A rechargeable rocking chair type aqueous lead ion battery

Abstract

The present invention provides a rechargeable rocking chair type aqueous lead ion battery, which is composed of a positive electrode, a negative electrode, a diaphragm therebetween, and an electrolyte containing lead ions and having ionic conductivity. The negative electrode is an electrode containing metallic lead. The active material of the positive electrode is one of manganese oxide, vanadium oxide, sulfur / selenide, Prussian blue analog, polyanion compound or organic electrode material. The electrolyte has a soluble lead salt as solute and water as solvent. The electrolyte has good compatibility with the positive electrode and the lead negative electrode, and the deposition / precipitation of lead shows a high coulomb efficiency, without electrolyte decomposition and other side reactions. The rechargeable rocking chair type aqueous lead ion battery can be charged and discharged in a relatively short time, showing excellent rate performance and long cycle stability as well as good safety.

Description

Technical Field

[0001] The invention belongs to the field of novel energy storage batteries, and in particular relates to a novel rechargeable rocking-chair type aqueous lead ion battery. Background Art

[0002] With the continuous increase in social needs, energy issues have become the primary issue in today's world. Fossil energy is becoming increasingly depleted, while renewable energy sources such as wind and solar energy are intermittent. Therefore, electrochemical energy storage technology has rapidly emerged. Lead-acid batteries, as a traditional energy storage battery system, are widely used in electric bicycles, automotive start-stop power supplies, and uninterruptible power supplies. However, due to the limitations of the reaction mechanism of lead-acid batteries themselves, their energy density can only reach 30-40% of their theoretical energy density, and the PbSO4 generated by the discharge product has poor conductivity, which further shortens the service life of lead-acid batteries. In recent years, the rapidly developing lithium-ion batteries have gradually replaced the use of lead-acid batteries, but as an organic electrolyte system, lithium-ion batteries frequently spontaneously combust and explode, posing a major safety hazard.

[0003] Compared with organic electrolytes, aqueous electrolytes have the significant advantages of high ionic conductivity, safety and low cost. + 、Na + , K + ), ammonium ion (NH4 + ) and multivalent carriers (such as Mg 2+ 、Al 3+ and Zn 2+ ) are being developed, but there are also many problems to be solved: (1) The development of positive and negative electrode materials for aqueous lithium batteries, aqueous sodium batteries, aqueous potassium batteries or aqueous ammonium ion batteries is difficult. The positive electrode materials and low-potential negative electrode materials often undergo water decomposition, resulting in hydrogen evolution and many side reactions. In addition, some positive and negative electrode materials have high solubility in aqueous electrolytes, which greatly limits the selection of electrode materials for aqueous lithium batteries, aqueous sodium batteries, aqueous potassium batteries or aqueous ammonium ion batteries; (2) Due to the high solubility of Mg 2+ Ions and Al 3+ There is less material for ion diffusion in the host, and the passivation and irreversible deposition of the magnesium negative electrode and the easy formation of a protective oxide film on the aluminum negative electrode hinder the Mg 2+ Ions and Al 3+The further diffusion of ions makes aqueous magnesium batteries and aqueous aluminum batteries unsuitable for large-scale promotion. (3) At present, the research on aqueous zinc-ion batteries is quite hot, but they also have problems such as negative electrode corrosion, hydrogen evolution, and dendrites, which seriously affect the cycle stability of the battery. For example, Chinese patent CN116581232A records that an aqueous zinc-ion symmetric battery prepared with pure zinc foil as the zinc negative electrode has a current density of 5 mA / cm 2 , capacity 1mAh / cm 2 Under normal circumstances, the charge and discharge cycle can only be 150 hours. Although researchers have used coatings, electrolyte regulation and other methods to alleviate these problems, they are still unable to solve the stability problem of the zinc negative electrode in essence.

[0004] The existence of the above problems seriously affects the practical application of aqueous batteries in the field of large-scale energy storage. Therefore, it is necessary to study a new type of energy storage battery. Summary of the invention

[0005] The object of the present invention is to provide a rechargeable rocking chair type aqueous lead ion battery, which can realize full charge and discharge in a short time, has good rate performance and has excellent long cycle stability.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] A rechargeable rocking chair type aqueous lead ion battery comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the negative electrode is an electrode containing metallic lead; and the electrolyte has a soluble lead salt as a solute and water as a solvent.

[0008] During the discharge process of the battery, the metal lead in the negative electrode can obtain electrons to become lead ions and be embedded in the positive electrode through the electrolyte.

[0009] The active material of the positive electrode is one or a mixture of manganese oxide, vanadium oxide, sulfur / selenide, Prussian blue analogs, polyanionic compounds or organic electrode materials.

[0010] The soluble lead salt is one or more of lead perchlorate trihydrate, lead acetate trihydrate, dibasic lead salicylate, lead citrate, lead nitrate, lead fluorosilicate or lead tetrafluoroborate; and its concentration is 0.01-10 mol / L.

[0011] The membrane is permeable to lead ions and is preferably filter paper or glass fiber.

[0012] Preferably, the negative electrode is an electrode containing metal lead foil, metal lead powder or metal lead alloy.

[0013] Preferably, the manganese oxide is α-MnO2, β-MnO2, γ-MnO2, δ-MnO2, K x MnO2 or Cax MnO2, the vanadium oxide is V2O5, NH4V4O 10 , K x V2O5 or Mg x V2O5, the sulfide is MoS2, the selenide is Cu2Se, the Prussian blue analog is CuHCF, NiHCF, CoHCF or MnHCF, and the polyanionic compound is Na3V2(PO4)3 or Na3V2(PO4) 3-x F x , the organic electrode material is polyaniline or calix[4]quinone, wherein 0 <x≤1;

[0014] More preferably, K x MnO2 is K 0.27 MnO2, Ca x MnO2 is Ca 0.28 MnO2, K x V2O5 is K 0.5 V2O5, Mg x V2O5 is Mg 0.19 V2O5, Na3V2(PO4) 3-x F x It is Na3V2(PO4)2F.

[0015] Preferably, the concentration of the soluble lead salt is 1 mol / L.

[0016] Preferably, the preparation method of the positive electrode is as follows:

[0017] The active material, conductive agent and binder of the positive electrode are mixed, dispersed in a solvent to form a slurry, uniformly coated on a current collector, and dried to obtain the product.

