A quasi-solid-state double-layer ionic thermal redox battery with high open-circuit voltage

Abstract

The application discloses a quasi-solid-state double-layer ionic thermal redox battery with high open-circuit voltage, comprising a structure design and a preparation method, and relates to the technical field of thermoelectric materials. In order to solve the problem that the current thermal redox battery is limited by low thermal power and causes limited voltage improvement, the application provides a new structure which can improve the open-circuit voltage of the thermal redox battery. The structure of the quasi-solid-state double-layer ionic thermal redox battery comprises gel one, gel two, a cold side electrode and a hot side electrode. Experimental verification shows that the constructed quasi-solid-state double-layer ionic thermal redox battery not only has stable and high open-circuit voltage, but also has further improved voltage when a temperature difference is applied. In addition, the material components required by the structure are simple, the configuration mode is easy, the preparation process has mild reaction conditions, the steps are simple, the process is green and environment-friendly, and the structure has universal applicability. The application provides a new way for preparing p-type and n-type ionic thermoelectric materials with high thermoelectric power.

Description

Technical Field

[0001] This invention relates to the field of thermoelectric materials technology, specifically to a quasi-solid-state bilayer ion thermal redox battery with high open-circuit voltage. Background Technology

[0002] Waste heat plays a crucial role in the energy industry. Waste heat resources are widely found in industries such as steel, chemicals, light industry, and food production, representing usable thermal energy released during production processes. In the industrial sector's utilization of fossil fuels, only 40% of the energy is effectively utilized, with the remaining 60% ultimately converted into waste heat. Improving energy efficiency and reducing carbon dioxide emissions are core pathways to achieving the "dual carbon" goal. Therefore, it is necessary to develop new technologies to effectively utilize available thermal energy resources for power generation. Electronic thermoelectric materials, utilizing narrow-bandgap semiconductors based on the Seebeck effect, play a vital role in converting thermal energy into useful electrical energy. However, the thermal power (S) of traditional electronic thermoelectric materials is low, only tens of microvolts per Kelvin (μV K). 1) This makes generating sufficient voltage in practical applications extremely difficult. In contrast, ion thermoelectric materials exhibit a huge Seebeck coefficient, reaching several millivolts per Kelvin (mV K). 1) Ion thermoelectric materials based on the Soret effect have a huge Seebeck coefficient, but they have the defect of not being able to generate a continuous current under a constant temperature difference (ΔT), and therefore cannot work continuously for a long time.

[0003] Thermal redox batteries (TGCs) based on the thermal redox effect are another type of ion thermoelectric material. By applying a temperature difference, the redox couples within the material (such as the p-type redox couple ferrocyanide / ferrocyanide [Fe(CN)64– / Fe(CN)63–]) can undergo oxidation or reduction reactions at the hot and cold electrodes, respectively (determined by the p / n type of the redox couple), thereby continuously generating current. Studies have shown that increasing the concentration difference of redox couple ions on the hot and cold sides can enhance the thermal power of thermal redox batteries. However, the above research is based on liquid systems, which pose a risk of leakage in practical applications, and the voltage increase is limited, far lower than that of thermally diffused systems.

[0004] Therefore, in view of the problems and shortcomings encountered by current thermoelectric materials, especially thermal redox batteries, in practical applications, improving the open-circuit voltage of thermal redox batteries to enhance their overall performance is of great practical significance. Summary of the Invention

[0005] The purpose of this invention is to provide a quasi-solid-state bilayer ion thermal redox battery with a high open-circuit voltage to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a quasi-solid-state bilayer ion thermal redox battery with high open-circuit voltage, comprising a quasi-solid-state bilayer ion thermal redox battery, wherein the quasi-solid-state bilayer ion thermal redox battery includes, from top to bottom, a hot-side electrode, a gel containing a single oxide ion, a gel containing a single reduction ion, and a cold-side electrode, wherein a high voltage is formed between the hot-side electrode and the cold-side electrode; if the quasi-solid-state bilayer ion thermal redox battery is p-type, then the gel containing a single oxide ion is located on the cold side, and the gel containing a single reduction ion is located on the hot side; if the quasi-solid-state bilayer ion thermal redox battery is n-type, then the gel containing a single oxide ion is located on the hot side, and the gel containing a single reduction ion is located on the cold side; both the cold-side electrode and the hot-side electrode are graphite disc electrodes, and are respectively bonded to the cold-side gel and the hot-side gel;

[0007] The preparation of the quasi-solid-state bilayer ion thermal redox battery includes the following steps:

[0008] Step 1: Select the type and method for preparing quasi-solid-state bilayer ion thermal redox batteries;

[0009] Step 2: Preparation of quasi-solid gels containing a single oxide or reduction ion;

[0010] Step 3: Thermal redox battery assembly and high open-circuit voltage testing.

