Hydrogen solid-state secondary battery with manganese-based positive electrode
By using MnO2 positive electrode and Pt/C negative electrode in hydrogen batteries, combining acidic electrolytes and clay solid electrolytes, the problem of low specific capacity of the existing hydrogen battery positive electrode materials is solved, and high specific capacity and excellent battery performance are achieved.
Patent Information
- Application Number
- CN202411380118.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2025-01-03
AI Technical Summary
The positive electrode material of existing hydrogen batteries is lower in specific capacity, limiting the large-scale application of batteries.
The MnO2 positive electrode, Pt/C negative electrode and solid electrolyte, including acid electrolyte and clay, is prepared by reaction of potassium permanganate, manganese source and water, and its specific capacity is increased through specific proportion and temperature control.
The MnO2 positive electrode with high specific capacity is realized, which improves the cycle stability, rate performance and low temperature performance of the battery. At the same time, the preparation method is simple, the energy consumption is low, the cost is low, and it is easy to industrialize.
Smart Images
Figure CN119253000A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of battery energy storage, and in particular to a hydrogen solid-state secondary battery with a manganese-based positive electrode. Background Art
[0002] Aqueous secondary batteries use water-based electrolytes and have the characteristics of high safety, high power density and environmental friendliness, making them one of the most promising energy storage technologies. However, existing aqueous battery technologies, such as lead-acid, nickel-hydrogen and flow batteries, still face challenges in terms of environment, resources, cycle life and other issues. Therefore, it is imperative to explore environmentally friendly, low-cost, highly safe and long-cycle-life aqueous secondary batteries.
[0003] Since 2018, Wei Chen et al. have reported a series of new aqueous secondary batteries - hydrogen batteries. + As a carrier (with the smallest ion radius), it has the fastest conduction rate in the electrolyte, which makes the battery have excellent rate performance. The hydrogen negative electrode can match different positive electrodes, such as the hydrogen negative electrode can match the embedded / extracted positive electrode. In the prior art, nickel-hydrogen (Ni-H2) batteries, Prussian blue (PBA)-H2 batteries and lithium manganese oxide hydrogen (LMO-H2) batteries have been developed in alkaline, acidic and neutral electrolytes, respectively. Among them, the positive electrode nickel hydroxide of the Ni-H2 battery has a low abundance in the earth's crust, and the positive electrode material PBA in the PBA-H2 battery and the lithium manganese oxide in the LMO-H2 battery have low specific capacity, which limits the large-scale application of the above batteries.
[0004] In summary, it is of great significance and value to find a positive electrode material that can deintercalate and deintercalate protons and has a high specific capacity to construct a hydrogen solid-state secondary battery. Summary of the invention
[0005] In view of this, the present invention provides a hydrogen solid-state secondary battery with a manganese-based positive electrode to solve the problem of low specific capacity of existing positive electrode materials.
[0006] In order to achieve the above object, the present invention adopts the following technical solution:
[0007] The present invention provides a hydrogen solid-state secondary battery with a manganese-based positive electrode, comprising a MnO2 positive electrode, a Pt / C negative electrode and a solid electrolyte; the solid electrolyte comprises an acidic electrolyte and clay.
[0008] Preferably, the method for preparing the MnO2 positive electrode comprises the following steps: mixing potassium permanganate, a manganese source and water, and reacting to obtain a MnO2 positive electrode.
[0009] Preferably, the mass volume ratio of the potassium permanganate, the manganese source and the water is 200-300 mg: 100-200 mg: 50-170 mL.
[0010] Preferably, the manganese source includes one or more of MnSO4, MnNO3, MnCl2, Mn2O3 and MnCO3.
[0011] Preferably, the reaction temperature is 100-150° C., and the reaction time is 10-15 hours.
[0012] Preferably, the mass ratio of the acidic electrolyte to the clay in the solid electrolyte is 0.5-1.5:1-5.