[0018] Among them, the conductive agent is conductive carbon black, activated carbon, porous carbon, BP-2000, VulcanXC-72, super carbon (Super P) or carbon nanotubes; the binder is polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC) or sodium alginate; the solvent is N-methylpyrrolidone (NMP) or water; the current collector is titanium foil, stainless steel foil, non-woven fabric or carbon paper.

[0019] More preferably, the mass ratio of the active material of the positive electrode to the conductive agent and the binder is 7:2:1.

[0020] More preferably, the conductive agent is SuperP.

[0021] More preferably, the binder is PVDF.

[0022] More preferably, the solvent is NMP.

[0023] More preferably, the current collector is a titanium foil, and its thickness is preferably 30 μm.

[0024] Preferably, the preparation method of the rechargeable rocking chair type aqueous lead ion battery of the present invention is as follows:

[0025] In a room temperature environment, the negative electrode shell, the lead negative electrode, the diaphragm, the electrolyte, the positive electrode, the gasket, the shrapnel, and the positive electrode shell are stacked in sequence, and 50 μL of the above electrolyte is dripped on the diaphragm between the positive electrode and the negative electrode to make it completely infiltrated, and the battery is packaged to obtain a rechargeable rocking chair type aqueous lead ion button battery; or the soft-package positive electrode side, the positive electrode, the diaphragm, the electrolyte, the lead negative electrode, and the soft-package negative electrode side are stacked in sequence, and the above electrolyte is dripped on the diaphragm between the positive electrode and the negative electrode to make it completely infiltrated, and the battery is packaged to obtain a rechargeable rocking chair type aqueous lead ion soft-package battery.

[0026] The present invention constructs for the first time a rechargeable rocking-chair-type aqueous lead-ion battery system, which uses an electrode containing metallic lead as the negative electrode, and is matched with a specific positive electrode active material and an aqueous electrolyte with high ionic conductivity to form a "rocking-chair-type" lead-ion battery: when discharging, the metallic lead obtains electrons from the positive electrode through an external circuit and becomes lead ions, and the lead ions are precipitated from the negative electrode and embedded in the positive electrode through the electrolyte. When charging, the lead ions are released from the positive electrode active material and deposited on the negative electrode through the electrolyte, and the charge and discharge cycle is carried out in this way.

[0027] The electrolyte in the rechargeable rocking chair type aqueous lead ion battery system of the present invention has good compatibility with the positive electrode and the negative electrode, the electrolyte has stable performance, high ionic conductivity, and the negative electrode containing metallic lead has excellent redox properties and stable reversible deposition and precipitation. The lead ions in the electrolyte can be quickly embedded / extracted in the specific positive electrode active material, the Pb deposition / precipitation coulomb efficiency is high, and the deposition and precipitation of lead ions are far away from the hydrogen evolution potential, there is no electrolyte decomposition, and there is no corrosion, hydrogen evolution and other side reactions at the negative electrode, so that the aqueous lead ion battery system of the present invention can be fully charged and discharged in a short time, and the rate performance is good. Under the condition of a current density of 100mA / g, it can be stably cycled 6000 times, and the long cycle stability and safety are far superior to conventional magnesium, aluminum, and zinc negative electrodes. In addition, the cost of metallic lead is relatively low, so the rechargeable rocking chair type aqueous lead ion battery of the present invention can be used as one of the backup options for large-scale energy storage batteries, and has broad application prospects.

[0028] In addition, based on the above-mentioned "rocking chair" reaction mechanism, the aqueous lead ion battery of the present invention overcomes the defects of the solid phase reaction of metallic lead, and the theoretical energy density and cycle life are also greatly improved compared with traditional lead-acid batteries. Based on the above-mentioned "rocking chair" reaction mechanism, the theoretical energy density of the aqueous lead ion battery of the present invention can be exerted to more than 90%, while the traditional lead-acid battery based on the solid phase reaction mechanism (solid phase conversion of Pb and PbSO4, PbO2 and PbSO4) can only exert 30%-40% of the theoretical energy density. Therefore, the aqueous lead ion battery of the present invention will provide a new direction for the transformation of lead-acid batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of the working principle of the rechargeable rocking chair type aqueous lead ion battery of the present invention.

[0030] Figure 2 It is the cyclic voltammetry curve of the lead negative electrode in the electrolyte in Example 1.

[0031] Figure 3 This is a test chart of the cyclic stability of metal lead negative electrode deposition in Example 1.

[0032] Figure 4 This is a cyclic voltammogram of the rechargeable rocking-chair aqueous lead-ion battery of Example 2 at a scan rate of 0.1 mV / s.

[0033] Figure 5 1 is a charge and discharge curve of the rechargeable rocking chair type aqueous lead ion battery of Example 2 at a current density of 20 mA / g.

[0034] Figure 6 This is a rate performance diagram of the rechargeable rocking-chair type aqueous lead-ion battery of Example 2 at different current densities.

[0035] Figure 7 This is a cycle performance diagram of the rechargeable rocking-chair aqueous lead-ion battery of Example 2 at a current density of 100 mA / g.

[0036] Figure 8 3 is a charge and discharge curve of the rechargeable rocking chair type aqueous lead ion battery of Example 3 at a current density of 5 mA / g.

[0037] Fig. 9 1 is a charge and discharge curve of the rechargeable rocking chair type aqueous lead ion battery of Example 4 at a current density of 20 mA / g.

[0038] Fig.10 This is a cyclic voltammogram of the rechargeable rocking-chair aqueous lead-ion battery of Example 5 at a scan rate of 0.1 mV / s.

[0039] Fig.111 is a charge and discharge curve of the rechargeable rocking chair type aqueous lead ion battery of Example 5 at a current density of 20 mA / g.

[0040] Fig.12 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 6 at a current density of 20 mA / g.

[0041] Fig.13 It is a cyclic voltammogram of the rechargeable rocking-chair type aqueous lead-ion battery of Example 7 at a scan rate of 0.1 mV / s.

[0042] Fig.14 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 7 at a current density of 20 mA / g.

[0043] Fig.15 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 8 at a current density of 20 mA / g.

[0044] Fig.16 This is a cyclic voltammogram of the rechargeable rocking-chair aqueous lead-ion battery of Example 9 at a scan rate of 0.1 mV / s.

[0045] Fig.17 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 9 at a current density of 20 mA / g.

