Composite material for aqueous ammonium ion / proton hybrid battery and preparation method and application thereof

Abstract

The invention relates to the technical field of battery materials, and particularly discloses a composite material for an aqueous ammonium ion / proton hybrid battery and a preparation method and application thereof. The conductive polymer coated manganese dioxide composite material is prepared by adopting an organic-inorganic interface reaction, the preparation process is simple and easy to operate, the required raw materials are low in cost and easy to obtain, and the synthesized material is a nanoscale material and has the advantages of good dispersity, high specific surface area, good conductivity, stable structure and the like; when the material is applied to the aqueous ammonium ion / proton mixed ion battery, the obtained battery material has excellent rate capability and stable cycle life, has a high application prospect, and provides a new design idea for the existing aqueous ammonium ion / proton mixed ion battery.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, specifically disclosing a composite material for aqueous ammonium ion / proton hybrid batteries, its preparation method, and its application. Background Technology

[0002] Developing rechargeable batteries is an important research direction for achieving clean energy and sustainable development. In recent years, driven by the pursuit of energy storage devices with high safety, high stability, and eco-friendliness, many researchers have turned their attention to aqueous ion batteries based on aqueous electrolytes, as they have the characteristics of being environmentally friendly, highly safe, and having high transmission efficiency, and have broad application prospects in the field of large-scale energy storage.

[0003] However, for aqueous metal ions (such as Li) + Zn 2+ Al 3+ The high level of attention paid to batteries has also led to a focus on aqueous non-metallic ions (such as H+). + H3O + NH4 + Research on batteries has been neglected to some extent. Therefore, researchers have recently shifted their focus to the field of aqueous non-metallic ion batteries. Among them, aqueous ammonium ion batteries and aqueous proton batteries have received widespread attention due to their advantages such as high intrinsic safety, low cost and sustainability. Specifically, they are: (1) low cost and environmentally friendly and sustainable; unlike metal ions, H + H3O + and NH4 + Composed solely of nitrogen (N) and hydrogen (H), it is a widely distributed sustainable resource in nature, and because of H... + H3O + NH4 + The base electrolyte is usually readily soluble in water and easily pyrolyzed, making battery recycling very simple, efficient, and inexpensive, greatly solving the problem of difficult recycling of traditional metal-ion batteries. (2) Rapid reaction kinetics; H + H3O + NH4 + It has a small hydration radius and a relatively light molar mass (<19 g·mol⁻¹). -1 Its diffusion rate is lower than that of most metal carriers, thus it has a fast and efficient diffusion rate, which is beneficial for improving the power density of the device.

[0004] Therefore, developing inexpensive, safe, and environmentally friendly aqueous non-metallic ion batteries, especially aqueous non-metallic ion hybrid batteries, has become an effective strategy for achieving large-scale energy storage. Summary of the Invention

[0005] In view of this, the present invention provides a composite material for aqueous ammonium ion / proton hybrid batteries, its preparation method and application.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: The first aspect of the present invention provides a composite material for an aqueous ammonium ion / proton hybrid battery, wherein the composite material for the aqueous ammonium ion / proton hybrid battery is a conductive polymer-coated manganese dioxide composite material.

[0007] Compared to existing technologies, this invention utilizes an organic-inorganic interfacial reaction to prepare a conductive polymer-coated manganese dioxide composite material for aqueous ammonium ion / proton hybrid batteries. The layered manganese dioxide structure possesses open two-dimensional ion channels capable of accommodating ion diffusion, facilitating the insertion / extraction of non-metallic charge carriers. Coating the surface of the layered manganese dioxide material with a highly conductive polymer not only improves the conductivity of the composite material and slows down the dissolution of manganese dioxide in the electrolyte, but also maintains the nanostructure of the material, increases its specific surface area, and provides more reactive sites, thus promoting ion transport and achieving higher storage capacity. When this conductive polymer-coated manganese dioxide composite material is applied to the preparation of aqueous ammonium ion / proton hybrid batteries, the resulting battery material exhibits excellent rate performance and stable cycle life, showing high application potential and providing a new design approach for existing aqueous non-metallic ion batteries.

