A battery of thermoelectric current collector structure and a method of manufacturing the same

Abstract

The application discloses a kind of thermoelectric current collector structure batteries and preparation method thereof, including positive shell and negative shell, and the power supply component being arranged between positive shell and negative shell, the power supply component includes P-type thermoelectric positive pole, diaphragm and N-type thermoelectric negative pole, and the application relates to the field of energy conversion technology.The thermoelectric current collector structure battery and preparation method thereof, by the cooperation of positive shell, negative shell, P-type thermoelectric positive pole, diaphragm, electrolyte and N-type thermoelectric negative pole, the construction of thermoelectric current collector battery is carried out, when waste heat is generated during battery operation, most of the carriers in P-type thermoelectric positive pole and N-type thermoelectric negative pole flow from hot end to cold end, which is the same as the direction of electron movement inside the battery, increases the battery current, achieves the purpose of fully utilizing the waste heat generated in the process of battery operation, converting heat energy into electrical energy, reducing the safety hazard caused by waste heat stacking, and effectively prolonging the service life of the battery.

Description

Technical Field

[0001] This invention relates to the field of energy conversion technology, specifically to a battery with a thermoelectric current collector structure and its preparation method. Background Technology

[0002] Traditional batteries generate a large amount of waste heat during charging and discharging, leading to energy waste and negative impacts on the battery and the environment. This waste heat not only accelerates battery aging and damage, shortening its lifespan, but also poses safety risks due to the high-temperature environment. Furthermore, the dissipation of waste heat can cause thermal pollution to the environment, affecting the ecological balance and human health.

[0003] As described in patent number CN117059904A, a lithium-ion battery and energy storage battery pack utilize a large-area coating of composite thermoelectric material to ensure that the thermoelectric material can convert thermal energy into electrical energy when the lithium-ion battery malfunctions, thereby reducing the economic losses of the battery pack.

[0004] Based on the search of the above information, it can be seen that the waste heat generated inside the battery is not utilized, resulting in low energy utilization and the possibility of explosion due to expansion. Therefore, a battery with a thermoelectric current collector structure and its preparation method are proposed. This method can effectively convert the waste heat generated inside the battery into electrical energy, reduce waste heat emissions and environmental pollution, extend the battery's service life, and improve the sustainability and economy of energy storage. Moreover, the preparation method is simple, energy-saving, environmentally friendly, and highly safe, and can be mass-produced. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] To address the shortcomings of existing technologies, this invention provides a battery with a thermoelectric current collector structure and its preparation method, which solves the problem that traditional batteries do not utilize the waste heat generated inside the battery, resulting in low energy utilization and the possibility of explosion due to expansion.

[0007] (II) Technical Solution

[0008] To achieve the above objectives, the present invention provides the following technical solution: a battery with a thermoelectric current collector structure, comprising a positive electrode shell and a negative electrode shell, and a power supply assembly disposed between the positive electrode shell and the negative electrode shell. The power supply assembly comprises a P-type thermoelectric positive electrode, a separator, and an N-type thermoelectric negative electrode. The separator is disposed between the P-type thermoelectric positive electrode and the N-type thermoelectric negative electrode, and an electrolyte is dripped onto the separator.

[0009] The present invention is further configured such that: a gasket is provided on the top of the N-type thermoelectric negative electrode, a spring is provided on the top of the gasket, the P-type thermoelectric positive electrode is disposed inside the positive electrode shell, and the top of the spring is in contact with the bottom of the negative electrode shell.

[0010] This invention also discloses a method for preparing a battery with a thermoelectric current collector structure, specifically including the following steps:

[0011] Step 1: Prepare P-type and N-type thermoelectric materials;

[0012] Step 2: Prepare a P-type thermoelectric positive electrode from the P-type thermoelectric material and an N-type thermoelectric negative electrode from the N-type thermoelectric material;

[0013] Step 3: Assemble the battery in the following order: positive electrode shell, P-type thermoelectric positive electrode, separator, electrolyte, N-type thermoelectric negative electrode, gasket, spring contact, and negative electrode shell.

[0014] First, place the positive electrode shell, P-type thermoelectric positive electrode, and separator in that order. Then, add the electrolyte. Next, place the N-type thermoelectric negative electrode, gasket, spring, and negative electrode shell in that order. Finally, use a machine to press the electrodes together. The pressure intensity is 100kPa-1000kPa, and the pressure is maintained for 1s-600s. This can improve the stability and tightness between the battery cells and the assembly, ensuring the safety and reliability of the battery.