[0046] Fig.18 1 is a charge and discharge curve of the rechargeable rocking chair type aqueous lead ion battery of Example 10 at a current density of 20 mA / g.

[0047] Fig.19 1 is a charge and discharge curve of the rechargeable rocking chair type aqueous lead ion battery of Example 11 at a current density of 20 mA / g.

[0048] Fig. 20 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 12 at a current density of 20 mA / g.

[0049] Fig.21 This is a cyclic voltammogram of the rechargeable rocking-chair aqueous lead-ion battery of Example 13 at a scan rate of 0.1 mV / s.

[0050] Fig. 22 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 13 at a current density of 20 mA / g.

[0051] Fig.23 This is a rate performance diagram of the rechargeable rocking-chair type aqueous lead-ion battery of Example 13 at different current densities.

[0052] Fig.24 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 14 at a current density of 10 mA / g.

[0053] Fig.25 It is a charge and discharge curve diagram of the rechargeable rocking-chair type aqueous lead ion battery of Example 15 at a current density of 20 mA / g.

[0054] Fig.26 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 16 at a current density of 20 mA / g.

[0055] Fig. 27 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 17 at a current density of 20 mA / g.

[0056] Fig.28 It is a charge and discharge curve diagram of the rechargeable rocking chair type aqueous lead ion battery of Example 18 at a current density of 20 mA / g.

[0057] Fig.29 This is a cyclic voltammogram of the rechargeable rocking-chair type aqueous lead-ion battery of Example 19 at a scan rate of 0.1 mV / s.

[0058] Fig.30 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 19 at a current density of 50 mA / g.

[0059] Fig.31 This is a cycle performance diagram of the rechargeable rocking-chair-type aqueous lead-ion battery of Example 19 at a current density of 1000 mA / g.

[0060] Fig.32 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 20 at a current density of 20 mA / g.

[0061] Fig.33 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 21 at a current density of 20 mA / g.

[0062] Fig.34 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 22 at a current density of 20 mA / g.

[0063] Fig.35 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 23 at a current density of 100 mA / g.

[0064] Fig.36 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 24 at a current density of 20 mA / g.

[0065] Fig.37 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 25 at a current density of 5 mA / g.

[0066] Fig.38 This is a charge and discharge curve of the rechargeable rocking-chair type aqueous lead ion battery of Example 26 at a current density of 10 mA / g.

[0067] Fig.39 It is a schematic diagram of the structure of the rechargeable rocking-chair type aqueous lead-ion soft-pack battery of Example 27.

[0068] Fig.40 This is the charge and discharge curve of the soft-pack battery of Example 27 at a current density of 20 mA / g.

[0069] Fig.41 This is a schematic diagram of charging a mobile phone using the soft-pack battery of Example 27. DETAILED DESCRIPTION

[0070] The present invention will be further described below in conjunction with the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes based on the present invention are within the protection scope of the present invention.

[0071] The processes and methods not described in detail in the following examples are conventional methods known in the art, and the reagents used in the examples are all analytically pure or battery grade, and can be purchased commercially or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the purpose of the present invention.

[0072] Example 1

[0073] A rechargeable rocking chair type aqueous lead ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte.

[0074] Preparation of positive electrode sheet: The active material of the positive electrode, Super P and PVDF binder were uniformly mixed in a mass ratio of 7:2:1, dispersed in NMP, ground for 1 hour to make a slurry, evenly coated on a titanium foil with a thickness of 30 µm, and dried at 70°C for 10 hours to obtain a positive electrode sheet.

[0075] Preparation of negative electrode: The negative electrode can be metal lead foil, metal lead sheet or metal lead powder. When using metal lead foil, the metal lead foil with a thickness of 50 µm is cut into a round sheet with a diameter of 16 mm and directly used as the negative electrode sheet.

[0076] Preparation of electrolyte: At room temperature, dissolve 4.601 g Pb(ClO4)2·3H2O in H2O to form 10 mL solution, shake thoroughly to completely dissolve the lead salt, and prepare 1 mol / L Pb(ClO4)2-H2O electrolyte.

[0077] Battery assembly: stack the negative electrode shell, negative electrode, diaphragm, electrolyte, positive electrode, gasket, spring, and positive electrode shell in order to form a laminated structure, drip 50 μL of electrolyte on the diaphragm between the positive and negative electrodes to wet the diaphragm, press and package, and the rechargeable rocking chair type aqueous lead ion battery of the present invention can be obtained.

[0078] The working principle of the obtained rechargeable rocking chair type aqueous lead ion battery is as follows Figure 1 The left side of the figure is a schematic diagram of the positive electrode material, and the right side is the lead negative electrode. When discharging, lead ions are precipitated from the negative electrode and embedded into the positive electrode through the electrolyte. When charging, lead ions are released from the positive electrode material and deposited into the negative electrode through the electrolyte, forming a "rocking chair" lead ion battery.

[0079] Furthermore, the following performance tests were performed on the obtained electrolyte in this embodiment:

[0080] (1) Electrolyte voltage window

[0081] The voltage window of the electrolyte was tested by a three-electrode electrolytic cell. An electrolytic cell was used as the electrolytic cell, lead foil (Pb) was used as the working electrode, Pt was used as the counter electrode, and Ag / AgCl was used as the reference electrode. 10 mL of the electrolyte prepared in this example was added, and the electrolytic cell system was tested by cyclic scanning voltammetry (CV). The scanning speed was set to 1.0 mV / s, and the test voltage range was -0.6~1.8 V. The data was recorded using a CHI760E electrochemical workstation.

[0082] The results are as follows Figure 2 As shown, the results show that the electrolyte 1 mol / L Pb(ClO4)2-H2O prepared in this example shows stable lead deposition / precipitation under low potential conditions, and the stable operating voltage window of the electrolyte is greater than 1.9V.

[0083] (2) Conductivity

[0084] The conductivity of the electrolyte was tested by AC impedance method, and the experimental data were recorded on CHI760E electrochemical workstation. The results showed that the conductivity of the electrolyte 1 mol / L Pb(ClO4)2-H2O prepared in this example was 148.8 mS / cm.

