A novel positive electrode material for proton battery and a preparation method thereof

Abstract

The application discloses a novel proton battery positive electrode material and a preparation method thereof. Iron source solution and phosphorus source solution are respectively prepared through an organic solution, and then the two solutions are mixed to perform a solvothermal reaction. After that, the product obtained in the reaction is washed and dried to obtain the novel proton battery positive electrode material. The material can be used to prepare a proton battery positive electrode sheet. The novel proton battery positive electrode material prepared by the application is a nanoparticle, the main component of which is iron phosphate. The particle morphology is uniform, and the specific surface area is large. The size of the particle is 50.0-200.0 nm. The proton battery prepared by using the novel proton battery positive electrode material has good electrochemical performance. The preparation method provided by the application is simple in process, raw materials are easy to obtain, and is suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention relates to a novel proton battery cathode material and its preparation method, belonging to the field of proton battery technology. Background Technology

[0002] With the rapid evolution of new electrochemical energy sources, battery energy storage technology has shown broad development prospects among existing electrochemical energy storage technologies. Compared to traditional rechargeable batteries, proton batteries represent a completely new battery system that can effectively meet the requirements of high energy density, excellent rate performance, superior low-temperature performance, abundant raw materials, low safety risks, low pollution, and easy recycling. It will be one of the important development directions for next-generation battery technology and has broad application prospects. Currently, research on proton battery cathode materials is still in the exploratory stage, and there is an urgent need for cathode materials with excellent electrochemical performance to lay a solid foundation for the construction of proton battery full-cell systems. Iron phosphate, as an electrode material with excellent electrochemical performance and large-scale production capability, can effectively store protons; therefore, we propose for the first time the application of iron phosphate electrode materials in proton battery systems. Using iron phosphate as the cathode material for proton batteries, combined with a low-concentration acidic electrolyte, a proton battery system with excellent electrochemical performance can be constructed. This will promote the development and application of environmentally friendly energy storage technologies, effectively solve the problems faced by traditional battery technologies, provide a research platform for the further development of proton batteries, and help the future market application of proton batteries. Summary of the Invention

[0003] This invention provides a novel proton battery cathode material with excellent electrochemical performance. Furthermore, the proton battery cathode electrode sheet prepared using this cathode material can enable the proton battery to operate stably and achieve good electrochemical performance without the need for high-concentration acid.

[0004] The technical solution adopted in this invention is as follows:

[0005] A method for preparing a novel proton battery cathode material includes the following steps:

[0006] (1) Take an organic solvent and water to prepare an iron source solution and a phosphorus source solution respectively with inorganic iron salt and phosphorus-containing inorganic acid. Then mix the iron source solution and phosphorus source solution and stir to form a precursor solution.

[0007] (2) The precursor solution obtained in step (1) is subjected to a solvothermal reaction at a temperature of 160-200℃ for 20-24h. The resulting product is then centrifuged, washed and dried to obtain a novel proton battery cathode material.

[0008] According to the above scheme, the organic solvent is selected from one or more of ethanol, ethylene glycol, propylene glycol and isopropanol.

[0009] According to the above scheme, the volume ratio of organic solvent to water in the precursor solution is (95-99):(1-5).

[0010] According to the above scheme, the molar concentration of inorganic iron salt in the precursor solution is 0.05-0.1 mol / L; the dispersion concentration of phosphorus-containing inorganic acid in the precursor solution is 0.025-0.1 g / mL.

[0011] According to the above scheme, the inorganic iron salt is selected from one or more of Fe2(SO4)3, FeSO4, FeCl3, FeCl2, Fe(NO3)3 and their hydrates.

[0012] According to the above scheme, the phosphorus-containing inorganic acid is H3PO4 and / or H4P2O7.

[0013] According to the above scheme, the novel proton battery cathode material is a nanoparticle, the main component of which is iron phosphate, and the particle has a uniform morphology; wherein the size of the nanoparticle is 50.0-200.0 nm.

[0014] The application method of the novel proton battery cathode material prepared according to the above scheme is as follows: the novel proton battery cathode material is mixed and ground with conductive additives and binders to form an electrode slurry, and then coated onto an electrode sheet with a coating tool. After drying, the novel proton battery electrode sheet is obtained; wherein the mass ratio of the novel proton battery cathode material, conductive agent and binder is (50-70):(30-20):(20-10); the conductive additive is selected from one of acetylene black, Ketjen black and graphite, and the binder is polytetrafluoroethylene.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0016] (1) The novel proton battery cathode material prepared by the preparation method provided by the present invention is a nanoparticle with uniform morphology and a size of 50.0-200.0 nm. Furthermore, the proton battery cathode electrode sheet prepared with this material can make the proton battery work stably without the need for high concentration of acid and has good electrochemical performance.