[0015] To extend battery life, the present invention further comprises: the P-type thermoelectric material including one of cuprous selenide, bismuth telluride, and cuprous sulfide, and the N-type thermoelectric material using one of silver selenide, silver sulfide, and bismuth selenide, ensuring that when the thermoelectric material uses temperature difference to regulate the movement of charge carriers and thus control the current direction, it can be in the same direction as the current inside the battery, thereby achieving the purpose of extending battery life.

[0016] The present invention is further configured such that the preparation method of the P-type thermoelectric material in step one includes:

[0017] S1. Add a salt solution containing the metal required for P-type thermoelectric material to an ethylene glycol solution containing the anion required for P-type thermoelectric material, heat and stir to react, and obtain a mixed solution containing the required P-type thermoelectric material.

[0018] S2. The mixed solution is subjected to solid-liquid separation, washing, vacuum drying and grinding in sequence to obtain P-type thermoelectric material;

[0019] The preparation method of the N-type thermoelectric material in step one includes:

[0020] S3. Add the salt solution containing the metal required for the N-type thermoelectric material to the ethylene glycol solution containing the required anion of the N-type thermoelectric material, heat and stir to react, and obtain a mixed solution containing the required N-type thermoelectric material.

[0021] S4. The mixed solution is subjected to solid-liquid separation, washing, vacuum drying and grinding in sequence to obtain N-type thermoelectric material.

[0022] In order to obtain a thermoelectric material free of impurities, the present invention is further configured such that the heating temperature in S1 and S3 is 20℃-800℃ and the stirring time is 1h-48h.

[0023] The solid-liquid separation in S2 and S4 includes centrifugation at a speed of not less than 4000 r / min for 2 min to 40 min;

[0024] The cleaning in S2 and S4 includes alternating use of deionized water, isopropanol, acetone and ethanol at a speed of not less than 4000 r / min for 2 min to 20 min.

[0025] The vacuum drying temperature in S2 and S4 is 50℃-800℃, and the time is 2h-48h.

[0026] The present invention is further configured such that the preparation method of the P-type thermoelectric positive electrode and the N-type thermoelectric negative electrode in step two includes:

[0027] S5. Mix and stir the P-type thermoelectric material, organic solvent and polymer binder according to the set mixing ratio to obtain the positive electrode mixed solvent. Mix and stir the N-type thermoelectric material, organic solvent and polymer binder according to the set mixing ratio to obtain the negative electrode mixed solvent.

[0028] S6. After uniformly coating the positive electrode mixed solvent onto the positive electrode of the battery using a pipette, place it in an oven to dry. After drying, obtain the P-type thermoelectric positive electrode. After uniformly coating the negative electrode mixed solvent onto the negative electrode of the battery using a pipette, place it in an oven to dry. After drying, obtain the N-type thermoelectric negative electrode.

[0029] The present invention is further configured such that the mixing ratio of the P-type thermoelectric material, organic solvent and polymer binder is: 0.01-2g: 10-500mL: 0.01-1mg;

[0030] The mixing ratio of the N-type thermoelectric material, organic solvent, and polymer binder is: 0.01-2g: 10-500mL: 0.01-1mg;

[0031] The organic solvent is one of N-methylpyrrolidine and ethylene carbonate, which can form a protective film to reduce electrode corrosion and wear, as well as regulate performance parameters such as carrier mobility, thereby ensuring the extension of battery life.

[0032] The polymer binder is one of styrene-butadiene rubber, polyvinylidene fluoride, silicon carbide gel, polycarbonate, polyvinyl alcohol, and polyvinylpyrrolidone, which can effectively suppress the expansion of positive and negative electrodes, reduce interfacial impedance, and promote carrier transport, thus ensuring the extension of battery life.

[0033] The stirring time in S5 is 1h-48h, and the drying temperature in S6 is 50℃-100℃, with a drying time of 1h-12h, to ensure the uniformity and film-forming properties of the thermoelectric material and extend the battery's service life.

[0034] To ensure the normal operation of the battery, the present invention is further configured such that the separator is one of glass cellulose, polyolefin, cellulose and polyethylene, which can prevent the positive and negative electrodes from directly contacting each other and causing a short circuit, and restrict the direction of current flow to ensure that the battery can operate normally.

