Aqueous battery positive electrode material of polyaniline doped with inorganic and organic dual acids

Abstract

The invention discloses an aqueous battery positive electrode material of inorganic and organic dual acid doped polyaniline, and belongs to the technical field of battery materials, a preparation method comprises the following steps: step 1, continuously stirring aniline and adding the aniline into a chloroform solution to obtain a mixed solution I, and then adding organic acid / organic acid salt into the mixed solution I and continuously stirring to obtain a mixed solution II; 2, respectively dissolving inorganic acid and (NH4) 2S2O8 in deionized water, respectively dropwise adding the mixed solution 2, and stirring to obtain a product; and 3, separating the product from the liquid, placing the obtained polymer in a watch glass to volatilize the solvent, cleaning with acetone, filtering with filter paper, and drying to obtain the aqueous battery positive electrode material. And high ion and electron conductivity and structural stability in the charging and discharging process are ensured. In addition, the PANI positive electrode material prepared by the strategy has a rich pore structure, and also provides a convenient path for intercalation and deintercalation of anions and cations in the charging and discharging process.

Description

Technical Field

[0001] The present application relates to the technical field of battery materials, and in particular to an aqueous battery positive electrode material of inorganic and organic dual acid-doped polyaniline. Background Art

[0002] Aqueous zinc-ion batteries are mainly composed of four parts: positive electrode, negative electrode, electrolyte and separator. Among them, the positive electrode material largely determines the working voltage and specific capacity of the battery. There are few polymer positive electrode materials suitable for aqueous zinc batteries, and polyaniline (PANI) is currently the most promising positive electrode material. In the preparation of PANI battery positive electrode materials reported so far, both chemical synthesis and electrochemical synthesis methods use a single acid system, and most of them are HCl. The specific capacity of the assembled aqueous zinc battery is usually less than 100mAh·g -1 In order to promote the development of grid-scale energy storage, it is urgent to develop PANI cathode materials with high capacity, long life, low cost and easy large-scale production in neutral / weakly acidic electrolytes. Summary of the invention

[0003] The purpose of the present application is to provide an aqueous battery positive electrode material of inorganic and organic dual acid doped polyaniline to solve the technical problem of low specific capacity of aqueous zinc batteries in the prior art.

[0004] The present invention provides an aqueous battery positive electrode material of inorganic and organic dual acid doped polyaniline. The preparation method of the aqueous zinc battery positive electrode material is as follows:

[0005] Step 1, adding aniline to a chloroform solution with continuous stirring to obtain a mixed solution 1, and then adding an organic acid / organic acid salt to the mixed solution 1 and continuing stirring to obtain a mixed solution 2;

[0006] Step 2, dissolving the inorganic acid and (NH4)2S2O8 in deionized water respectively, adding the mixture dropwise to the mixed solution 2 respectively, and stirring to obtain the product;

[0007] Step 3: Separate the product from the liquid, place the obtained polymer in a watch glass to volatilize the solvent, wash with acetone, filter with filter paper, and dry to obtain an aqueous battery positive electrode material.

[0008] Preferably, the organic acid / organic acid salt in step 1 includes one or more of dodecyl sulfonic acid, ammonium dodecyl sulfate, dodecylbenzenesulfonic acid, camphorsulfonic acid, naphthalenesulfonic acid, p-toluenesulfonic acid, p-aminobenzenesulfonic acid, sulfosalicylic acid, citric acid, malic acid, oxalic acid, phytic acid, tartaric acid and 2,4-dinitronaphthol-7-sulfonic acid, and salts of the above various organic acids.

[0009] Preferably, in step 2, the inorganic acid includes one or more of HCl, HBr, H2SO4, HClO4, HNO3, H3PO4, H2MoO4, phosphomolybdic acid, and HBF4.

[0010] Preferably, in step 2, when sulfuric acid is dissolved in deionized water, the volume ratio of sulfuric acid to deionized water is: 1.5 mL:25 mL.

