10 h to obtain the positive electrode sheet.

[0136] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 22.

[0137] The assembled button cell was subjected to a voltage test of 0.1 mV·s within a voltage range of 0.2–1.1 V. -1 Cyclic voltammetry tests were performed. The test results are shown in Figure 23.

[0138] At 100, 200, 500, 800, 1000, 2000, 5000, 8000, 10000 mA·g -1 The rate performance of the battery was tested at the current density. The test results are shown in Figure 24.

[0139] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a voltage range of 0.2–1.1 V and tested at 2000 mA·g. -1 The long-cycle test was performed. The test results are shown in Figure 25.

[0140] Example 14 uses PbI2@C A SP-631 is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0141] Preparation of cathode materials: PbI2, C A Super P was weighed at a mass ratio of 6:3:1 and placed into a ball mill. The ball milling conditions were 400 r / min for 8 h. After ball milling, the material was scraped onto weighing paper to obtain PbI2@C. A &SP-631.

[0142] Preparation of the positive electrode: The positive electrode active material PbI2@C A &SP-631, SA and SBR adhesives are calculated according to a mass ratio of 9:0.5:0.5. First, a certain mass of PbI2@C is weighed. A&SP-631 and SA are ground in an agate mortar for 15 min and mixed evenly. Then, a certain mass of SBR and an appropriate amount of deionized water are added and ground for 60 min to make a slurry active material. This slurry is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air oven and dried at 60 °C for 10 h to obtain the positive electrode sheet.

[0143] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 26.

[0144] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 1000 mA·g under a voltage range of 0.2–1.1 V. -1 The long-cycle test was performed. The test results are shown in Figure 27.

[0145] Example 15 uses PbI2@C A SP-721 is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0146] Preparation of cathode materials: PbI2, C A Super P was weighed at a mass ratio of 7:2:1 and placed into a ball mill. The ball milling conditions were 400 r / min for 8 h. After ball milling, the material was scraped onto weighing paper to obtain PbI2@C. A &SP-721.

[0147] Preparation of the positive electrode: The positive electrode active material PbI2@C A The mass ratio of SP-721, SA, and SBR binders is calculated according to a mass ratio of 9:0.5:0.5. First, a certain mass of PbI2@C is weighed. A &SP-721 and SA are ground in an agate mortar for 15 min and mixed evenly. Then, a certain mass of SBR and an appropriate amount of deionized water are added and ground for 60 min to make a slurry active material. This slurry is then evenly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a forced-air drying oven and dried at 60 °C for 10 h to obtain the positive electrode sheet.

[0148] Under a voltage range of 0.2–1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a test at 100 mA·g. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 28.

[0149] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 1000 mA·g under a voltage range of 0.2–1.1 V. -1 The long-cycle test was performed. The test results are shown in Figure 29.

[0150] Example 16 with I 30% @C A Lead foil is used as the negative electrode, with the positive electrode being the active material and the negative electrode being the lead foil. 1 mol L -1 Pb(CH3COO)2-H2O was used as the electrolyte, and a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0151] The I mentioned 30% @C A The specific synthesis method of the cathode material is prepared according to the method in Example 1.

[0152] Under a voltage range of 0.2–1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a test at 100 mA·g. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 30.

[0153] At 100, 300, 1000, 2000, 5000 mA·g -1 The rate performance of the battery was tested at the current density. The test results are shown in Figure 31.

[0154] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a voltage range of 0.2–1.1 V and tested at 5000 mA·g. -1 The long-cycle test was performed. The test results are shown in Figure 32.

[0155] Example 17 uses I 40% @C A Lead foil is used as the negative electrode, with the positive electrode being the active material and the negative electrode being the lead foil. 1 mol L -1 Pb(CH3COO)2-H2O was used as the electrolyte, and a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0156] The I mentioned 40% @C A The specific synthesis method of the cathode material is prepared according to the method in Example 2.

[0157] Under a voltage range of 0.2–1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a test at 100 mA·g. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 33.

[0158] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V.-1 The long-cycle test was performed. The test results are shown in Figure 34.

[0159] Example 18 uses PbBr2@SP as the positive electrode active material and lead foil as the negative electrode, 1 mol L -1 Pb(CH3COO)2-H2O was used as the electrolyte, and a rechargeable aqueous lead-bromine battery was assembled according to the method in Example 1.

[0160] The specific synthesis method of the PbBr2@SP cathode material is prepared according to the method in Example 11.

[0161] The rechargeable aqueous lead-bromine battery assembled in this embodiment was subjected to a voltage test of 0.1 mV·s within a voltage range of 0.2~1.5 V. -1 The cyclic voltammetry test results are shown in Figure 35.