[0011] Preferably, the quasi-solid-state bilayer ion thermal redox battery in step one includes P-type thermal redox batteries and n-type thermal redox batteries, and the method includes a mixing method or an immersion method.

[0012] Preferably, when the hybrid method is used to prepare the P-type thermal redox battery in step S1, the specific method of step S2 is as follows:

[0013] A1: Select a certain p-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion, respectively.

[0014] A2: Select a gellifiable polymer material, add it to the solution prepared in A1, stir to dissolve, and then pour it into a mold to solidify in a certain environment;

[0015] A3: Demold the gel containing a single oxide ion and a single reduction ion prepared in A2, mechanically attach them to both sides of the bilayer gel to assemble the electrodes, and obtain a p-type quasi-solid-state bilayer ion thermal redox battery.

[0016] Preferably, when the hybrid method is used to prepare the n-type thermal redox battery in step S1, the specific method of step S2 is as follows:

[0017] B1: Select a certain type n-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion respectively.

[0018] B2: Select a gelatable polymer material, add it to the solution prepared in B1, stir to dissolve, and then pour it into a mold to solidify in a certain environment;

[0019] B3: Demold the gel containing a single oxide ion and a single reduction ion prepared in B2, mechanically attach them to both sides of the bilayer gel to assemble the electrodes, and obtain an n-type quasi-solid-state bilayer ion thermal redox battery.

[0020] Preferably, when the immersion method is used to prepare the p-type thermal redox battery in step S1, the specific method of step S2 is as follows:

[0021] C1. Select a gellifiable polymer material, add a solvent, stir and heat to dissolve, and then pour it into a mold to solidify in a certain environment;

[0022] C2. Select a certain p-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion, respectively.

[0023] C3. The blank gel prepared in step 1 is demolded and immersed in electrolyte solutions containing single oxide ions and single reduction ions respectively in step 2; after a period of time, it is taken out and mechanically bonded to both sides of the bilayer gel to assemble the electrode, thus obtaining a p-type quasi-solid-state bilayer ion thermal redox battery.

[0024] Preferably, when the immersion method is used to prepare the p-type thermal redox battery in step S1, the specific method of step S2 is as follows:

[0025] D1. Select a gellifiable polymer material, add a solvent, stir and heat to dissolve, and then pour it into a mold to solidify in a certain environment;

[0026] D2. Select a certain type n-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion, respectively.

[0027] D3. The blank gel prepared in D1 is demolded and immersed in electrolyte solutions containing a single oxide ion and a single reduction ion, respectively, in D2. After a period of time, the two solutions are removed and mechanically bonded to both sides of the bilayer gel to assemble the electrodes, thus obtaining an n-type quasi-solid-state bilayer ion thermal redox battery.

[0028] Preferably, in step B1, the PVA solution is heated to 40-80°C in a water bath and stirred for 1 hour to ensure complete dissolution.

[0029] Preferably, in step B4, the freezing temperature of the polytetrafluoroethylene mold is -5 to -10°C, and it needs to be frozen for 1 hour.

[0030] Preferably, in step C6, the solution water bath temperature is 70-90°C.

[0031] Compared with the prior art, the beneficial effects of the present invention are:

[0032] This invention employs a mixing or soaking method to prepare a gel containing a single oxidation or reduction ion, and then assembles the gel and electrodes to obtain a quasi-solid-state bilayer ion thermal redox battery with a high open-circuit voltage.

[0033] This invention selects typical redox pairs, employs simple gel preparation and processing methods, and combines them with graphite electrodes to construct a quasi-solid-state bilayer ion thermal redox battery with a stable and high open-circuit voltage, which will further increase when the temperature difference is established.

[0034] The materials of this invention are simple in composition, easy to prepare, and the preparation process is mild, simple, and environmentally friendly. It also has universal applicability, providing a new approach for preparing high thermoelectric power p-type and n-type ion thermoelectric materials. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the composition of a quasi-solid-state bilayer ion thermal redox battery with high open-circuit voltage according to the present invention.