[0011] Preferably, in step 2, when (NH4)2S2O8 is dissolved in deionized water, the ratio of the mass of (NH4)2S2O8 to the volume of deionized water is 0.3g:25mL.

[0012] Preferably, in step three, the specific step of drying is to place the polymer in a vacuum oven at 60° C. and dry it for 24 hours.

[0013] The present application provides an aqueous battery positive electrode material prepared according to the above-mentioned inorganic-organic dual acid-doped polyaniline aqueous battery positive electrode material.

[0014] Therefore, the present application provides an inorganic-organic dual acid-doped polyaniline aqueous battery positive electrode material, which has the following beneficial effects:

[0015] 1. Select inorganic and organic dual acid (sulfuric acid (H2SO4) / ammonium dodecyl sulfate (ALS) or H2SO4 / sodium dodecyl sulfate (SDS)) for doping, and use a simple one-pot method to chemically synthesize dual acid-doped polyaniline (H2SO4 / ALS-PANI or H2SO4 / SDS-PANI). The doping of organic acid ALS or its salt SDS can change the morphology of PANI, while the introduction of inorganic acid H2SO4 can improve the conductivity of PANI. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the synthesis route of the co-doped polyaniline positive electrode material of Example 1 of the present application;

[0017] Figure 2 The comparison results of the cycle performance of the batteries of Example 1, Comparative Examples 1.1 and 1.2;

[0018] Figure 3 The morphology comparison diagrams of the batteries of Example 1, Comparative Examples 1.1 and 1.2, wherein a is the SEM image of H2SO4-PANI of Comparative Example 1.1; b is the SEM image of ALS-PANI of Comparative Example 1.2; c is the SEM image of H2SO4 / ALS-PANI obtained in Example 1;

[0019] Figure 4 The comparison results of the cycle performance of the batteries of Example 2, Comparative Examples 2.1 and 2.2 are shown;

[0020] Figure 5 The morphology comparison diagrams of the batteries of Example 2, Comparative Examples 2.1 and 2.2, wherein a is the SEM image of P-PANI of Comparative Example 2.1; b is the SEM image of SDS-PANI of Comparative Example 2.2; c is the SEM image of H2SO4 / SDS-PANI obtained in Example 2;

[0021] Figure 6 The specific capacity curves of the batteries of Example 2, Comparative Examples 2.1 and 2.2 at different current densities;

[0022] Figure 7 The H2SO4 / SDS-PANI of Example 2 was prepared at 5Ag -1 Cycle performance diagram of

[0023] Figure 8 For the SDS-PANI of Comparative Example 2.2, 5Ag -1 Cycle performance diagram. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further illustrated by the following examples.

[0025] Example 1

[0026] At room temperature, 1 mL of aniline was added to a reaction bottle containing 50 mL of chloroform solution under constant stirring. 2.3 g of ALS was added to the reaction bottle and continued to stir for 15 minutes. 1.8 mL of H2SO4 was dissolved in 25 mL of deionized water and 0.3 g of (NH4)2S2O8 (APS) was dissolved in 25 mL of deionized water, and added dropwise to the mixed solution. The solution gradually turned green, indicating the formation of PANI. Stirring was continued for 24 hours to terminate the reaction. The product was separated from the liquid, and the polymer was placed in a watch glass to volatilize the solvent. The dark green precipitate was washed with acetone and filtered with filter paper. The polymer was placed in a vacuum oven and dried at 60°C for 24 hours to obtain dual-doped PANI (H2SO4 / ALS-PANI).

[0027] Aqueous zinc battery 5A·g assembled with H2SO4 / ALS-PANI as cathode and 1M ZnSO4 electrolyte -1 The capacity is 223.5 mAh g -1 The capacity retention rate after 4000 cycles is 97.7%, and the specific capacity is almost the highest capacity reported so far (118 mAh g -1 ) and the cycle performance is 35%-40% higher than that of the single acid doping system.