[0013] Preferably, the acidic electrolyte includes H3PO4 and / or H2SO4; the clay includes one or more of Mg2H2(SiO3)3·3.0H2O, H2Al2O6Si·1.19H2O and H4Al2O9Si2·0.32H2O.
[0014] Preferably, the volume concentration of the acidic electrolyte is 10% to 85%.
[0015] Preferably, the Pt in the Pt / C negative electrode accounts for 15% to 50% of the total mass of the Pt / C negative electrode.
[0016] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:
[0017] The present invention discloses a MnO2 positive electrode capable of reversibly deintercalating protons, the positive electrode having a high specific capacity, which is beneficial to improving the specific capacity of a battery, wherein the specific capacity of a battery prepared using the MnO2 positive electrode of the present invention can be as high as 334.51 mAh / g. At the same time, by applying the MnO2 positive electrode to a new hydrogen solid-state secondary battery system, the battery has excellent cycle stability, rate performance and low-temperature performance. In addition, the preparation method of the MnO2 positive electrode of the present invention is simple, consumes less energy, has low cost, is not limited by resources, is green and environmentally friendly, and is easy to realize industrialization. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.
[0019] Figure 1 A schematic diagram showing the charging and discharging process of the hydrogen solid-state secondary battery assembled in Example 1;
[0020] Figure 2This is a scanning electron microscope image of the MnO2 positive electrode obtained in Example 1 magnified 20,000 times;
[0021] Figure 3 This is a scanning electron microscope image of the MnO2 positive electrode obtained in Example 1 magnified 30,000 times;
[0022] Figure 4 This is a scanning electron microscope image of the MnO2 positive electrode obtained in Example 1 magnified 100,000 times;
[0023] Figure 5 The X-ray element spectrum of the MnO2 positive electrode obtained in Example 1 (the horizontal coordinate is the angle / °, and the vertical coordinate is the intensity / au);
[0024] Figure 6 The charge and discharge curve of the hydrogen solid-state secondary battery assembled in Example 2 at a current density of 10 mA (the horizontal axis is the specific capacity / mAh·g -1 , the ordinate is voltage / V);
[0025] Figure 7 is the X-ray diffraction pattern of the solid electrolyte in Example 3 (the abscissa is angle / °, the ordinate is intensity / au);
[0026] Figure 8 The charge and discharge curve of the hydrogen solid-state secondary battery assembled in Example 4 at a current density of 10 mA (the horizontal axis is the specific capacity / mAh·g -1 , the vertical axis is voltage / V). DETAILED DESCRIPTION
[0027] The present invention provides a hydrogen solid-state secondary battery with a manganese-based positive electrode, comprising a MnO2 positive electrode, a Pt / C negative electrode and a solid electrolyte; the solid electrolyte comprises an acidic electrolyte and clay.
[0028] In the present invention, the method for preparing the MnO2 positive electrode comprises the following steps: mixing potassium permanganate, a manganese source and water, and reacting to obtain the MnO2 positive electrode.
[0029] In the present invention, the method for preparing the MnO2 positive electrode preferably includes the following steps: firstly mixing potassium permanganate with part of water, then mixing a manganese source with the remaining part of water, and finally mixing the two mixed solutions and reacting them to obtain a MnO2 positive electrode.
[0030] In the present invention, the mass volume ratio of the potassium permanganate, the manganese source and the water is 200-300 mg: 100-200 mg: 50-170 mL, preferably 220-280 mg: 120-180 mg: 60-150 mL, further preferably 235-270 mg: 130-165 mg: 70-120 mL, and more preferably 250-260 mg: 150-160 mg: 80-100 mL.
[0031] In the present invention, the manganese source includes one or more of MnSO4, MnNO3, MnCl2, Mn2O3 and MnCO3.
[0032] In the present invention, the reaction temperature is 100-150°C, preferably 105-140°C, further preferably 110-135°C, more preferably 115-120°C; the reaction time is 10-15h, preferably 11-14h, more preferably 12h.