[0035] The present invention is further configured such that the electrolyte is one of zinc trifluoromethanesulfonate and zinc sulfate, which can generate a potential difference between the two electrodes of the battery and maintain the stable performance of the battery, thus ensuring the normal operation of the battery.

[0036] (III) Beneficial Effects

[0037] This invention provides a battery with a thermoelectric current collector structure and its fabrication method. It has the following beneficial effects:

[0038] (1) This invention constructs a thermoelectric current collector battery by combining a positive electrode shell, a negative electrode shell, a P-type thermoelectric positive electrode, a separator, an electrolyte, and an N-type thermoelectric negative electrode. When the battery generates waste heat during operation, the majority carriers in the P-type thermoelectric positive electrode and the N-type thermoelectric negative electrode flow from the hot end to the cold end, which is the same as the direction of electron movement inside the battery. This increases the battery current and makes full use of the waste heat generated during battery operation to convert thermal energy into electrical energy. This reduces the safety hazards caused by waste heat accumulation and effectively extends the battery life.

[0039] (2) The present invention can realize the construction of thermoelectric current collector battery by sequentially assembling positive electrode shell, P-type thermoelectric positive electrode, separator, electrolyte, N-type thermoelectric negative electrode and negative electrode shell. The preparation method is simple, more energy-saving and environmentally friendly, safe and reliable, and also has the advantage of being suitable for mass production. Attached Figure Description

[0040] Figure 1 This is a schematic diagram showing the unfolded structure of the present invention;

[0041] Figure 2 This is a schematic diagram of the process of the present invention;

[0042] Figure 3 This is a schematic diagram illustrating the performance of silver selenide in Embodiment 1 of the present invention;

[0043] Figure 4 This is a schematic diagram illustrating the performance of cuprous selenide in Embodiment 1 of the present invention;

[0044] Figure 5This is a schematic diagram illustrating the performance of the battery with the thermoelectric current collector structure obtained in Embodiment 1 of the present invention;

[0045] Figure 6 This is a schematic diagram illustrating the performance of silver sulfide in Embodiment 2 of the present invention;

[0046] Figure 7 This is a schematic diagram illustrating the performance of bismuth telluride in Embodiment 2 of the present invention;

[0047] Figure 8 This is a schematic diagram illustrating the performance of the battery with the thermoelectric current collector structure obtained in Embodiment 2 of the present invention;

[0048] Figure 9 This is a schematic diagram illustrating the performance of bismuth selenide in Embodiment 3 of the present invention;

[0049] Figure 10 This is a schematic diagram illustrating the performance of cuprous sulfide in Embodiment 3 of the present invention;

[0050] Figure 11 This is a schematic diagram of the performance of the battery with the thermoelectric current collector structure obtained in Embodiment 3 of the present invention.

[0051] In the diagram, 1 is the positive electrode shell; 2 is the negative electrode shell; 3 is the power supply assembly; 4 is the P-type thermoelectric positive electrode; 5 is the diaphragm; 6 is the N-type thermoelectric negative electrode; 7 is the gasket; 8 is the spring; and 9 is the electrolyte. Detailed Implementation

[0052] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0053] Please see Figure 1-11 The present invention provides the following technical solutions:

[0054] Example 1

[0055] A method for fabricating a battery with a thermoelectric current collector structure specifically includes the following steps:

[0056] Step 1: Preparation of P-type thermoelectric material:

[0057] A Cu(NO3)2 aqueous solution was added to an ethylene glycol solution containing selenium ions. The reaction temperature was 80℃, and the mixture was continuously heated and stirred for 3 hours to obtain a solution containing cuprous selenide. The solution was centrifuged at 5000 r / min for 10 min, and the supernatant was removed. The solution was then washed alternately with deionized water and anhydrous ethanol, and centrifuged again at 6000 r / min for 10 min to extract the precipitate. The precipitate was then dried in a vacuum drying oven at 60℃ for 24 hours. After grinding, cuprous selenide powder was obtained, which is a P-type thermoelectric material. The performance diagram is attached. Figure 4 As shown;

[0058] Preparation of N-type thermoelectric materials:

[0059] An aqueous solution of AgNO3 was added to an ethylene glycol solution containing selenium ions. The reaction was carried out at 50°C with continuous heating and stirring for 2 hours to obtain a solution containing silver selenide. The solution was centrifuged at 5000 rpm for 10 minutes, and the supernatant was removed. The solution was then washed alternately with deionized water and anhydrous ethanol, and centrifuged again at 6000 rpm for 10 minutes to extract the precipitate. The precipitate was then dried in a vacuum drying oven at 50°C for 24 hours. After grinding, silver selenide powder was obtained, which is an N-type thermoelectric material. The performance diagram is attached. Figure 3 As shown;

[0060] Step 2: Mix P-type thermoelectric material, N-methylpyrrolidone and polyvinylidene fluoride at a ratio of 0.15g:2mL:20mg for 12h to obtain positive electrode mixed solvent. Then, use a pipette to evenly coat the positive electrode mixed solvent onto the positive electrode of the battery and place it in a 60℃ oven for drying. After drying, obtain P-type thermoelectric positive electrode 4.

[0061] N-type thermoelectric material, N-methylpyrrolidone and polyvinylidene fluoride were mixed and stirred for 12 hours at a ratio of 0.15g:2mL:20mg to obtain a negative electrode mixed solvent. The negative electrode mixed solvent was then uniformly coated onto the negative electrode of the battery using a pipette and placed in a 60℃ oven for drying. After drying, N-type thermoelectric negative electrode 6 was obtained.

[0062] Step 3: Place the positive electrode shell 1, P-type thermoelectric positive electrode 4, and polyethylene separator in that order, then add ZnSO4 electrolyte. Next, place the N-type thermoelectric negative electrode 6, gasket 7, spring sheet 8, and negative electrode shell 2 in that order. Finally, use a machine to press the electrode under a pressure of 500 kPa for 20 seconds to obtain a battery with a thermoelectric current collector structure. The performance diagram is attached. Figure 5 As shown.

[0063] Example 2

[0064] A method for fabricating a battery with a thermoelectric current collector structure specifically includes the following steps:

[0065] Step 1: Preparation of P-type thermoelectric material:

[0066] An ethylene glycol solution containing Bi(NO3)5 was added to an ethylene glycol solution containing tellurium ions. The reaction was carried out at 240℃ with continuous heating and stirring for 5 hours to obtain a solution containing Bi2Te. The solution was centrifuged at 8000 r / min for 15 min, and the supernatant was removed. The solution was then washed alternately with acetone and anhydrous ethanol, and centrifuged again at 8000 r / min for 20 min to extract the precipitate. The precipitate was then dried in a vacuum drying oven at 80℃ for 24 hours. After grinding, bismuth telluride powder, i.e., a P-type thermoelectric material, was obtained. The performance diagram is attached. Figure 7 As shown;

[0067] Preparation of N-type thermoelectric materials:

[0068] An aqueous solution of AgNO3 was added to an ethylene glycol solution containing sulfide ions. The reaction temperature was 90℃, and the mixture was continuously heated and stirred for 15 hours to obtain a solution containing Ag2S. The solution was centrifuged at 6000 rpm for 5 minutes to remove the supernatant. The solution was then washed alternately with deionized water and anhydrous ethanol, followed by centrifugation at 8000 rpm for 20 minutes to extract the precipitate. The precipitate was then dried in a vacuum drying oven at 100℃ for 12 hours. After grinding, silver sulfide powder, i.e., N-type thermoelectric material, was obtained. The performance diagram is attached. Figure 6 As shown;

[0069] Step 2: Mix P-type thermoelectric material, N-methylpyrrolidone and polyvinyl alcohol in a ratio of 0.18g:2mL:20mg and stir for 10h to obtain positive electrode mixed solvent. Then, use a pipette to evenly coat the positive electrode mixed solvent onto the positive electrode of the battery and place it in an 80℃ oven for drying. After drying, obtain P-type thermoelectric positive electrode 4.

[0070] N-type thermoelectric material, N-methylpyrrolidone and polyvinyl alcohol were mixed and stirred for 10 hours at a ratio of 0.18g:2mL:20mg to obtain a negative electrode mixed solvent. The negative electrode mixed solvent was then uniformly coated onto the negative electrode of the battery using a pipette and placed in an 80℃ oven for drying. After drying, N-type thermoelectric negative electrode 6 was obtained.