[0008] A second aspect of the present invention provides a method for preparing a composite material for an aqueous ammonium ion / proton hybrid battery, comprising the following steps: S1. Dissolve the manganese source in deionized water to obtain solution A; S2. Disperse the small organic monomer in an organic solvent to obtain solution B; S3. Mix solution A and solution B, let stand at 3~6℃, separate solid and liquid, wash the solid filter material to obtain the precursor; S4. The precursor is dried at -50~-60℃ to obtain a composite material for aqueous ammonium ion / proton hybrid batteries.

[0009] The preparation process of the composite material for aqueous ammonium ion / proton hybrid batteries described in this invention is simple and easy to operate. The required raw materials are inexpensive and readily available. The synthesized material is a nanoscale material with advantages such as good dispersibility, high specific surface area, good conductivity, and stable structure, which is beneficial to improving the electrochemical performance of the material.

[0010] Preferably, in S1, the mass-to-volume ratio of the manganese source and deionized water is 0.1g:100mL to 0.15g:100mL.

[0011] Preferably, in S2, the volume ratio of the small organic molecule monomer to the organic solvent is 1:100 to 5:100.

[0012] More preferably, in S3, the volume ratio of solution A to solution B is 1:1 to 1:1.1.

[0013] Preferably, in S1, the manganese source is potassium permanganate.

[0014] Preferably, in S2, the organic small molecule monomer is any one of aniline monomer, pyrrole monomer, or thiophene monomer.

[0015] Preferably, in S2, the organic solvent is carbon tetrachloride.

[0016] Preferably, in step S3, the settling time is 22 to 50 hours.

[0017] Preferably, in step S4, the heat preservation time for the drying process is 45-50 hours.

[0018] A third aspect of the present invention provides an aqueous ammonium ion / proton hybrid electrode, comprising the aforementioned composite material for aqueous ammonium ion / proton hybrid batteries.

[0019] The fourth aspect of this invention provides a method for preparing the aqueous ammonium ion / proton hybrid electrode, comprising the following steps: Step 1: Clean and degrease the titanium foil discs to obtain pretreated titanium foil discs; Step 2: Mix the aqueous ammonium ion / proton hybrid battery composite material, polyvinylidene fluoride and acetylene black evenly, add methylpyrrolidone, and sonicate to obtain electrode slurry; Step 3: Coat the electrode slurry onto the surface of the pretreated titanium foil and dry it to obtain an aqueous ammonium ion / proton mixed electrode.

[0020] Preferably, in step two, the mass ratio of the aqueous ammonium ion / proton hybrid battery composite material, polyvinylidene fluoride, and acetylene black is 6~8:1:2.

[0021] Preferably, in step two, the mass-to-volume ratio of the aqueous ammonium ion / proton hybrid battery composite material to the methylpyrrolidone is 1g:1mL to 1g:3mL.

[0022] Preferably, in step three, the coating thickness is 50~100μm.

[0023] The fifth aspect of the present invention provides the application of the aqueous ammonium ion / proton hybrid electrode in the preparation of an aqueous ammonium ion / proton hybrid ion battery.