[0028] Comparative Example 1.1

[0029] Preparation steps of H2SO4-PANI;

[0030] At room temperature, 1 mL of aniline was added to a reaction bottle containing 50 mL of chloroform solution under constant stirring. 1.8 mL of H2SO4 was dissolved in 25 mL of deionized water and 0.3 g of (NH4)2S2O8 was dissolved in 25 mL of deionized water, and then added dropwise to the mixed solution. The solution gradually turned green, indicating the formation of PANI. Stirring was continued for 24 hours to terminate the reaction. The product was separated from the liquid, and the polymer was placed in a watch glass to evaporate the solvent. The dark green precipitate was washed with acetone and filtered with filter paper. The polymer was placed in a vacuum oven and dried at 60°C for 24 hours to obtain sulfuric acid-doped PANI (H2SO4-PANI).

[0031] Comparative Example 1.2

[0032] Preparation steps of ALS-PANI;

[0033] At room temperature, add 1 mL of aniline to a reaction bottle containing 50 mL of chloroform solution while stirring continuously. Add 2.3 g of ALS to the reaction bottle and continue stirring for 15 minutes. Dissolve 0.3 g of (NH4)2S2O8 in 25 mL of deionized water and add dropwise to the mixed solution. The solution gradually turns green, indicating the formation of PANI. Continue stirring for 24 hours to end the reaction. Separate the product from the liquid, place the polymer in a watch glass to evaporate the solvent, wash the dark green precipitate with acetone, and filter with filter paper. Dry the polymer in a vacuum oven at 60°C for 24 hours to obtain ALS-PANI.

[0034] Example 2

[0035] At room temperature, 1 mL of aniline was added to a reaction bottle containing 50 mL of chloroform solution under constant stirring. 2.3 g of SDS was added to the reaction bottle and continued to stir for 15 minutes. 1.8 mL of H2SO4 was dissolved in 25 mL of deionized water and 0.3 g of (NH4)2S2O8 (APS) was dissolved in 25 mL of deionized water, and then added dropwise to the mixed solution. The solution gradually turned green, indicating the formation of PANI. The reaction was terminated by stirring for 24 hours. The product was separated from the liquid, and the polymer was placed in a watch glass to volatilize the solvent. The dark green precipitate was washed with acetone and filtered with filter paper. The polymer was placed in a vacuum oven and dried at 60°C for 24 hours to obtain dual-doped PANI (H2SO4 / SDS-PANI).

[0036] Aqueous zinc battery 5A·g assembled with H2SO4 / SDS-PANI as cathode and 1M ZnSO4 electrolyte -1 The capacity is 136.57 mAh g -1The capacity retention rate after 10,000 cycles is 89.3%. Under the same conditions, the capacity of the undoped polyaniline (P-PANI) positive electrode material battery is 44.17 mAh g -1 The capacity of the single doped SDS-PANI as the positive electrode is 78.46 mAh g -1 The capacity retention rate after 10,000 cycles is 69.47%. -1 The capacity is 114.19 mAh g -1 The capacity retention rate after 10,000 cycles is 89.6%, which shows that the dual-doped PANI has good rate performance and long cycle stability.

[0037] Comparative Example 2.1

[0038] Preparation steps of P-PANI;

[0039] At room temperature, 1 mL of aniline was added to a reaction bottle containing 50 mL of chloroform solution under constant stirring. 0.3 g of (NH4)2S2O8 was dissolved in 25 mL of deionized water. After the above solution was added dropwise, the solution gradually turned green, indicating the formation of PANI. Stirring was continued for 24 hours to terminate the reaction. The product was separated from the liquid, and the polymer was placed in a watch glass to evaporate the solvent. The dark green precipitate was washed with acetone and filtered with filter paper. The polymer was placed in a vacuum oven and dried at 60°C for 24 hours to obtain undoped PANI (P-PANI).