[0036] Figure 2 The single cold-side electrode or reduced ion gel prepared in Examples 2-5;

[0037] Figure 3 This is a schematic diagram of the operation of a quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to the present invention.

[0038] Figure 4 This image shows the voltage versus temperature difference between the quasi-solid-state bilayer ion thermal redox battery (DTGB) in Example 1 of the present invention and a conventional single-layer thermal redox battery (TGC).

[0039] Figure 5 Images showing the voltage sustaining time of a quasi-solid-state bilayer ion thermal redox battery (DTGB) and a conventional monolayer thermal redox battery (TGC) in Embodiment 1 of the present invention;

[0040] Figure 6Examples 1-4 of this invention, which describe a quasi-solid-state bilayer ion thermal redox battery with high open-circuit voltage, present high open-circuit voltage data.

[0041] In the picture:

[0042] 1. Gel 1; 2. Gel 2; 3. Cold side electrode; 4. Hot side electrode. Detailed Implementation

[0043] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments 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.

[0044] Example 1

[0045] Reference Figure 1-6 As shown: A quasi-solid-state bilayer ion thermal redox battery with high open-circuit voltage includes a quasi-solid-state bilayer ion thermal redox battery. The bilayer quasi-solid-state thermal redox battery includes, from top to bottom, a hot-side electrode 4, a gel containing a single oxide ion 1, a gel containing a single reduction ion 2, and a cold-side electrode 3. A high voltage is formed between the hot-side electrode 4 and the cold-side electrode 3. If the quasi-solid-state bilayer ion thermal redox battery is p-type, then the gel containing a single oxide ion 1 is located on the cold side, and the gel containing a single reduction ion 2 is located on the hot side. If the quasi-solid-state bilayer ion thermal redox battery is n-type, then the gel containing a single oxide ion 1 is located on the hot side, and the gel containing a single reduction ion 2 is located on the cold side. Both the cold-side electrode 3 and the hot-side electrode 4 are graphite disc electrodes and are respectively bonded to the cold-side gel and the hot-side gel.

[0046] The fabrication of a quasi-solid-state bilayer ion thermal redox battery includes the following steps:

[0047] Step 1: Select the type and method for preparing quasi-solid-state bilayer ion thermal redox batteries;

[0048] Step 2: Preparation of quasi-solid gels containing a single oxide or reduction ion;

[0049] Step 3: Thermal redox battery assembly and high open-circuit voltage testing:

[0050] In step one, the types of quasi-solid-state bilayer ion thermal redox batteries include P-type thermal redox batteries and n-type thermal redox batteries, and the methods include mixing or immersion.

[0051] Example 2

[0052] This embodiment provides a P-type thermal redox battery prepared based on a hybrid method, and the preparation method of the P-type thermal redox battery is as follows:

[0053] A1. Prepare 20 ml of potassium ferricyanide solution and 0.2 mol L⁻¹ potassium ferrocyanide solution respectively, using ethylene glycol and deionized water as solvents, with a mass ratio of 1:5.

[0054] A2. Add 3g of gelatin to each and stir in a water bath at 40℃ for 2 hours. Then, take 1ml of the mixed solution each time and drop it into a polytetrafluoroethylene mold. The mold is a 4*4 array, and the diameter of each unit cylinder is 14mm.

[0055] A3. Add 2-3 drops of 0.5% glutaraldehyde solution to each unit;

[0056] A4. Then place it in a refrigerator and cool at 0-2℃ for 3 hours. After that, remove it from the mold to obtain p-type potassium ferrocyanide and potassium ferrous cyanide gelatin hydrogel. Figure 2 a)

[0057] A5. The demolded potassium ferrocyanide hydrogel and potassium ferricyanide hydrogel are bonded together, with the potassium ferrocyanide hydrogel serving as the hot working end and the potassium ferricyanide hydrogel serving as the cold working end. The two are bonded together to obtain a p-type potassium ferrocyanide and potassium ferricyanide bilayer hydrogel.

[0058] The electrodes are made of graphite discs, which, due to their good viscosity, can make good contact with the electrodes. This ultimately achieves an open-circuit voltage of 0.2V at a temperature difference of 0K, and the voltage increases further when a temperature difference is applied.