[0024] In summary, this invention utilizes an organic-inorganic interfacial reaction to prepare a composite material for an aqueous ammonium ion / proton hybrid battery. Manganese dioxide is coated with a conductive polymer to obtain a nanoscale conductive material. This aqueous ammonium ion / proton hybrid battery composite material possesses advantages such as good dispersibility, high specific surface area, good conductivity, and structural stability. The battery prepared using this composite material exhibits excellent electrochemical performance, providing a new approach for the design of existing aqueous non-metallic ion batteries. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the XRD structure of the composite material for an aqueous ammonium ion / proton hybrid battery provided in Embodiment 1 of the present invention; Figure 2 TEM image of the composite material for aqueous ammonium ion / proton hybrid batteries provided in Example 1 of this invention; Figure 3 This is an electrochemical test diagram of the composite material for an aqueous ammonium ion / proton hybrid battery provided in Example 1 of the present invention; Figure 4 This is an electrochemical test diagram of the composite material for an aqueous ammonium ion / proton hybrid battery provided in Example 2 of the present invention. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are merely one embodiment of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1 This embodiment provides a method for preparing a polyaniline-coated manganese dioxide composite material for an aqueous ammonium ion / proton hybrid battery, comprising the following steps: S1. Dissolve 0.4g of potassium permanganate in 400mL of deionized water to obtain solution A; S2. Disperse 8 mL of aniline monomer in 400 mL of carbon tetrachloride to obtain solution B; S3. Mix solutions A and B. The mixture will separate into two layers: solution A is on top and is purplish-black, while solution B is on the bottom and is transparent. There is a clear interface between the two layers. Place the mixture in a refrigerator at 5°C and let it stand for 24 hours. After the reaction is complete, a black flocculent precipitate can be observed to form in the upper layer. Filter the precipitate and wash it three times with deionized water and ethanol, respectively, to obtain the precursor. S4. The precursor is freeze-dried at -50°C for 48 hours to obtain a polyaniline-coated manganese dioxide composite material for aqueous ammonium ion / proton hybrid batteries.

[0028] Example 2 This embodiment provides a method for preparing a polypyrrole-coated manganese dioxide composite material for an aqueous ammonium ion / proton hybrid battery, comprising the following steps: S1. Dissolve 0.2g of potassium permanganate in 200mL of deionized water to obtain solution A; S2. Disperse 2 mL of pyrrole monomer into 200 mL of carbon tetrachloride to obtain solution B; S3. Mix solutions A and B. The mixture will separate into two layers: solution A is on top and is purplish-black, while solution B is on the bottom and is transparent. There is a clear interface between the two layers. Place the mixture in a refrigerator at 3°C ​​and let it stand for 48 hours. After the reaction is complete, a black flocculent precipitate will be observed in the upper layer. Filter the precipitate and wash it three times with deionized water and ethanol, respectively, to obtain the precursor. S4. The precursor is freeze-dried at -40°C for 45 hours to obtain a polypyrrole-coated manganese dioxide composite material for aqueous ammonium ion / proton hybrid batteries.

[0029] Example 3 This embodiment provides a method for preparing a polypyrrole-coated manganese dioxide composite material for an aqueous ammonium ion / proton hybrid battery, comprising the following steps: S1. Dissolve 0.4g of potassium permanganate in 400mL of deionized water to obtain solution A; S2. Disperse 8 mL of pyrrole monomer in 600 mL of carbon tetrachloride to obtain solution B; S3. Mix solutions A and B. The mixture will separate into two layers: solution A is on top and is purplish-black, while solution B is on the bottom and is transparent. There is a clear interface between the two layers. Place the mixture in a refrigerator at 4°C and let it stand for 36 hours. After the reaction is complete, a black flocculent precipitate will be observed in the upper layer. Filter the precipitate and wash it three times with deionized water and ethanol, respectively, to obtain the precursor. S4. The precursor is freeze-dried at -50°C for 45 hours to obtain a polypyrrole-coated manganese dioxide composite material for aqueous ammonium ion / proton hybrid batteries.