[0040] Comparative Example 2.2

[0041] Preparation steps of SDS-PANI;

[0042] At room temperature, 1 mL of aniline was added to a reaction bottle containing 50 mL of chloroform solution under constant stirring. 2.3 g of SDS was added to the reaction bottle and continued to stir for 15 minutes. 0.3 g of (NH4)2S2O8 was dissolved in 25 mL of deionized water and added dropwise to the mixed solution. The solution gradually turned green, indicating the formation of PANI. Stirring was continued for 24 hours to terminate the reaction. The product was separated from the liquid, the polymer was placed in a watch glass to evaporate the solvent, and the dark green precipitate was washed with acetone and filtered with filter paper. The polymer was placed in a vacuum oven and dried at 60°C for 24 hours to obtain SDS-doped PANI (SDS-PANI).

[0043] Therefore, the present application provides an inorganic-organic dual acid-doped polyaniline aqueous battery positive electrode material, which ensures high ionic and electronic conductivity and structural stability during the charge and discharge process. In addition, the PANI positive electrode material prepared by this strategy has a rich pore structure, which also provides a convenient path for the insertion and removal of anions and cations during the charge and discharge process.

[0044] In the description of this specification, the description with reference to the terms "an experimental example", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the experimental example or example are included in at least one experimental example or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same experimental example or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more experimental examples or examples in a suitable manner.

[0045] Finally, it should be noted that the above experimental examples are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred experimental examples, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. An aqueous battery positive electrode material of inorganic and organic dual acid doped polyaniline, characterized in that: The preparation method of the positive electrode material of the aqueous battery is as follows: Step 1, adding aniline to a chloroform solution with continuous stirring to obtain a mixed solution 1, and then adding an organic acid / organic acid salt to the mixed solution 1 and continuing stirring to obtain a mixed solution 2; Step 2, dissolving the inorganic acid and (NH4)2S2O8 in deionized water respectively, adding the mixture dropwise to the mixed solution 2 respectively, and stirring to obtain the product; Step 3: Separate the product from the liquid, place the obtained polymer in a watch glass to volatilize the solvent, wash with acetone, filter with filter paper, and dry to obtain an aqueous battery positive electrode material.

2. The aqueous battery positive electrode material of inorganic-organic dual acid-doped polyaniline according to claim 1, characterized in that: The organic acid / organic acid salt in step 1 includes one or more of dodecyl sulfonic acid, ammonium dodecyl sulfate, dodecylbenzenesulfonic acid, camphorsulfonic acid, naphthalenesulfonic acid, p-toluenesulfonic acid, p-aminobenzenesulfonic acid, sulfosalicylic acid, citric acid, malic acid, oxalic acid, phytic acid, tartaric acid and 2,4-dinitronaphthol-7-sulfonic acid, and salts of the above organic acids.

3. The aqueous battery positive electrode material of inorganic-organic dual acid-doped polyaniline according to claim 2, characterized in that: In step 2, the inorganic acid includes one or more of HCl, HBr, H2SO4, HClO4, HNO3, H3PO4, H2MoO4, phosphomolybdic acid, and HBF4.

4. The aqueous battery positive electrode material of inorganic-organic dual acid-doped polyaniline according to claim 1, characterized in that: In step 2, when sulfuric acid is dissolved in deionized water, the volume ratio of sulfuric acid to deionized water is: 1.5 mL:25 mL.

5. The aqueous battery positive electrode material of inorganic-organic dual acid-doped polyaniline according to claim 1, characterized in that: In step 2, when (NH4)2S2O8 is dissolved in deionized water, the mass ratio of (NH4)2S2O8 to the volume of deionized water is 0.3g:25mL.

6. The aqueous battery positive electrode material of inorganic-organic dual acid-doped polyaniline according to claim 1, characterized in that: In step 3, the specific step of drying is to put the polymer into a vacuum oven at 60° C. and dry it for 24 hours.

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