[0059] Example 3

[0060] This example provides an n-type thermal redox battery prepared using a hybrid method, the preparation method of which is as follows:

[0061] B1. Prepare two sets of 20g PVA solutions with 15% by mass of dimethyl sulfoxide as solvent. Then, place the PVA solutions in a water bath at 60℃ and stir for 1 hour to completely dissolve them.

[0062] B2. Take 4 mmol of ferric perchlorate and ferrous perchlorate respectively, and add 5 g of deionized water to prepare 0.8 mol L-1 solutions of ferric perchlorate and ferrous perchlorate respectively.

[0063] B3. Add the ferric perchlorate and ferrous perchlorate solutions to the two groups of completely dissolved PVA solutions respectively, and continue to stir in a water bath for 1 hour.

[0064] B4. Add 1 ml of the mixed solution dropwise into the polytetrafluoroethylene mold each time, and then place it in the freezer at -8℃ for 1 hour. Then place the polytetrafluoroethylene mold at room temperature to allow the sample to thaw. Repeat the freeze-thaw process 3 times.

[0065] B5. Demold the gel sample, using the ferric perchlorate gel as the hot working end and the ferrous perchlorate gel as the cold working end, then bond the two together to obtain an n-type polyvinyl alcohol hydrogel of ferric perchlorate and ferrous perchlorate. Figure 2 b).

[0066] The demolded ferric perchlorate Fe(ClO4)3 hydrogel and ferrous perchlorate Fe(ClO4)2 hydrogel were bonded together, and the electrode was a graphite disc electrode to achieve an open circuit voltage of 0.23V.

[0067] Example 4

[0068] This example provides a p-type thermal redox battery prepared by an immersion method, the preparation method of which is as follows:

[0069] C1. Take a mixture of 3g PVA and 17g deionized water and stir it in a 100°C water bath for 12 hours until the PVA is completely dissolved.

[0070] C2. Place the mixed solution into a pre-made polytetrafluoroethylene mold, and freeze the polytetrafluoroethylene mold in a -17°C freezer for 12 hours.

[0071] C3. Thaw at 25°C for 12 hours, repeat this freeze-thaw cycle three times to obtain pure PVA hydrogel;

[0072] C4. The prepared PVA hydrogel was divided into two groups, and one group was soaked in 0.05 mol potassium ferricyanide solution.

[0073] C5. One group was immersed in a 0.05 mol potassium ferrocyanide solution;

[0074] C6. Heat the solution in a water bath to 80°C and soak for 6 hours;

[0075] C7. Obtain p-type potassium ferrocyanide polyvinyl alcohol PVA gel and potassium ferrocyanide polyvinyl alcohol PVA gel containing a single redox ion. Figure 2 c).

[0076] By bonding the two gels together and using graphite electrodes, an open-circuit voltage of 0.19V was achieved.

[0077] Example 5

[0078] This example provides a p-type thermal redox battery prepared by an immersion method, the preparation method of which is as follows:

[0079] D1. Weigh 2.4g of AAM and dissolve it in 9.6g of deionized water. Add 0.024g of initiator APS, 0.1wt% of AAM and 0.024g of crosslinking agent MBA, 0.1wt% of AAM to the solution. Stir magnetically for 1 hour to obtain the gel precursor solution.

[0080] D2. The prepared precursor liquid was dropped into a polytetrafluoroethylene mold and initiated at 60°C for 12 hours to obtain polyacrylamide hydrogel.

[0081] D3. Immerse the prepared hydrogels in 0.05M potassium ferricyanide and 0.05M potassium ferrocyanide solutions for 12 hours respectively, then remove and bond the two gels together. Figure 2 d).

[0082] Using graphite electrodes, an open-circuit voltage of 0.21V was achieved.

[0083] In this invention, a gel containing a single oxidation or reduction ion is prepared by a mixing or soaking method. The gel and electrode are then assembled to obtain a quasi-solid-state bilayer ion-thermal redox battery with a high open-circuit voltage. Furthermore, by using a simple gel preparation and processing method, combined with a graphite electrode, the constructed quasi-solid-state bilayer ion-thermal redox battery exhibits a stable and high open-circuit voltage, which further increases when a temperature difference is established. Moreover, the material composition is simple, the configuration method is easy, the preparation process has mild reaction conditions, simple steps, is green and environmentally friendly, and has universal applicability. This provides a new approach for preparing high thermoelectric power p-type and n-type ion thermoelectric materials.