[0085] (3) Stability of electrolyte on lead negative electrode

[0086] Cyclic stability test of electrolyte in Pb / Pb symmetrical battery: Lead foil is used for both working electrode and counter electrode. Filter paper is used as a separator between the two lead foils, 50μL electrolyte is added, and a Pb / Pb symmetrical battery is assembled to test the stability of the electrolyte during long-term cycling. The test was conducted using the CT2001A blue battery test system at 1 mA / cm 2 The battery was cyclically charged and discharged at a current density of . In each cycle, it was first discharged at a constant current for 30 minutes and then charged at a constant current for 30 minutes.

[0087] The results are as follows Figure 3 As shown in the figure, it can be seen that the electrolyte prepared in this embodiment can be stably circulated for more than 3000 hours in the Pb / Pb symmetrical battery.

[0088] Example 2

[0089] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using α-MnO2 as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0090] The specific synthesis method of the α-MnO2 positive electrode material is as follows:

[0091] Dissolve 0.9878 g KMnO4 and 0.4226 g MnSO4·H2O in 80 mL deionized water and stir for 30 min to form a purple solution. Transfer the obtained slurry to a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner and heat at 160°C for 12 h. After cooling to room temperature, wash with deionized water and ethanol three times each, and finally freeze-dry for 12 h to obtain the sample.

[0092] Battery performance testing: Cyclic voltammetry test was performed using a CHI760E electrochemical workstation with a voltage range of 0.2~1.2 V; constant current charge and discharge test was performed on the battery using a Blue Battery Test System at room temperature with a voltage range of 0.2~1.2 V; rate performance test was performed at current densities of 20, 50, 80, 100, 200, 500, 800 and 1000 mA / g; long cycle stability test was performed at a current density of 100 mA / g. Test results are as follows Figure 4-Figure 7 .

[0093] Figure 4 : This is the cyclic voltammetry curve at a scan rate of 0.1 mV / s. It can be seen from the figure that in the second cycle and subsequent cycles, an obvious reduction peak appears at 0.73V and an obvious oxidation peak appears at 0.98V. The curves of the first three cycles have good overlap, indicating that the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment has high stability.

[0094] Figure 5 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure. The charge and discharge current density is 20 mA / g. The discharge capacity of the second cycle is 297.33 mAh / g, the discharge capacity is 299.79 mAh / g, and the coulombic efficiency can reach 99%.

[0095] Figure 6 The figure shows the rate performance at different current densities. It can be seen from the figure that the cycle capacity at different rates has basically no attenuation. After 5 cycles at a current density of 1000 mA / g, the specific capacity can reach 66 mAh / g, and after returning to a current density of 20 mA / g, the specific capacity can still be restored. It can be seen that the battery system has good rate performance and cycle stability.

[0096] Figure 7 This is a cycle stability test at a current density of 100mA / g. It can be seen that after 6,000 cycles, its coulombic efficiency can still reach 100% and the capacity retention rate reaches 80%. Compared with the 500-1,000 cycle life of traditional lead-acid batteries, the 6,000 cycle life of this system is a great improvement, showing a high application value.

[0097] Example 3

[0098] The electrolyte of Example 2 was replaced with 0.05 mol / L (C6H5O7)2Pb3-H2O as the electrolyte, and the rechargeable rocking chair type aqueous lead ion battery prepared in this example was subjected to constant current charge and discharge test at a voltage range of 0.2-1.2 V. The test results are shown in FIG. Figure 8 .

[0099] Figure 8 This is the constant current charge and discharge curve of the 1st, 2nd and 3rd cycles of the aqueous lead-ion battery under the condition of current density 5mA / g. It can be seen that the discharge specific capacity of the second cycle is 77.77mAh / g and the charge specific capacity is 46.29Ah / g.

[0100] Example 4

[0101] The electrolyte of Example 2 was replaced by 1 mol / LPb(CH3COO)2-H2O as the electrolyte, and the rechargeable rocking chair type aqueous lead ion battery prepared in this example was subjected to constant current charge and discharge test at a voltage range of 0.2-1.2 V. The test results are shown in FIG. Fig. 9 .

[0102] Fig. 9The constant current charge and discharge curves for 1, 2, and 3 cycles at a current density of 20 mA / g. The discharge specific capacity of the second cycle is 163.94 mAh / g, and the charge specific capacity is 169.56 mAh / g; the discharge specific capacity of the third cycle is 152.64 mAh / g, and the charge specific capacity is 163.61 mAh / g.

[0103] Example 5

[0104] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using β-MnO2 as the positive electrode active material, an electrode containing metal lead powder as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0105] The specific synthesis method of the β-MnO2 positive electrode material is as follows:

[0106] β-MnO2 was synthesized by hydrothermal method. 0.1M KMnO4 (30 mL) and 0.6 M MnSO4·H2O (30 mL) were stirred continuously at room temperature for 30 minutes. The mixture was placed in a 100mL stainless steel autoclave with polytetrafluoroethylene lining and reacted at 140℃ for 12h. The obtained product was washed with water and anhydrous ethanol three times each, and finally dried at 80℃ for 10 h to obtain the β-MnO2 sample.

[0107] Cyclic voltammetry was performed on the β-MnO2 electrode at a voltage range of 0.2-1.2 V. Fig.10 .

[0108] Under the condition of voltage range of 0.2-1.2 V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.11 .

[0109] Fig.10 This is the cyclic voltammetry curve of the β-MnO2 electrode at a scan rate of 0.1 mV / s. It can be seen from the figure that in the second and subsequent cycles, an obvious reduction peak appears at 0.75V and an obvious oxidation peak appears at 0.97V. The curves of the first three cycles have good overlap, indicating that the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment has high stability.

[0110] Fig.11 The constant current charge and discharge curves of the 1st, 2nd and 3rd cycles under the condition of current density 20mA / g. The discharge specific capacity of the second cycle is 223.02mAh / g, the charge specific capacity is 197.38mAh / g, and the coulombic efficiency can reach 88%; the discharge specific capacity of the third cycle is 204.87 mAh / g, the charge specific capacity is 192.54 mAh / g, and the coulombic efficiency can reach 96%.

[0111] Example 6

[0112] The electrolyte of Example 5 was replaced with 1 mol / L Pb(CH3COO)2-H2O as the electrolyte, and the prepared rechargeable rocking chair type aqueous lead ion battery was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.12 .