[0030] Example 4 This embodiment provides a method for preparing a polyaniline-coated manganese dioxide composite material for an aqueous ammonium ion / proton hybrid battery, comprising the following steps: S1. Dissolve 0.4g of potassium permanganate in 400mL of deionized water to obtain solution A; S2. Disperse 8 mL of aniline monomer into 580 mL of carbon tetrachloride to obtain solution B; S3. Mix solutions A and B. The mixture will separate into two layers: solution A is on top and is purplish-black, while solution B is on the bottom and is transparent. There is a clear interface between the two layers. Place the mixture in a refrigerator at 5°C and let it stand for 32 hours. After the reaction is complete, a black flocculent precipitate will be observed in the upper layer. Filter the precipitate and wash it three times with deionized water and ethanol, respectively, to obtain the precursor. S4. The precursor is freeze-dried at -55°C for 47 hours to obtain a polyaniline-coated manganese dioxide composite material for aqueous ammonium ion / proton hybrid batteries.

[0031] Example 5 This embodiment provides a polyaniline-coated manganese dioxide electrode for an aqueous ammonium ion / proton hybrid battery, specifically including the following: Step 1: Place the polished titanium foil disc (thickness 0.03mm, diameter 10mm) in ethanol and sonicate it multiple times to remove impurities such as oxides and grease from its surface, to obtain a pretreated titanium foil disc. Step 2: Polyvinylidene fluoride, acetylene black, and the polyaniline-coated manganese dioxide composite material for the aqueous ammonium ion / proton hybrid battery obtained in Example 1 are ground and mixed evenly at a mass ratio of 1:2:7. Methylpyrrolidone is added as a solvent at a mass-to-volume ratio of 1g:2mL to the polyaniline-coated manganese dioxide composite material for the aqueous ammonium ion / proton hybrid battery obtained in Example 1. The mixture is ultrasonicated for 0.5h and magnetically stirred for 1h to obtain an electrode slurry. Step 3: The electrode slurry is uniformly coated on the surface of the pretreated titanium foil with a coating thickness of 50 μm, and then dried in an oven at 70°C for 10 h to obtain a polyaniline-coated manganese dioxide electrode for an aqueous ammonium ion / proton hybrid battery.

[0032] Example 6 This embodiment provides a polypyrrole-coated manganese dioxide electrode for an aqueous ammonium ion / proton hybrid battery, specifically including the following: Step 1: Place the polished titanium foil disc (thickness 0.03mm, diameter 10mm) in ethanol and sonicate it multiple times to remove impurities such as oxides and grease from its surface, to obtain a pretreated titanium foil disc. Step 2: Polyvinylidene fluoride, acetylene black, and the polypyrrole-coated manganese dioxide composite material for the aqueous ammonium ion / proton hybrid battery obtained in Example 2 are ground and mixed evenly at a mass ratio of 1:2:7. Methylpyrrolidone is added as a solvent at a mass-to-volume ratio of 1g:2mL to the polypyrrole-coated manganese dioxide composite material for the aqueous ammonium ion / proton hybrid battery obtained in Example 2. The mixture is ultrasonicated for 0.5h and magnetically stirred for 1h to obtain an electrode slurry. Step 3: The electrode slurry is uniformly coated on the surface of the pretreated titanium foil with a coating thickness of 50 μm, and then dried in an oven at 70°C for 10 h to obtain a polypyrrole-coated manganese dioxide electrode for an aqueous ammonium ion / proton hybrid battery.

[0033] To further demonstrate the technical effects of the present invention, the polyaniline-coated manganese dioxide composite material used in the aqueous ammonium ion / proton hybrid battery obtained in Example 1 was characterized by XRD and TEM. The results are as follows: Figures 1-2 As shown, all diffraction peaks in the XRD pattern correspond to δ The standard spectrum of MnO2 (JCPDS, No. 13-0105) indicates that the synthesized composite material has a two-dimensional layered structure. In the electron microscopy image, the amorphous polyaniline wrapped around the surface of the well-crystallized MnO2 nanoparticles plays an "isolation" role, avoiding the formation of large-sized MnO2 bulk particles, realizing the nano-modification of the material and maintaining its high dispersion.