[0162] Under a voltage range of 0.2–1.5 V, the rechargeable aqueous lead-bromine battery assembled in this embodiment was subjected to a test at 100 mA·g. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 36.

[0163] Example 19 with I 30% @C A Lead foil is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0164] The I mentioned 30% @C A The specific synthesis method of the positive electrode material is as follows: 0.3 g of elemental iodine is placed in an agate mortar and ground into powder. This powder is then placed in the lining of a reaction vessel, and 0.6 g of carbon material A is added. The reaction is carried out at 80 °C for 12 h. After the reaction is complete, the reaction vessel is opened and the mixture is left exposed to continue reacting at 60 °C for 2 h. This yields I₂. 30% @C A powder.

[0165] The positive electrode sheet was prepared according to the method in Example 1.

[0166] Under a voltage range of 0.2–1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a test at 100 mA·g. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 37.

[0167] Under a voltage range of 0.2~1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a test of 0.1 mV·s. -1 Cyclic voltammetry tests were performed. The test results are shown in Figure 38.

[0168] At 100, 200, 300, 500, 800, 1000, 2000, 3000, 5000, 8000, 10000 mA·g -1 The rate performance of the battery was tested at the current density. The test results are shown in Figure 39.

[0169] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a voltage range of 0.2–1.1 V and tested at 2000 mA·g. -1 The long-cycle test was performed. The test results are shown in Figure 40.

[0170] Example 20 with I 30% @C A As the positive electrode active material, a lead alloy (Pb7Bi3) is used as the negative electrode, 1 mol L -1 Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0171] The I mentioned 30% @C A The specific synthesis method of the cathode material is prepared according to the method in Example 1.

[0172] The specific preparation method of the Pb7Bi3 anode is as follows: Pb7Bi3 is prepared in a glove box. According to the Pb-Bi binary phase diagram, 3.018 g of metallic bismuth is heated to a liquid state at 280 °C. Subsequently, 6.982 g of metallic lead is added, mixed with the liquid bismuth, and stirred continuously. After a period of reaction, it is allowed to cool naturally, finally yielding 10 g of Pb7Bi3 sample. The sample is placed on aluminum foil, heated to melt, and then evenly spread on the surface of the aluminum foil with a brush. After the sample cools naturally, it is cut into circular electrode sheets with a diameter of 12 mm using a cutting machine.

[0173] Under a voltage range of 0.2–1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a test at 100 mA·g. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 41.

[0174] Under a voltage range of 0.2–1.1 V, the rechargeable aqueous lead-iodine battery assembled in this embodiment was subjected to a 5000 mA·g test. -1 The long-cycle test was performed. The test results are shown in Figure 42.

[0175] Example 21 with I 30% @C A Lead powder (Pb powder) is used as the positive electrode active material, and lead powder (Pb powder) is used as the negative electrode. 1 mol L -1Using Pb(ClO4)2-H2O as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method in Example 1.

[0176] The I mentioned 30% @C A The specific synthesis method of the cathode material is prepared according to the method in Example 1.

[0177] The specific preparation method of the lead powder negative electrode is as follows: Preparation of negative electrode: First, lead powder, Super P and PVDF binder are placed in an agate mortar at a mass ratio of 8:1:1 and ground for 30 min and mixed evenly. Then, an appropriate amount of NMP is added and ground for 10 min to make a paste-like active material. This paste is then uniformly coated onto a titanium foil with a thickness of 30 µm. Finally, the coated electrode sheet is placed in a vacuum oven and dried at 60 °C for 10 h to obtain the negative electrode.

[0178] The rechargeable aqueous lead-iodine battery prepared in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 43.

[0179] Example 22 with I 30% @C A Lead foil is used as the positive electrode active material, and lead foil is used as the negative electrode. 1 mol L -1 Using Pb(ClO4)2-acetonitrile (Acetonitrile, abbreviated as ACN) as the electrolyte, a rechargeable aqueous lead-iodine battery was assembled according to the method of Example 1.

[0180] The I mentioned 30% @C A The specific synthesis method of the cathode material is prepared according to the method in Example 1.

[0181] 1 mol L -1 Preparation of Pb(ClO4)2-ACN electrolyte: First, prepare a clean, dry empty bottle and mark the 10 mL ACN mark. Then, at room temperature, pour 4.601 g of Pb(ClO4)2·3H2O solid into the empty bottle and add ACN to the mark. Finally, shake thoroughly until the lead salt is completely dissolved, preparing 10 mL of 1 mol·L⁻¹ electrolyte. -1 Pb(ClO4)2-ACN electrolyte.