[0113] Fig.12 The constant current charge and discharge curves for 1, 2, and 3 cycles at a current density of 20 mA / g. The discharge specific capacity of the second cycle is 107.68 mAh / g, and the charge specific capacity is 115.05 mAh / g; the discharge specific capacity of the third cycle is 102.37 mAh / g, and the charge specific capacity is 115.15 mAh / g.

[0114] Example 7

[0115] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using γ-MnO2 as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0116] The specific synthesis method of the γ-MnO2 positive electrode material is as follows:

[0117] γ-MnO2 was synthesized by hydrothermal method. 0.02mol (NH4)2S2O8 and 0.02mol MnSO4·H2O were dissolved in 80mL deionized water, stirred continuously at room temperature for 30 minutes, and the obtained solution was poured into a 100mL stainless steel autoclave with polytetrafluoroethylene lining, heated at 90℃ for 24h, washed with deionized water and ethanol several times, and then dried at 60℃ overnight to obtain the γ-MnO2 sample.

[0118] Cyclic voltammetry was performed on the γ-MnO2 electrode at a voltage range of 0.2-1.3 V. The test results are shown in Fig.13 .

[0119] Under the condition of voltage range of 0.2-1.3 V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.14 .

[0120] Fig.13 : This is the cyclic voltammetry curve at a scan rate of 0.1 mV / s. It can be seen from the figure that in the second and subsequent cycles, an obvious reduction peak appears at 0.74V and an obvious oxidation peak appears at 0.97V. The curves of the first three cycles have good overlap, indicating that the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment has high stability.

[0121] Fig.14 The constant current charge and discharge curves for 1, 2, and 3 cycles at a current density of 20 mA / g. The discharge specific capacity of the second cycle is 278.38 mAh / g, the charge specific capacity is 272.15 mAh / g, and the coulombic efficiency can reach 97%; the discharge specific capacity of the third cycle is 272.79 mAh / g, the charge specific capacity is 268.59 mAh / g, and the coulombic efficiency can reach 98%.

[0122] Example 8

[0123] 1 mol / L Pb(CH3COO)2-H2O was used as the electrolyte to replace the electrolyte of Example 7, and the prepared rechargeable rocking chair type aqueous lead ion battery was subjected to constant current charge and discharge test.

[0124] Fig.15 It is the constant current charge and discharge curve of 1, 2 and 3 cycles at a current density of 20mA / g. The discharge specific capacity of the second cycle is 213.01mAh / g, and the charge specific capacity is 212.21mAh / g; the discharge specific capacity of the third cycle is 195.76mAh / g, and the charge specific capacity is 199.37mAh / g.

[0125] Example 9

[0126] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using δ-MnO2 as the positive electrode active material, lead foil as the negative electrode, and 0.5 mol / L PbSiF6-H2O as the electrolyte.

[0127] The specific synthesis method of the δ-MnO2 positive electrode is as follows:

[0128] δ-MnO2 was synthesized by hydrothermal method. 0.012 mol KMnO4 and 0.002 mol MnSO4·H2O were uniformly mixed in 60 mL deionized water. The resulting solution was then placed in a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner and heated at 160 °C for 12 hours. The black precipitate was filtered and rinsed several times with deionized water, then vacuum dried at 60 °C overnight to obtain the δ-MnO2 sample.

[0129] The cyclic voltammetry test of the δ-MnO2 electrode was carried out in the voltage range of 0.2~1.2 V. The test results are shown in Fig.16 .

[0130] Under the condition of voltage range of 0.2-1.2 V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.17 .

[0131] Fig.16: This is the cyclic voltammetry curve at a scan rate of 0.1 mV / s. It can be seen from the figure that in the second and subsequent cycles, an obvious reduction peak appears at 0.76V and an obvious oxidation peak appears at 0.97V. The curves of the first three cycles have good overlap, indicating that the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment has high stability.

[0132] Fig.17 The constant current charge and discharge curves for 1, 2, and 3 cycles at a current density of 20 mA / g. The discharge specific capacity of the second cycle is 153.75 mAh / g, the charge specific capacity is 143.72 mAh / g, and the coulombic efficiency can reach 93%; the discharge specific capacity of the third cycle is 144.67 mAh / g, the charge specific capacity is 142.98 mAh / g, and the coulombic efficiency can reach 98%.

[0133] Example 10

[0134] The electrolyte of Example 9 was replaced with 1 mol / L Pb(CH3COO)2-H2O as the electrolyte, and the prepared rechargeable rocking chair type aqueous lead ion battery was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.18 .

[0135] Fig.18 It is the constant current charge and discharge curve of 1, 2 and 3 cycles at a current density of 20mA / g. The discharge specific capacity of the second cycle is 110.84mAh / g, and the charge specific capacity is 118.63mAh / g; the discharge specific capacity of the third cycle is 112.43mAh / g, and the charge specific capacity is 133.98mAh / g.

[0136] Embodiment 11

[0137] K 0.27 MnO2 was used as the positive electrode active material, lead foil was used as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O was used as the electrolyte. A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0138] The K 0.27 The specific synthesis method of MnO2 positive electrode is as follows:

[0139] 120 mg KMnO4 was dissolved in 16 mL deionized water, stirred for 5 min, poured into a 30 mL stainless steel autoclave with a polytetrafluoroethylene liner, and kept at 180 °C for 12 h. The obtained product was washed several times with deionized water and then dried under vacuum at 60 °C for 12 h.

[0140] The rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test under the condition of voltage range of 0.1-1.3 V. The test results are shown in FIG. Fig.19 .

[0141] Fig.19 The constant current charge and discharge curves for 1, 2, and 3 cycles at a current density of 20 mA / g show that the discharge specific capacity of the second cycle is 251.39 mAh / g, the charge specific capacity is 233.03 mAh / g, and the coulombic efficiency can reach 92%; the discharge specific capacity of the third cycle is 226.49 mAh / g, the charge specific capacity is 220.7 mAh / g, and the coulombic efficiency can reach 97%.

[0142] Example 12

[0143] Using Ca 0.28 MnO2 was used as the positive electrode active material, lead foil was used as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O was used as the electrolyte. A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0144] The Ca 0.28 The specific synthesis method of MnO2 positive electrode is as follows:

[0145] 0.002 mol CaCl2, 0.012 mol KMnO4 and 0.002 mol MnSO4·H2O were dissolved in 60 mL deionized water, stirred evenly and transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and kept at 160 °C for 12 h. Finally, the product was centrifuged, washed and dried in a vacuum at 60 °C for 12 h.