[0034] Electrochemical tests were performed on the aqueous ammonium ion / proton hybrid batteries obtained in Examples 5-6 using polyaniline-coated manganese dioxide electrodes and polypyrrole-coated manganese dioxide electrodes. A conventional three-electrode system was used as the electrochemical testing device, with either the polyaniline-coated manganese dioxide electrode or the polypyrrole-coated manganese dioxide electrode used as the working electrode, a graphite carbon rod as the counter electrode, and Ag / AgCl as the reference electrode. The electrolyte was a weakly acidic 1 mol·L⁻¹ solution. -1 An aqueous solution of (NH4)2SO4 was tested using a Chenhua CHI-660E electrochemical workstation. Charge-discharge tests were performed within the 0–1.2 V voltage range, and the results are as follows: Figures 3-4 As shown. From Figures 3-4 It can be seen that the aqueous ammonium ion / proton hybrid battery prepared using the polyaniline-coated manganese dioxide electrode of the aqueous ammonium ion / proton hybrid battery obtained in Example 6 achieves a performance of 0.2 A·g -1 0.5A·g -1 1A·g -1 2A·g -1 ,4A·g -1 The specific capacity at current density is 145 mAh·g -1 114mAh·g -1 90mAh·g -1 72mAh·g -1 and 56mAh·g -1 ; The aqueous ammonium ion / proton hybrid battery prepared using the polypyrrole-coated manganese dioxide electrode obtained in Example 6, at 0.1 A·g -1The discharge specific capacity at current density is 174 mAh·g -1 .

[0035] The above are all preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A composite material for an aqueous ammonium ion / proton hybrid battery, characterized in that, The composite material used in the aqueous ammonium ion / proton hybrid battery is a conductive polymer-coated manganese dioxide composite material.

2. A method for preparing a composite material for an aqueous ammonium ion / proton hybrid battery, characterized in that, Includes the following steps: S1. Dissolve the manganese source in deionized water to obtain solution A; S2. Disperse the small organic monomer in an organic solvent to obtain solution B; S3. Mix solution A and solution B, let stand at 3~6℃, separate solid and liquid, wash the solid filter material to obtain the precursor; S4. The precursor is dried at -50~-60℃ to obtain a composite material for aqueous ammonium ion / proton hybrid batteries.

3. The method for preparing the composite material for an aqueous ammonium ion / proton hybrid battery as described in claim 2, characterized in that, In S1, the mass-to-volume ratio of the manganese source to deionized water is 0.1g:100mL to 0.15g:100mL; In S2, the volume ratio of the organic small molecule monomer to the organic solvent is 1:100 to 5:

100.

4. The method for preparing the composite material for an aqueous ammonium ion / proton hybrid battery as described in claim 3, characterized in that, In S3, the volume ratio of solution A to solution B is 1:1 to 1:1.

1.

5. The method for preparing the composite material for an aqueous ammonium ion / proton hybrid battery as described in claim 2, characterized in that, In S1, the manganese source is potassium permanganate.

6. The method for preparing the composite material for an aqueous ammonium ion / proton hybrid battery as described in claim 2, characterized in that, In S2, the organic small molecule monomer is any one of aniline monomer, pyrrole monomer or thiophene monomer; In S2, the organic solvent is carbon tetrachloride.

7. The method for preparing the composite material for an aqueous ammonium ion / proton hybrid battery as described in claim 2, characterized in that, In S3, the settling time is 22~50h.

8. The method for preparing the composite material for an aqueous ammonium ion / proton hybrid battery as described in claim 2, characterized in that, In S4, the heat preservation time for the drying process is 45~50h.

9. An aqueous ammonium ion / proton hybrid electrode, characterized in that, The composite material for aqueous ammonium ion / proton hybrid batteries as described in claim 1.

10. The application of the aqueous ammonium ion / proton hybrid electrode as described in claim 9 in the preparation of an aqueous ammonium ion / proton hybrid ion battery.

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