[0071] Step 3: Place the positive electrode shell 1, P-type thermoelectric positive electrode 4, and polyethylene separator in that order, then add ZnSO4 electrolyte. Next, place the N-type thermoelectric negative electrode 6, gasket 7, spring sheet 8, and negative electrode shell 2 in that order. Finally, use a machine to press the electrode under a pressure of 600 kPa for 20 seconds to obtain a battery with a thermoelectric current collector structure. The performance diagram is attached. Figure 8 As shown.

[0072] Example 3

[0073] A method for fabricating a battery with a thermoelectric current collector structure specifically includes the following steps:

[0074] Step 1: Preparation of P-type thermoelectric material:

[0075] A Cu(NO3)2 aqueous solution was added to an ethylene glycol solution containing sulfide ions. The reaction temperature was 160℃, and the mixture was continuously heated and stirred for 10 hours to obtain a solution containing cuprous sulfide. The solution was centrifuged at 5000 rpm for 5 minutes to remove the supernatant. After washing with deionized water and anhydrous ethanol alternately, the solution was centrifuged again at 8000 rpm for 20 minutes to extract the precipitate. The precipitate was then dried in a vacuum drying oven at 60℃ for 24 hours. After grinding, cuprous sulfide powder was obtained, which is a P-type thermoelectric material. The performance diagram is attached. Figure 10 As shown;

[0076] Preparation of N-type thermoelectric materials:

[0077] An ethylene glycol solution containing Bi(NO3)5 was added to an ethylene glycol solution containing selenium ions. The reaction temperature was 280℃, and the mixture was continuously heated and stirred for 6 hours to obtain a solution containing bismuth selenide. The solution was centrifuged at 6000 rpm for 5 minutes, and the supernatant was removed. The solution was then washed alternately with isopropanol and anhydrous ethanol, and centrifuged again at 8000 rpm for 5 minutes to extract the precipitate. The precipitate was then dried in a vacuum drying oven at 140℃ for 12 hours. After grinding, bismuth selenide powder, i.e., N-type thermoelectric material, was obtained. The performance diagram is attached. Figure 9 As shown;

[0078] Step 2: Mix P-type thermoelectric material, N-methylpyrrolidone and polyvinylpyrrolidone at a ratio of 0.18g:2mL:18mg for 12h to obtain positive electrode mixed solvent. Then, use a pipette to evenly coat the positive electrode mixed solvent onto the positive electrode of the battery and place it in a 120℃ oven for drying. After drying, obtain P-type thermoelectric positive electrode 4.

[0079] N-type thermoelectric material, N-methylpyrrolidone and polyvinylpyrrolidone were mixed and stirred for 12 hours in a ratio of 0.18g:2mL:18mg to obtain a negative electrode mixed solvent. The negative electrode mixed solvent was then uniformly coated onto the negative electrode of the battery using a pipette and placed in a 120℃ oven for drying. After drying, N-type thermoelectric negative electrode 6 was obtained.

[0080] Step 3: Place the positive electrode shell 1, P-type thermoelectric positive electrode 4, and polyethylene separator in that order. Then, add zinc trifluoromethanesulfonate electrolyte. Next, place the N-type thermoelectric negative electrode 6, gasket 7, spring 8, and negative electrode shell 2 in that order. Finally, use a machine to press the electrode under a pressure of 500 kPa for 20 seconds to obtain a battery with a thermoelectric current collector structure. The performance diagram is attached. Figure 11 As shown.

Claims

1. A thermoelectric current collector structure battery comprising a positive electrode case (1) and a negative electrode case (2), and a power supply assembly (3) disposed between the positive electrode case (1) and the negative electrode case (2), characterized by: The power supply assembly (3) comprises a P-type thermoelectric positive electrode (4), a diaphragm (5) and an N-type thermoelectric negative electrode (6), the diaphragm (5) is arranged between the P-type thermoelectric positive electrode (4) and the N-type thermoelectric negative electrode (6), and electrolyte (9) is added on the diaphragm (5); The P-type thermoelectric positive electrode (4) comprises a P-type thermoelectric material; the P-type thermoelectric material comprises one of cuprous selenide, bismuth telluride and cuprous sulfide; The N-type thermoelectric negative electrode (6) comprises an N-type thermoelectric material; the N-type thermoelectric material adopts one of silver selenide, silver sulfide and bismuth selenide; The electrolyte (9) is one of zinc trifluoromethane sulfonate and zinc sulfate.