[0146] Under the condition of voltage range of 0.2-1.2 V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig. 20 .

[0147] Fig. 20 The constant current charge and discharge curves for 1, 2, and 3 cycles at a current density of 50 mA / g show that the discharge capacity of the second cycle is 118.47 mAh / g, the charge capacity is 134.18 mAh / g, and the coulombic efficiency can reach 88%; the discharge capacity of the third cycle is 119.17 mAh / g, the charge capacity is 112.84 mAh / g, and the coulombic efficiency can reach 94%.

[0148] Embodiment 13

[0149] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using V2O5 as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(CH3COO)2-H2O as the electrolyte.

[0150] Under the condition of a voltage range of 0.05-1.2 V, a cyclic voltammetry test was performed on the rechargeable rocking chair type aqueous lead ion battery prepared in this example.

[0151] Under the condition of a voltage range of 0.1-1.2 V, a constant current charge and discharge test was performed on the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment.

[0152] The rate performance of the rechargeable rocking chair type aqueous lead ion battery prepared in this example was tested at current densities of 20, 50, 100, 200, 500 and 1000 mA / g. Figure 21-23 .

[0153] Fig.21 This is the cyclic voltammetry curve at a scan rate of 0.1 mV / s. It can be seen from the figure that in the second and subsequent cycles, an obvious reduction peak appears at 0.44 V and an obvious oxidation peak appears at 0.73 V.

[0154] Fig. 22 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure, and the charge and discharge current density is 20 mA / g. The charge capacity of the second cycle is 119.22 mAh / g, the discharge capacity is 132.86 mAh / g, and the coulombic efficiency can reach 90%.

[0155] Fig.23 This is the rate performance diagram of the rechargeable rocking chair water-based lead ion battery. As can be seen from the figure, the capacity of the five cycles at different rates has basically not decayed. After five cycles at a current density of 1000 mA / g, the specific capacity can reach 30 mAh / g, and after returning to a current density of 50 mA / g, the specific capacity can still be restored. It can be seen that the battery under this system has very good rate performance and cycle stability.

[0156] Embodiment 14

[0157] The electrolyte of Example 13 was replaced by 1 mol / L Pb(BF4)2-H2O as the electrolyte, and the rechargeable rocking chair type aqueous lead ion battery prepared in this example was subjected to constant current charge and discharge test at a voltage range of 0.1-1.0V. The test results are shown in FIG. Fig.24 .

[0158] Fig.24 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure, and the charge and discharge current density is 10 mA / g. The charge capacity of the second cycle is 72.02 mAh / g, the discharge capacity is 74.26 mAh / g, and the coulombic efficiency can reach 97%.

[0159] Embodiment 15

[0160] NH4V4O10 As the positive electrode active material, lead foil as the negative electrode, 1 mol / L Pb(ClO4)2-H2O as the electrolyte, and a rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0161] The NH4V4O 10 The specific synthesis method of the positive electrode is as follows:

[0162] 3 mmol NH4VO3 was dissolved in 15 mL deionized water and stirred at 80 °C for 30 min to form solution A. 3 mmol H2C2O4 was dissolved in 15 mL deionized water and stirred evenly before adding to the above solution A. After stirring for 10 min, it was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave and kept at 180 °C for 8 hours. Finally, the product was centrifuged, washed, and dried in a vacuum at 60 °C for 12 hours.

[0163] The rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test under the condition of voltage range of 0.01-1.3 V. The test results are shown in FIG. Fig.25 .

[0164] Fig.25 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure, and the charge and discharge current density is 20 mA / g. The charge and discharge specific capacities of the first cycle are 281.42 and 213.33 mAh / g respectively.

[0165] Example 16

[0166] Using K 0.5 V2O5 was used as the positive electrode active material, lead foil was used as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O was used as the electrolyte. A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0167] The K 0.5 The specific synthesis method of V2O5 positive electrode is as follows:

[0168] 1mmol (0.1818g) V2O5, 13.5mmol (2.241g) KI and 30mmol (2.2365g) KCl were mixed in 30mL deionized water and stirred for 60min. Then, the obtained mixed solution was added into a 50mL polytetrafluoroethylene-lined stainless steel autoclave, sealed and heated in a 200℃ forced air oven for 24h. After the reaction was completed, the obtained precipitate was washed with deionized water and ethanol three times each. Finally, the product was dried in a vacuum oven at 80℃ for 24h to obtain K 0.5 V2O5.

[0169] The rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test under the condition of voltage range of 0.01-1.3 V. The test results are shown in FIG. Fig.26 .

[0170] Fig.26 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure, and the charge and discharge current density is 20 mA / g. The charge capacity of the second cycle is 101.37 mAh / g, and the discharge capacity is 100.13 mAh / g.

[0171] Embodiment 17

[0172] Using Mg 0.19 V2O5 was used as the positive electrode active material, lead foil was used as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O was used as the electrolyte. A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0173] The Mg 0.19 The specific synthesis method of V2O5 positive electrode is as follows:

[0174] 0.7692 g Mg(NO3)2·6H2O (0.003 mol) and 0.1818 g V2O5 (0.001 mol) were weighed and added to 60 mL deionized water. After vigorous stirring for 1 hour, the resulting orange solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave, placed in an oven, and then stored at 180°C for 12 hours. The light yellow flocculent precipitate was centrifuged, washed with water and ethanol several times, and then dried at 80°C for 6 hours. After drying, Mg 0.19 V2O5 samples.

[0175] The rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test under the condition of voltage range of 0.01-1.15 V. The test results are shown in FIG. Fig. 27 .

[0176] Fig. 27 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown below. The charge and discharge current density is 20 mA / g. The charge capacity of the second cycle is 82.41 mAh / g, the discharge capacity is 85.92 mAh / g, and the coulombic efficiency can reach 96%. The charge capacity of the third cycle is 84.04 mAh / g, the discharge capacity is 86.95 mAh / g, and the coulombic efficiency can reach 96%.