[0017] (2) The raw materials provided by the present invention are readily available, the production process is simple, and it is green and environmentally friendly, and it is expected to be industrialized on a large scale. Attached Figure Description

[0018] Figure 1 The image shows the transmission electron microscope (TEM) spectrum of the novel proton battery cathode material prepared in Example 1 at 1.0 μm.

[0019] Figure 2 The image shows the transmission electron microscope (TEM) pattern of the novel proton battery cathode material prepared in Example 1 at 200.0 nm.

[0020] Figure 3 The image shows the X-ray diffraction pattern of the novel proton battery cathode material prepared in Example 1.

[0021] Figure 4 Cyclic voltammetry curves of a proton battery positive electrode sheet prepared with the novel proton battery positive electrode material prepared in Example 1 and combined with a graphite negative electrode under a three-electrode system test. Detailed Implementation

[0022] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the present invention is not limited to the following embodiments.

[0023] All reagents and raw materials used in this invention were purchased from Aladdin Company; the purity of all solvents used in this invention is ≥99.9%; unless otherwise specified, all chemical reagents used in the embodiments of this invention were obtained through conventional commercial channels.

[0024] Example 1

[0025] A method for preparing a novel proton battery cathode material includes the following steps:

[0026] (1) Add 5.0 mmol of ferrous sulfate and 2.5 g of phosphoric acid to 50.0 mL of 99% ethanol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0027] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 180°C for 24 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0028] Preparation of novel proton cell electrode sheets:

[0029] Take 0.7g of the novel proton battery positive electrode material obtained in step (2), 0.2g of conductive additive acetylene black and 0.1g of binder polytetrafluoroethylene (PVDF), grind and mix them in 1.0mL of N-methylpyrrolidone (NMP) to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0030] The novel proton battery cathode material prepared in Example 1 was subjected to transmission electron microscopy (TEM) testing, and the results are as follows: Figure 1-2 As shown in the figure, the size of the novel proton battery cathode material nanoparticles is between 50.0 and 200.0 nm.

[0031] X-ray diffraction tests were performed on the novel proton battery cathode material prepared in Example 1, and the results are as follows: Figure 3As shown in the figure, the prepared nanoparticles are mainly iron phosphate.

[0032] Cyclic voltammetry tests were conducted on the proton battery positive electrode sheet prepared with the novel proton battery positive electrode material prepared in Example 1, combined with a graphite negative electrode, in a three-electrode system. The results are as follows: Figure 4 As shown. From Figure 4 As can be seen from the data, using the mercury porosimetry electrode as the reference electrode, the electrode material exhibits symmetrical redox peaks around 0.0V, and the electrochemical reaction that occurs has good reversibility and a large specific capacity, indicating that the novel proton battery cathode material prepared in this embodiment has good electrochemical performance.

[0033] Example 2

[0034] A method for preparing a novel proton battery cathode material includes the following steps:

[0035] (1) Add 5.0 mmol of ferric sulfate and 2.5 g of phosphoric acid to 50.0 mL of 99% ethylene glycol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0036] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 170°C for 20 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0037] Preparation of novel proton cell electrode sheets:

[0038] Take 0.6g of the novel proton battery positive electrode material obtained in step (2), 0.3g of conductive additive acetylene black and 0.2g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0039] Example 3

[0040] A method for preparing a novel proton battery cathode material includes the following steps:

[0041] (1) Add 5.0 mmol of ferric chloride and 2.5 g of pyrophosphate to 50.0 mL of 99% isopropanol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0042] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 200°C for 22 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0043] Preparation of novel proton cell electrode sheets:

[0044] Take 0.6g of the novel proton battery positive electrode material obtained in step (2), 0.3g of conductive additive acetylene black and 0.2g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0045] Example 4

[0046] A method for preparing a novel proton battery cathode material includes the following steps:

[0047] (1) Add 5.0 mmol of ferric nitrate and 2.5 g of phosphoric acid to 50.0 mL of 99% propylene glycol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0048] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 180°C for 24 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0049] Preparation of novel proton cell electrode sheets:

[0050] Take 0.7g of the novel proton battery positive electrode material obtained in step (2), 0.2g of conductive additive acetylene black and 0.1g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0051] Example 5

[0052] A method for preparing a novel proton battery cathode material includes the following steps:

[0053] (1) Add 5.0 mmol of ferrous chloride and 2.5 g of pyrophosphate to 50.0 mL of 99% isopropanol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0054] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 160°C for 24 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0055] Preparation of novel proton cell electrode sheets:

[0056] Take 0.7g of the novel proton battery positive electrode material obtained in step (2), 0.2g of conductive additive acetylene black and 0.1g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0057] Example 6

[0058] A method for preparing a novel proton battery cathode material includes the following steps:

[0059] (1) Add 5.0 mmol of ferric sulfate and 2.5 g of pyrophosphate to 50.0 mL of 99% ethanol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0060] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 180°C for 20 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0061] Preparation of novel proton cell electrode sheets:

[0062] Take 0.7g of the novel proton battery positive electrode material obtained in step (2), 0.2g of conductive additive acetylene black and 0.1g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0063] Example 7

[0064] A method for preparing a novel proton battery cathode material includes the following steps:

[0065] (1) Add 5.0 mmol of ferrous chloride and 2.5 g of phosphoric acid to 50.0 mL of 99% ethylene glycol aqueous solution, stir thoroughly and mix evenly to obtain the precursor solution.