2. A thermoelectric current collector structure battery according to claim 1, wherein: The top of the N-type thermoelectric negative electrode (6) is provided with a gasket (7), the top of the gasket (7) is provided with a spring (8), the P-type thermoelectric positive electrode (4) is arranged in the inside of the positive electrode shell (1), and the top of the spring (8) is in contact with the bottom of the negative electrode shell (2).

3. A method for manufacturing a thermoelectric current collector structure battery, applied to the thermoelectric current collector structure battery of claim 2, characterized in that: The preparation method specifically comprises the following steps: Step one, preparation of P-type thermoelectric material and N-type thermoelectric material; Step two, the P-type thermoelectric material is prepared into a P-type thermoelectric positive electrode (4), and the N-type thermoelectric material is prepared into an N-type thermoelectric negative electrode (6); Step three, the battery is assembled in the order of the positive electrode shell (1), the P-type thermoelectric positive electrode (4), the diaphragm (5), the electrolyte (9), the N-type thermoelectric negative electrode (6), the gasket (7), the spring (8) and the negative electrode shell (2).

4. A method of making a battery of thermoelectric current collectors according to claim 3, wherein: The preparation method of the P-type thermoelectric material in the step one comprises: S1, a salt solution containing the metal required by the P-type thermoelectric material is added into an ethylene glycol solution containing the anion required by the P-type thermoelectric material, and after heating and stirring reaction, a mixed solution containing the required P-type thermoelectric material is obtained; S2, the mixed solution is sequentially subjected to solid-liquid separation, washing, vacuum drying and grinding to obtain the P-type thermoelectric material; The preparation method of the N-type thermoelectric material in the step one comprises: S3, a salt solution containing the metal required by the N-type thermoelectric material is added into an ethylene glycol solution containing the anion required by the N-type thermoelectric material, and after heating and stirring reaction, a mixed solution containing the required N-type thermoelectric material is obtained; S4, the mixed solution is sequentially subjected to solid-liquid separation, washing, vacuum drying and grinding to obtain the N-type thermoelectric material.

5. A method of making a battery of thermoelectric current collectors according to claim 4, wherein: The heating temperature in S1 and S3 is 20-800℃, and the stirring time is 1-48h; The solid-liquid separation in S2 and S4 comprises centrifugation at a speed of not less than 4000r / min for 2-40min; The washing in S2 and S4 comprises alternating use of deionized water, isopropyl alcohol, acetone and ethanol for centrifugal washing at a speed of not less than 4000r / min for 2-20min; The vacuum drying temperature in S2 and S4 is 50-800℃, and the time is 2-48h.

6. The method of claim 3, wherein: The preparation method of the P-type thermoelectric positive electrode (4) and the N-type thermoelectric negative electrode (6) in the step two comprises: S5, the P-type thermoelectric material, the organic solvent and the polymer binder are mixed and stirred according to the set mixing ratio to obtain a positive electrode mixed solvent, and the N-type thermoelectric material, the organic solvent and the polymer binder are mixed and stirred according to the set mixing ratio to obtain a negative electrode mixed solvent; S6, after using the pipette to evenly coat the positive electrode mixed solvent on the battery positive electrode, put into the oven for drying, after drying to obtain P-type thermoelectric positive electrode (4), using the pipette to evenly coat the negative electrode mixed solvent on the battery negative electrode, put into the oven for drying, after drying to obtain N-type thermoelectric negative electrode (6).

7. A method of making a battery of thermoelectric current collectors according to claim 6, wherein: The mixing ratio of the P-type thermoelectric material, organic solvent and polymer binder is: 0.01-2g: 10-500mL: 0.01-1mg; The mixing ratio of the N-type thermoelectric material, organic solvent and polymer binder is: 0.01-2g: 10-500mL: 0.01-1mg; The organic solvent is one of N-methyl pyrrolidine and ethylene carbonate; The polymer binder is one of butadiene styrene rubber, polyvinylidene fluoride, silicon carbon gel, polycarbonate, polyvinyl alcohol and polyvinyl pyrrolidone; The stirring time in S5 is 1h-48h, and the drying temperature in S6 is 50℃-100℃, and the drying time is 1h-12h.

8. The method of claim 3, wherein: The diaphragm (5) is one of glass cellulose, polyolefin, cellulose and polyethylene.

Images