[0182] The rechargeable organic lead-iodine battery assembled in this embodiment was subjected to a test at 100 mA·g under a voltage range of 0.2–1.1 V. -1 The constant current charge-discharge test was performed. The test results are shown in Figure 44.

[0183] The test results of Examples 1-22 are summarized in Table 4: Table 4 Negative electrode material Positive electrode material Voltage (V) Discharge capacity (mAh g) I2 -1 Energy density (Wh kg) I2 -1 Lead foil I2@C A 0.8~0.88240.6204.5 Lead foil I2@C B 0.8~0.88163.02140.2 Lead foil I2@C C 0.8~0.88146.8121.8 Lead foil I2@C D 0.8~0.88178.4155.2 Lead foil Br2@MXene 1.25~1.37 0.49 0.8 Lead foil TBAI3 0.8~0.889 4.88 3.1 Lead foil TBABr3 1.25~1.313 9.6178.7 Lead foil PbI2@C A &SP-5410.7~0.78139.7100.6 Lead foil PbBr2@C A &SP-5411.25~1.3148.3182.4Pb7Bi3 alloy I2@C A 0.8~0.88238.8200.6 Lead powder I2@C A 0.8~0.88196.7169.2 Lead foil I2@C A 0.8~0.88156.8131.7 As shown in Figures 1-44, the halogen-containing (X = I, Br) cathode materials prepared under different process conditions in each embodiment all exhibited similar charge-discharge curves and cyclic voltammetry curves, and the values ​​at corresponding positions belonged to I. 0 / I - or Br 0 / Br - The redox peaks indicate that these materials all achieve reversible halogen redox reactions. Taking Figure 3 as an example, this battery exhibits excellent rate performance. At current densities ranging from 100 to 10000 mA g... -1 When varying within the range (specifically including 100, 200, 500, 800, 1000, 2000, 5000, 8000, and 10000 mA g), -1 ), I 30% @C A The positive electrode can provide 238.7, 237.7, 232.0, 227.7, 226.0, 224.7, 218.0, 210.7 and 205.5 mAh g, respectively. -1 High discharge capacity. When the current density returns to 100 mA g... -1At that time, the discharge capacity can still be restored to 237.7 mAh g. -1 This demonstrates that the battery possesses excellent rate performance, supporting rapid charge and discharge over a short period. Furthermore, as shown in Figure 4, even at 8000 mA g... -1 After 50,000 cycles at high current density, I 30% @C A The positive electrode can still maintain 174 mAh g -1 The reversible capacity and capacity retention rate of up to 99% further demonstrate that the battery has excellent long-cycle stability.

[0184] Energy density formula = Voltage (V) × Specific capacity (mAh g) -1 ) with I 30% @C A Taking the positive electrode as an example, the theoretical energy density (Ea) of this battery can be obtained from the formula. 理 = 0.85 (V) × 211 (mAh g) -1 = 179.35 Wh kg -1 .

[0185] I 30% @C A The capacity of the positive electrode is contributed by activated carbon. According to the charge-discharge curves in Figure 1, the actual capacity of the battery is 240.6 - 37.4 = 203.2 mAh g. -1 That is, the actual energy density (E) of the battery. 实 )=0.85(V)×203.2(mAh g -1 = 172.72 Wh kg -1 .

[0186] η=E 实 / E 理 =172.72 Wh kg -1 / 179.35 Wh kg -1 =96%, indicating that the battery can achieve more than 90% of the theoretical energy density.

[0187] The embodiments described above are merely illustrative of specific implementations of the present invention, and while the descriptions are detailed, they should not be construed as limiting the scope of protection of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A high-rate, long-cycle lead-halogen battery, characterized in that, The device includes a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode is a lead-containing electrode; the electrolyte uses a soluble lead salt as a solute and water or an organic liquid as a solvent; the active material of the positive electrode is selected from any of the following: (a) a halogen composite material, wherein the halogen composite material is formed by supporting a halogen X2 on a carrier material, wherein the halogen X2 is Br2 or I2; wherein the carrier material is selected from carbon materials or ligand framework materials; (b) a halogen-containing compound; (c) a halogen-containing compound composite material, wherein the halogen-containing compound composite material is formed by supporting a halogen-containing compound on a carbon material; wherein, in the... In either category (a) or category (c), the carbon material is selected from at least one of graphene, carbon nanotubes, carbon fibers, activated carbon, porous carbon, mesoporous carbon, and biochar; in category (a), the ligand framework material is selected from at least one of metal-organic frameworks, covalent organic frameworks, two-dimensional transition metal carbides, nitrides, carbonitrides, etc.; in either category (b) or (c), the halogenated compound is selected from at least one of PbX2, triiodine / tetramethyl bromide quaternary ammonium salt, triiodine / tetraethyl bromide quaternary ammonium salt, and triiodine / tetrabutyl bromide quaternary ammonium salt, wherein X is Br or I.