[0066] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 200°C for 20 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0067] Preparation of novel proton cell electrode sheets:

[0068] Take 0.6g of the novel proton battery positive electrode material obtained in step (2), 0.3g of conductive additive acetylene black and 0.2g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0069] Example 8

[0070] A method for preparing a novel proton battery cathode material includes the following steps:

[0071] (1) Add 5.0 mmol of ferrous sulfate and 2.5 g of pyrophosphate to 50.0 mL of 99% isopropanol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0072] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 180°C for 24 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0073] Preparation of novel proton cell electrode sheets:

[0074] Take 0.7g of the novel proton battery positive electrode material obtained in step (2), 0.2g of conductive additive acetylene black and 0.1g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0075] Example 9

[0076] A method for preparing a novel proton battery cathode material includes the following steps:

[0077] (1) Add 5.0 mmol of ferrous sulfate and 2.5 g of phosphoric acid to 50.0 mL of 99% propylene glycol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0078] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 200°C for 24 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0079] Preparation of novel proton cell electrode sheets:

[0080] Take 0.6g of the novel proton battery positive electrode material obtained in step (2), 0.3g of conductive additive acetylene black and 0.2g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0081] Example 10

[0082] A method for preparing a novel proton battery cathode material includes the following steps:

[0083] (1) Add 5.0 mmol of ferric nitrate and 2.5 g of pyrophosphate to 50.0 mL of 99% ethanol aqueous solution, stir thoroughly and mix them evenly to obtain the precursor solution.

[0084] (2) The precursor solution obtained in step (1) is transferred to a reaction vessel and reacted at 180°C for 22 hours. After natural cooling, it is washed three times by centrifugation with deionized water and dried in an oven at 80°C for 2 hours to obtain a novel proton battery cathode material.

[0085] Preparation of novel proton cell electrode sheets:

[0086] Take 0.7g of the novel proton battery positive electrode material obtained in step (2), 0.2g of conductive additive acetylene black and 0.1g of binder polytetrafluoroethylene, grind and mix them in 1.0mL of N-methylpyrrolidone to form a slurry, coat it on titanium foil with a coating tool with a thickness of 150.0μm, and dry it in an oven at 80℃ for 2h to obtain the proton battery positive electrode sheet.

[0087] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A proton battery, comprising a positive electrode material and an acidic electrolyte, characterized in that, The method for preparing the cathode material includes the following steps: (1) Take an organic solvent and water to prepare an iron source solution and a phosphorus source solution respectively with inorganic iron salt and phosphorus-containing inorganic acid, and then mix the iron source solution and phosphorus source solution and stir to form a precursor solution; (2) The precursor solution obtained in step (1) is subjected to a solvothermal reaction at a temperature of 160-200℃ for 20-24h. The resulting product is then centrifuged, washed and dried to obtain the cathode material. The volume ratio of organic solvent to water in the precursor solution is (95-99):(1-5); the molar concentration of inorganic iron salt in the precursor solution is 0.05-0.1 mol / L; and the dispersion concentration of phosphorus-containing inorganic acid in the precursor solution is 0.025-0.1 g / mL. The cathode material is nanoparticles, the main component of which is iron phosphate, and the size of the nanoparticles is 50.0-200.0 nm.

2. A proton battery according to claim 1, characterized in that, The organic solvent is selected from one or more of ethanol, ethylene glycol, propylene glycol, and isopropanol.

3. A proton battery according to claim 1, characterized in that, The inorganic iron salt is selected from one or more of Fe2(SO4)3, FeSO4, FeCl3, FeCl2, Fe(NO3)3 and their hydrates.

4. A proton battery according to claim 1, characterized in that, The phosphorus-containing inorganic acid is H3PO4 and / or H4P2O7.

5. A proton battery according to claim 1, characterized in that, The positive electrode material is mixed with conductive additives and binders and ground into an electrode slurry. The slurry is then coated onto the electrode sheet using a coating tool and dried to obtain the proton battery electrode sheet. The mass ratio of the positive electrode material, conductive additives and binders is (50-70):(30-20):(20-10).

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