[0033] In the present invention, after obtaining the MnO2 positive electrode, the steps of washing the MnO2 positive electrode with water, washing with alcohol, centrifuging, filtering and drying the MnO2 positive electrode are also included, and the MnO2 positive electrode can reversibly embed and release protons.
[0034] In the present invention, the mass ratio of the acidic electrolyte to the clay in the solid electrolyte is 0.5-1.5:1-5, preferably 0.8-1.3:1.5-4.5, more preferably 1-1.25:2-4, and more preferably 1.1-1.2:2.5-3.5.
[0035] In the present invention, the acidic electrolyte includes H3PO4 and / or H2SO4; the clay includes one or more of Mg2H2(SiO3)3·3.0H2O, H2Al2O6Si·1.19H2O and H4Al2O9Si2·0.32H2O.
[0036] In the present invention, the volume concentration of the acidic electrolyte is 10% to 85%, preferably 20% to 70%, more preferably 35% to 55%, and even more preferably 45%.
[0037] In the present invention, the Pt in the Pt / C negative electrode accounts for 15% to 50% of the total mass of the Pt / C negative electrode, preferably 20% to 45%, more preferably 30% to 40%, and more preferably 32%.
[0038] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0039] Example 1
[0040] First, prepare the MnO2 positive electrode. Add 253.5 mg potassium permanganate (KMnO4) into 90 mL of deionized water and stir. Then add 158 mg MnSO4 into the remaining 75 mL of deionized water to form a colorless transparent solution. Then, mix the two mixed solutions under continuous stirring to obtain a dark purple precursor solution. Finally, pour the dark purple precursor solution into a Teflon-lined hydrothermal reactor and transfer it to an oven. Heat the reaction at 120°C for 12 hours. After water washing, alcohol washing, centrifugation, filtration, and drying, the MnO2 positive electrode is obtained.
[0041] Then, the positive electrode sheet, the Pt / C negative electrode sheet and the solid electrolyte membrane are prepared.
[0042] The preparation method of the positive electrode sheet is as follows: the positive electrode active material MnO2, the conductive agent acetylene black and the binder PTFE are rolled into a film in a ratio of 7:2:1 to form an electrode, wherein the current collector is a titanium mesh and the active material loading is 5 mg cm -2 , the diameter of the positive electrode is 19mm.
[0043] The preparation method of the Pt / C negative electrode sheet is as follows: Pt / C negative electrode catalyst powder and binder PTFE are rolled into a film in a ratio of 8:2 to form an electrode, wherein the current collector is a titanium mesh and the Pt loading is 1 mg cm -2 The diameter of the Pt / C negative electrode piece is 19 mm; Pt in the Pt / C negative electrode accounts for 40% of the total mass of the Pt / C negative electrode.
[0044] The preparation method of the solid electrolyte membrane is as follows: bentonite H2Al2O6Si·1.19H2O and acidic electrolyte H3PO4 are mixed in a mass ratio of 1:1 to prepare a gel-packed solid electrolyte membrane, wherein the concentration of the acidic electrolyte H3PO4 is 63%.
[0045] Finally, assemble the battery. The assembly order of the battery is: positive electrode plate, solid electrolyte membrane and Pt / C negative electrode plate.
[0046] The charging and discharging process principle of the hydrogen solid-state secondary battery with manganese-based positive electrode assembled in Example 1 is as follows Figure 1 As shown, during the first charge process, the positive electrode material MnO2 is embedded in H + , converted into MnOOH, the protons in the solid electrolyte membrane react to generate hydrogen under the catalysis of the negative electrode catalyst Pt; during the discharge process, the hydrogen reacts on the negative electrode catalyst Pt to generate protons that are transferred to the solid electrolyte, and are conducted through the Grotthuss mechanism to be released to the positive electrode material MnOOH to generate MnO2. In the second and subsequent charge and discharge processes, the positive electrode is the embedding of protons in MnO2 (discharge process) and the release of protons in MnOOH (charge process), and the negative electrode is the oxidation and reduction reaction of protons.