2. The high-rate, long-cycle lead-halogen battery according to claim 1, characterized in that, The negative electrode is an electrode containing lead foil, lead powder, or a lead alloy.

3. The high-rate, long-cycle lead-halogen battery according to claim 1, characterized in that, In category (a), the loading of halogen X2 is 30-40 wt%; in category (c), the content of the halogen-containing compound is 50-70%; the carbon material is at least one of activated carbon, porous carbon, mesoporous carbon, and biochar; wherein the porous carbon is ZIF-8 or ZIF-8 pyrolysis carbon, and the biochar is biochar prepared from coconut shell.

4. The high-rate, long-cycle lead-halogen battery according to claim 3, characterized in that, The specific processing method for preparing biomass alkaline char from coconut shells is as follows: The raw coconut shells are washed with deionized water and dried thoroughly in a 105 °C oven for 12 h. Then, the dried coconut shells are ball-milled at 800 r / min for 8 h to pulverize them. A 50% KOH solution is prepared, and 10 g of dried coconut shell powder is mixed with 20 g of the 50% KOH solution at an impregnation ratio of 1:

2. The mixture is thoroughly stirred to ensure the coconut shells are completely impregnated by the alkali solution. The resulting paste is left to stand at room temperature for 24 h, then dried at 105 °C to obtain a dry solid mixed with an activator. The obtained dry solid is activated in a tube furnace, heated to 800 °C at a rate of 5 °C / min, and held for 3 h. The activated solid is repeatedly soaked and rinsed with 0.1 M dilute hydrochloric acid until pH=7, then repeatedly rinsed with deionized water until no chloride ions are detected by silver nitrate test. Finally, it is placed in a 105 °C oven. Biomass alkali char can be obtained by thoroughly drying it in an oven at °C.

5. The high-rate, long-cycle lead-halogen battery according to claim 3, characterized in that, The specific processing method of the ZIF-8 pyrolysis carbon is as follows: First, 1.53 g Zn(NO3)2·6H2O and 3.72 g 2-methylimidazole are dissolved in 70 mL of methanol and stirred magnetically for 15 min to form a solution; then, Zn(NO3)2·6H2O is added dropwise to the 2-methylimidazole solution under stirring, and stirring is continued at room temperature for 1 h, followed by standing for 12 h. The resulting white ZIF-8 crystals are centrifuged, washed several times with deionized water and methanol to obtain the precipitate, and finally dried at 60°C for 12 h; the ZIF-8 crystals prepared according to the above method are heated to 900 °C at a heating rate of 5 °C / min under a N2 atmosphere and held for 4 h to obtain ZIF-8 pyrolysis carbon.

6. The high-rate, long-cycle lead-halogen battery according to claim 1, characterized in that, The soluble lead salt is one or more of lead perchlorate, lead acetate, lead salicylate, lead citrate, lead nitrate, lead fluorosilicate, or lead tetrafluoroborate; the concentration of the soluble lead salt is 0.01~10 mol / L.

7. The high-rate, long-cycle lead-halogen battery according to claim 1, characterized in that, The membrane is permeable to lead ions and is made of filter paper or glass fiber.

8. The method for preparing a high-rate, long-cycle lead-halogen battery according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Provide a positive electrode, a negative electrode, an electrolyte, and a separator as described in any one of claims 1-7; S2. Stack the negative electrode shell, a lead-containing negative electrode, a separator, a positive electrode, and a positive electrode shell in that order; S3. Add a lead-ion electrolyte to the separator; S4. Seal to form a button cell or a pouch cell.

9. The method according to claim 8, characterized in that, The positive electrode is prepared by the following steps: mixing positive electrode active material, conductive agent, and binder into a slurry at a mass ratio of (7-9):(0.5-2):(0.5-1); It is coated onto the current collector and then dried to form a shape.

10. The method according to claim 9, characterized in that, The conductive agent is conductive carbon black, activated carbon, porous carbon, acetylene black BP-2000, Ketjen black KB, Vulcan XC-72, super carbon black Super P, or carbon nanotubes; the binder is polyvinylidene fluoride PVDF, sodium carboxymethyl cellulose CMC, sodium alginate SA, or styrene-butadiene rubber SBR.

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