[0084] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A quasi-solid-state bilayer ion thermal redox battery with high open-circuit voltage, characterized in that: The quasi-solid-state bilayer ion thermal oxidation-reduction battery includes, from top to bottom, a hot-side electrode (4), a gel containing a single oxide ion (1), a gel containing a single reduction ion (2), and a cold-side electrode (3). A high voltage is formed between the hot-side electrode (4) and the cold-side electrode (3). If the quasi-solid-state bilayer ion thermal oxidation-reduction battery is p-type, the gel containing a single oxide ion (1) is located on the cold side, and the gel containing a single reduction ion (2) is located on the hot side. If the quasi-solid-state bilayer ion thermal oxidation-reduction battery is n-type, the gel containing a single oxide ion (1) is located on the hot side, and the gel containing a single reduction ion (2) is located on the cold side. Both the cold-side electrode (3) and the hot-side electrode (4) are graphite disc electrodes and are respectively bonded to the cold-side gel and the hot-side gel. The preparation of the quasi-solid-state bilayer ion thermal redox battery includes the following steps: S1. Select the type and method for preparing quasi-solid-state bilayer ion thermal redox batteries; S2. Preparation of quasi-solid gels containing a single oxide or reduction ion; S3, thermal redox battery assembly and high open-circuit voltage detection.

2. The quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 1, characterized in that: In step S1, the types of quasi-solid-state bilayer ion thermal redox batteries include P-type thermal redox batteries and n-type thermal redox batteries, and the methods include mixing or immersion.

3. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 1, characterized in that: When the hybrid method is used to prepare a P-type thermal redox battery in step S1, the specific method of step S2 is as follows: A1: Select a certain p-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion, respectively. A2: Select a gellifiable polymer material, add it to the solution prepared in A1, stir to dissolve, and then pour it into a mold to solidify in a certain environment; A3: Demold the gel containing a single oxide ion and a single reduction ion prepared in A2, mechanically attach them to both sides of the bilayer gel to assemble the electrodes, and obtain a p-type quasi-solid-state bilayer ion thermal redox battery.

4. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to any one of claims 1, characterized in that: When the hybrid method is used to prepare an n-type thermal redox battery in step S1, the specific method of step S2 is as follows: B1: Select a certain type n-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion respectively. B2: Select a gelatable polymer material, add it to the solution prepared in B1, stir to dissolve, and then pour it into a mold to solidify in a certain environment; B3: Demold the gel containing a single oxide ion and a single reduction ion prepared in B2, mechanically attach them to both sides of the bilayer gel to assemble the electrodes, and obtain an n-type quasi-solid-state bilayer ion thermal redox battery.

5. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 3, characterized in that: When the immersion method is used to prepare a p-type thermal redox battery in step S1, the specific method of step S2 is as follows: C1. Select a gellifiable polymer material, add a solvent, stir and heat to dissolve, and then pour it into a mold to solidify in a certain environment; C2. Select a certain p-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion, respectively. C3. The blank gel prepared in step 1 is demolded and immersed in electrolyte solutions containing single oxide ions and single reduction ions respectively in step 2; after a period of time, the two are taken out and mechanically bonded to both sides of the bilayer gel to assemble the electrode, thus obtaining a p-type quasi-solid-state bilayer ion thermal redox battery.

6. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 3, characterized in that: When the immersion method is used to prepare a p-type thermal redox battery in step S1, the specific method of step S2 is as follows: D1. Select a gellifiable polymer material, add a solvent, stir and heat to dissolve, and then pour it into a mold to solidify in a certain environment; D2. Select a certain type n-type thermal redox ion pair, select a solvent that can dissolve the thermal redox ion pair, and prepare electrolyte solutions with a certain concentration containing a single oxide ion and a single reduction ion, respectively. D3. The blank gel prepared in D1 is demolded and immersed in electrolyte solutions containing single oxide ions and single reduction ions in D2 respectively; after a period of time, the two are taken out and mechanically bonded to both sides of the bilayer gel to assemble the electrode, thus obtaining an n-type quasi-solid-state bilayer ion thermal redox battery.

7. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 4, characterized in that: In step B1, the PVA solution is heated to 40-80℃ in a water bath and stirred for 1 hour to ensure complete dissolution.

8. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 4, characterized in that: In step B4, the PTFE mold is frozen at -5 to -10°C for 1 hour.

9. A quasi-solid-state double-layer ion thermal redox battery with high open-circuit voltage according to claim 5, characterized in that: In step C6, the solution water bath temperature is 70-90℃.

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