[0047] After testing, the scanning electron microscope image of the MnO2 positive electrode in this embodiment 1 is as follows Figures 2 to 4 As shown, from Figures 2 to 4 It can be seen that the MnO2 positive electrode presents a block morphology with a width of 1.5 to 2.5 μm, which is conducive to improving the mechanical properties and stability of the material, so that the material has a longer life and better stability during use, and can maintain a good structure in the proton insertion and extraction reaction, and the structure is not easy to collapse, providing better electrochemical performance. That is, the MnO2 positive electrode material prepared in Example 1 presents a block morphology, which is conducive to improving the specific capacity of the material, thereby making the battery have a higher specific capacity; the X-ray element energy spectrum is as follows Figure 5 As shown, from Figure 5 It can be seen that pure phase manganese dioxide was successfully synthesized in this Example 1.
[0048] The chemical reaction of the hydrogen solid-state secondary battery with manganese-based positive electrode assembled in this embodiment is as follows:
[0049] Positive electrode: MnO2+H + +e - =MnOOH
[0050] Negative electrode: H2-2e - =H +
[0051] Overall reaction: 2MnO2+H2=2MnOOH
[0052] Example 2
[0053] The MnO2 positive electrode prepared in Example 1 is used, and the preparation process of the positive electrode plate, the Pt / C negative electrode plate and the solid electrolyte membrane and the battery assembly process are the same as those in Example 1 to assemble a hydrogen solid-state secondary battery with a manganese-based positive electrode. The difference between Example 2 and Example 1 is that the solid electrolyte is H2SO4 and sepiolite Mg2H2(SiO3)3·3.0H2O in a mass ratio of 1:1; the volume concentration of the acidic electrolyte H2SO4 is 63%; and Pt in the Pt / C negative electrode accounts for 40% of the total mass of the Pt / C negative electrode.
[0054] After testing, the charge and discharge curve of the hydrogen solid-state secondary battery with a manganese-based positive electrode assembled in Example 2 at a current density of 10 mA is as follows: Figure 6 As shown, from Figure 6 It can be seen that the charge and discharge voltage range is between 1.0 and 1.8 V, and the specific capacity is 334.34 mAh / g.
[0055] Example 3
[0056] The MnO2 positive electrode prepared in Example 1 is used, and the preparation process of the positive electrode plate, the Pt / C negative electrode plate and the solid electrolyte membrane and the battery assembly process are the same as those in Example 1 to assemble a hydrogen solid secondary battery with a manganese-based positive electrode. The difference between Example 3 and Example 1 is that the solid electrolyte is H3PO4 and sepiolite Mg2H2(SiO3)3·3.0H2O in a mass ratio of 1:1; the volume concentration of the acidic electrolyte H3PO4 is 63%; and Pt in the Pt / C negative electrode accounts for 40% of the total mass of the Pt / C negative electrode.
[0057] After testing, the X-ray diffraction pattern of the solid electrolyte in the hydrogen solid secondary battery with manganese-based positive electrode assembled in Example 3 is as follows: Figure 7 As shown, from Figure 7 It can be confirmed that the solid electrolyte in this embodiment is composed of sepiolite Mg2H2(SiO3)3·3.0H2O and H3PO4.
[0058] Example 4
[0059] First, prepare the MnO2 positive electrode. Add 253.5 mg potassium permanganate (KMnO4) into 90 mL of deionized water and stir. Then add 187 mg MnNO3 into the remaining 75 mL of deionized water to form a colorless transparent solution. Then, mix the two mixed solutions under continuous stirring to obtain a dark purple precursor solution. Finally, pour the dark purple precursor solution into a Teflon-lined hydrothermal reactor and transfer it to an oven. Heat the reaction at 120°C for 10 hours. After water washing, alcohol washing, centrifugation, filtration, and drying, the MnO2 positive electrode is obtained.