[0177] Example 18

[0178] Using MoS2 as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte, a rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0179] The specific synthesis method of the MoS2 positive electrode is as follows:

[0180] 0.24 g sodium molybdate dihydrate (Na2MoO4·2H2O) and 0.18 g thiourea (CH4N2S) were dissolved in 40 mL ethanol, and 0.1 g PVP (MW= 58000) was added and stirred for 12 hours until the mixed liquid became a milky suspension, and then placed in a 100 mL polytetrafluoroethylene-lined reactor. Then placed in an electric blast drying oven, kept at 230°C for 36 hours, and the reactor was cooled naturally to room temperature, and washed five times with deionized water and anhydrous ethanol to fully remove other impurities, placed in a vacuum drying oven and heated to 70°C for 12 hours, and fully dried to obtain a MoS2 sample.

[0181] Under the condition of voltage range of 0.2-1.3 V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.28 .

[0182] Fig.28 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown below. The charge and discharge current density is 20 mA / g. The charge capacity of the second cycle is 148.25 mAh / g, and the discharge capacity is 143.40 mAh / g. The charge capacity of the third cycle is 151.91 mAh / g, and the discharge capacity is 147.00 mAh / g.

[0183] Embodiment 19

[0184] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using CuHCF as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0185] The specific synthesis method of the CuHCF is:

[0186] 0.2 mol / L of copper sulfate pentahydrate and 0.1 mol / L of potassium ferrocyanide were added dropwise to the aqueous solution, and the mixture was allowed to stand for 1 hour after the addition, and then ultrasonically treated for 30 minutes and aged for 24 hours. The aged sample was centrifuged, washed with water and ethanol several times, and freeze-dried for 12 hours to obtain CuHCF.

[0187] Under the condition of a voltage range of 0.2-1.25 V, a cyclic voltammetry test was performed on the rechargeable rocking chair type aqueous lead ion battery prepared in this example.

[0188] Under the condition of a voltage range of 0.2-1.25 V, a constant current charge and discharge test was performed on the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment.

[0189] At a current density of 1000 mA / g, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was tested for cycle performance. The test results are shown in FIG. Figure 29-31 .

[0190] Fig.29 This is the cyclic voltammetry curve at a scan rate of 0.1 mV / s. It can be seen from the figure that in the second and subsequent cycles, obvious reduction peaks appear at 0.45V and 1.07V, and obvious oxidation peaks appear at 0.76V and 1.09V.

[0191] Fig.30 The charge and discharge curves for the 1st, 2nd and 3rd cycles are shown in the figure. The charge and discharge current density is 50 mA / g. After the second cycle, the charge capacity is 79.7 mAh / g and the discharge capacity is 78.4 mAh / g.

[0192] Fig.31 This is a cycle performance diagram of a rechargeable rocking chair type aqueous lead ion battery at a current density of 1000 mA / g. As can be seen from the figure, after 100 cycles, the capacity retention rate reaches 100%, showing excellent cycle stability.

[0193] Embodiment 20

[0194] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1 using NiHCF as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0195] The specific synthesis method of the NiHCF is:

[0196] 40 mL 10mM Ni(NO3)2 and 40 mL 5mM K3Fe(CN)6 were simultaneously added dropwise to 40 mL deionized water. The mixture was continuously stirred at room temperature for 2 hours. The precipitate was washed 3 times with deionized water and then freeze-dried in a vacuum for 12 hours to obtain a NiHCF sample.

[0197] Under the condition of voltage range of 0.1-1.2V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.32 .

[0198] Fig.32 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure. The charge and discharge current density is 20 mA / g. After the second cycle, the charge capacity is 63.82 mAh / g, the discharge capacity is 63.02 mAh / g, and the coulombic efficiency reaches 98%.

[0199] Embodiment 21

[0200] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using CoHCF as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0201] The specific synthesis method of the CoHCF is:

[0202] 0.1 mmol K3Fe(CN)6 and 0.7 g sodium dodecyl sulfate (SDS) were dissolved in 20 mL deionized water. Then, 20 mL 1 mM Co(CH3COO)2·4H2O aqueous solution was slowly added dropwise to the mixed solution. After aging at room temperature for 24 h, a yellowish brown precipitate was obtained, which was washed three times with deionized water. Finally, the collected powder was freeze-dried for 48 hours to obtain the product.

[0203] Under the condition of voltage range of 0.1-1.2V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.33 .

[0204] Fig.33 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure, and the charge and discharge current density is 20 mA / g. After the second cycle, the charge capacity is 40.88 mAh / g, the discharge capacity is 37.68 mAh / g, and the coulombic efficiency reaches 92%.

[0205] Embodiment 22

[0206] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using MnHCF as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0207] The specific synthesis method of the MnHCF is:

[0208] 1mmol MnSO4·H2O and 15mmol potassium citrate were dissolved in 100mL deionized water to form solution A, and 1mmol K4Fe(CN)6·3H2O was dissolved in 100mL deionized water to form solution B. Then, solution B was slowly dripped into solution A and magnetically stirred for 12h. The obtained precipitate was centrifuged and thoroughly washed with deionized water. Finally, the product was obtained after vacuum drying at 110℃ for 12h.

[0209] Under the condition of voltage range of 0.5-1.3V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.34 .

[0210] Fig.34The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown in the figure, and the charge and discharge current density is 20 mA / g. After the first cycle of activation, the charge capacity of the second cycle is 46.98 mAh / g, the discharge capacity is 42.36 mAh / g, and the coulombic efficiency reaches 90%.

[0211] Embodiment 23

[0212] Using Na3V2(PO4)3 as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte, a rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1.

[0213] The specific synthesis method of Na3V2(PO4)3 is as follows:

[0214] 1.83 g V2O5 and 3.78 g H2C2O4·H2O were added to a mixed solution of 100 ml ethanol and water (ratio 1:1), and then 3.60 g NaH2PO4 was added and stirred until the mixture was uniform. Then, the mixture was stirred thoroughly at 80°C to completely evaporate the solvent, and the obtained gel was placed in a vacuum drying oven at 120°C and dried for 10 hours to obtain a precursor. The precursor was then fully ground and pressed into a sheet, and finally, it was pre-calcined at 400°C for 4 hours in an argon atmosphere, and then heated to 750°C and calcined for 6 hours to finally obtain the Na3V2(PO4)3 positive electrode material.

[0215] Under the condition of voltage range of 0.4~1.1V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.35 .

[0216] Fig.35 The charge and discharge curves for the first two cycles are shown in the figure, with a charge and discharge current density of 100 mA / g. It can be seen from the figure that after the first charge to remove the sodium ions, the discharge platform is around 0.7V, and the charge specific capacity is 89.74 mAh / g, and the discharge specific capacity is 76.18 mAh / g.

[0217] Embodiment 24

[0218] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1 using Na3V2(PO4)2F as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0219] The specific synthesis method of Na3V2(PO4)2F is as follows:

[0220] Na3V2(PO4)2F was synthesized by solid phase method. First, 2mmol V2O5 and 6mmol H2C2O4·H2O were added to a beaker containing 30ml distilled water, stirred at 80℃ until the solution became transparent, and then 6mmol NH4H2PO4 was added. After evaporating the solution to dryness, it was dried in an oven at 80℃ overnight to obtain a fluffy precursor, which was transferred to a tube furnace after grinding and calcined at 400℃ for 3h in an argon atmosphere and then calcined at 650℃ for 6h to obtain the precursor. Finally, the obtained precursor was evenly ground and mixed with NaF, and then calcined in a tube furnace at 600℃ in an argon atmosphere for 2h to obtain the Na3V2(PO4)2F sample.

[0221] Under the condition of voltage range of 0.1-1.2V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.36 .

[0222] Fig.36 The charge and discharge curves for the first two cycles are shown in the figure, with a charge and discharge current density of 20 mA / g. As can be seen from the figure, there is almost no capacity after the first discharge, indicating that a large number of sodium ions occupy the active sites, and the capacity after charging is 111.90 mAh / g. The discharge capacity of the second cycle is 83.63 mAh / g, the charging platform is about 1.0 V, and the discharge capacity is 86.59 mAh / g.

[0223] Embodiment 25

[0224] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1, using commercial polyaniline PANI as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(CH3COO)2-H2O as the electrolyte.

[0225] Under the condition of voltage range of 0.05-0.9 V, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are shown in FIG. Fig.37 .

[0226] Fig.37 The charge and discharge curves of the 1st, 2nd and 3rd cycles are shown, and the charge and discharge current density is 5mA / g. After the first cycle of activation, the charge capacity after the second cycle is 165.64mAh / g, and the discharge capacity is 157.71mAh / g. After the second cycle, the charge capacity is 162.56mAh / g, and the discharge capacity is 153.64mAh / g.

[0227] Embodiment 26

[0228] A rechargeable rocking chair type aqueous lead ion battery was assembled according to the method of Example 1 using commercial calix[4]quinone as the positive electrode active material, lead foil as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O as the electrolyte.

[0229] Under the condition of voltage range of 0.1~1.1VV, the rechargeable rocking chair type aqueous lead ion battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.38 .

[0230] Fig.38 The charge and discharge curve of the first cycle, the charge and discharge current density is 10 mA / g. It can be seen from the figure that the first discharge platform is near 0.5V, and the charge capacity is 184.3 mAh / g, the discharge capacity is 182.3 mAh / g, and the coulombic efficiency reaches 98.9%.

[0231] Embodiment 27

[0232] The α-MnO2 prepared in Example 2 was used as the positive electrode active material, the lead foil was used as the negative electrode, and 1 mol / L Pb(ClO4)2-H2O was used as the electrolyte. The soft-pack positive electrode side, the positive electrode, the separator, the electrolyte, the lead negative electrode, and the soft-pack negative electrode side were stacked in sequence, and 50 μL of the above electrolyte was dripped on the separator between the positive electrode and the negative electrode to make it completely infiltrated. The battery was packaged to obtain a rechargeable rocking chair type aqueous lead ion soft pack battery ( Fig.39 ).

[0233] Under the condition of voltage range of 0.3-1.2V, the rechargeable rocking chair type aqueous lead ion soft pack battery prepared in this embodiment was subjected to constant current charge and discharge test. The test results are as follows: Fig.40 .

[0234] Fig.40 This is the charge and discharge curve of the first cycle, and the charge and discharge current density is 50 mA / g. It can be seen from the figure that the charge specific capacity is 200mAh / g and the discharge specific capacity is 255mAh / g.

[0235] Fig.41 It is a schematic diagram of four soft-pack batteries connected in series. It can be seen that the battery capacity of the rechargeable rocking chair type aqueous lead ion soft-pack battery prepared in this embodiment is sufficient to charge a smart phone, showing good application value.

[0236] The specific embodiments described above further illustrate the purpose and technical solutions of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made by ordinary technicians in this field should be included in the scope of protection of this invention.

Claims

1. A rechargeable rocking chair type aqueous lead ion battery, characterized in that: The invention comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the negative electrode is an electrode containing metallic lead; the electrolyte has a soluble lead salt as a solute and water as a solvent; the active material of the positive electrode is one or a mixture of vanadium oxide, sulfide, selenide, Prussian blue analogue, polyanionic compound or organic electrode material; the diaphragm can pass lead ions; During the discharge process of the battery, the metal lead in the negative electrode obtains electrons to become lead ions which are embedded in the positive electrode through the electrolyte; during the charging process, the lead ions are released from the positive electrode active material and deposited in the negative electrode through the electrolyte; the charge and discharge cycle is carried out in this way; The battery is charged and discharged at a constant current density; The soluble lead salt is one or more of lead perchlorate trihydrate, lead acetate trihydrate, dibasic lead salicylate, lead citrate, lead fluorosilicate or lead tetrafluoroborate.

2. The rechargeable rocking chair type aqueous lead ion battery according to claim 1, characterized in that: The negative electrode is an electrode containing metal lead foil, metal lead powder or metal lead alloy.

3. The rechargeable rocking chair type aqueous lead ion battery according to claim 1, characterized in that: The vanadium oxide is V2O5, NH4V4O 10 , K x V2O5 or Mg x V2O5, the sulfide is MoS2, the selenide is Cu2Se, the Prussian blue analog is FeHCF, CuHCF, NiHCF, CoHCF or MnHCF, and the polyanionic compound is Na3V2(PO4)3 or Na3V2(PO4) 3-x F x , the organic electrode material is polyaniline or cup[4]quinone, wherein 0< x ≤1.

4. The rechargeable rocking chair type aqueous lead ion battery according to claim 1, characterized in that: The concentration of the soluble lead salt is 0.01-10 mol / L.

5. The rechargeable rocking chair type aqueous lead ion battery according to claim 1, characterized in that: The diaphragm is filter paper or glass fiber.

Images