[0060] Then, the same preparation process of the positive electrode sheet, the Pt / C negative electrode sheet and the solid electrolyte membrane and the battery assembly process as in Example 1 were used to assemble a hydrogen solid-state secondary battery with a manganese-based positive electrode. Among them, there are the following differences between this Example 4 and Example 1: the solid electrolyte is H2SO4 and bentonite H2Al2O6Si·1.19H2O in a mass ratio of 1:1.5; the volume concentration of the acidic electrolyte H2SO4 is 63%; and Pt in the Pt / C negative electrode accounts for 40% of the total mass of the Pt / C negative electrode.
[0061] After testing, the charge and discharge curve of the hydrogen solid-state secondary battery with a manganese-based positive electrode assembled in Example 4 at a current density of 10 mA is as follows: Figure 8 As shown, from Figure 8 It can be seen that the charge and discharge voltage range is between 1.0 and 1.8 V, and the specific capacity is 334.23 mAh / g.
[0062] Example 5
[0063] First, prepare the MnO2 positive electrode. Add 253.5 mg potassium permanganate (KMnO4) into 90 mL of deionized water and stir. Then add 132 mg MnCl2 into the remaining 75 mL of deionized water to form a colorless transparent solution. Then, mix the two mixed solutions under continuous stirring to obtain a dark purple precursor solution. Finally, pour the dark purple precursor solution into a Teflon-lined hydrothermal reactor and transfer it to an oven. Heat the reaction at 120°C for 10 hours. After water washing, alcohol washing, centrifugation, filtration, and drying, the MnO2 positive electrode is obtained.
[0064] Then, the same preparation process of the positive electrode sheet, the Pt / C negative electrode sheet and the solid electrolyte membrane and the battery assembly process as in Example 1 were used to assemble a hydrogen solid secondary battery with a manganese-based positive electrode. Among them, there are the following differences between this Example 5 and Example 1: the solid electrolyte is H2SO4 and bentonite H4Al2O9Si2·0.32H2O in a mass ratio of 1:2; the volume concentration of the acidic electrolyte H2SO4 is 63%; and Pt in the Pt / C negative electrode accounts for 40% of the total mass of the Pt / C negative electrode.
[0065] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A hydrogen solid-state secondary battery with a manganese-based positive electrode, characterized in that: The hydrogen solid-state secondary battery with a manganese-based positive electrode comprises a MnO2 positive electrode, a Pt / C negative electrode and a solid electrolyte; The solid electrolyte includes an acidic electrolyte and clay.
2. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that: The preparation method of the MnO2 positive electrode comprises the following steps: Potassium permanganate, a manganese source and water are mixed and reacted to obtain a MnO2 positive electrode.
3. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 2, characterized in that: The mass volume ratio of the potassium permanganate, the manganese source and the water is 200-300 mg: 100-200 mg: 50-170 mL.
4. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 3, characterized in that: The manganese source includes one or more of MnSO4, MnNO3, MnCl2, Mn2O3 and MnCO3.
5. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 4, characterized in that: The reaction temperature is 100-150° C., and the reaction time is 10-15 hours.
6. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to any one of claims 1 to 5, characterized in that: The mass ratio of the acidic electrolyte to the clay in the solid electrolyte is 0.5-1.5:1-5.
7. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 6, characterized in that: The acidic electrolyte includes H3PO4 and / or H2SO4; The clay includes one or more of Mg2H2(SiO3)3·3.0H2O, H2Al2O6Si·1.19H2O and H4Al2O9Si2·0.32H2O.
8. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 7, characterized in that: The volume concentration of the acid electrolyte is 10% to 85%.
9. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 8, characterized in that: The Pt in the Pt / C negative electrode accounts for 15% to 50% of the total mass of the Pt / C negative electrode.