Preparation method of high-energy and long-lasting organic electrode and deep-sea energy storage battery
By anchoring 2,2'-bipyridine-4,4'-dicarboxylic acid in the conductive network of polyvinylidene fluoride and conductive carbon black, the organic electrode was solved by improving the organic electrode in potassium ion by high-energy ball milling method. The problems of poor cycle stability and low energy density in the battery achieve high energy and durability of organic electrodes, which are suitable for deep-sea energy storage batteries.
Patent Information
- Application Number
- CN202411312276.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-20
- Publication Date
- 2024-12-10
- Estimated Expiration
- 2044-09-20
AI Technical Summary
Existing organic electrodes have poor cycle stability and low energy density problems in potassium ion batteries, which limit their application in deep-sea energy storage batteries. Traditional optimization strategies such as polymerization and carbon nanotube/graphene composite require strict synthesis control. and high cost.
Using 2,2'-bipyridine-4,4'-dicarboxylic acid (BDA) as the active material, combined with high-energy ball milling method, it is anchored in a conductive network composed of polyvinylidene fluoride and conductive carbon black, through Improved ball milling process improves weak intermolecular forces and conductivity, achieving high energy and durable organic electrode preparation.
It improves the cyclic stability and actual capacity of organic electrodes, reduces production costs, achieves high energy density and long cycle life, and is suitable for deep-sea energy storage batteries.
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Figure CN118841568B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of electrochemical technology, and in particular to a method for preparing a high-energy and durable organic electrode and a deep-sea energy storage battery thereof. Background Art
[0002] The marine environment is rich in clean energy resources, such as wind energy, solar energy and wave energy. The use of a coupling utilization system of multiple new clean energy sources will be an important direction for deep-sea energy supply. However, the supply of clean energy is greatly affected by the environment and is often unstable. Therefore, the development of low-cost distributed energy storage systems is particularly important for marine energy supply. Among the many energy storage technologies, rechargeable batteries are considered to be the most suitable large-scale energy storage solutions due to their long life, high energy efficiency and simple process. Potassium-ion batteries have received widespread attention as an emerging technology in the field of energy storage due to their richer potassium content in the earth's crust and their redox potential close to that of lithium. They have huge energy storage potential. However, the radius of potassium ions is larger than that of lithium ions, and the insertion / extraction of large-sized potassium ions will cause severe volume changes in the electrodes, destroying the cycle stability.
[0003] Organic materials have flexible molecular structures and abundant intermolecular weak forces, and can easily accept the transmission of large-sized ions without significant volume changes. Redox-active organic materials are endowed with simple electron / ion storage mechanisms through reversible coordination reactions, so they can be widely used in different battery systems. In addition, organic materials also have many ideal characteristics, such as abundant resources, low toxicity, environmental friendliness, easy synthesis and processing, and recyclability. However, there are still many challenges in the practical application of organic electrodes in potassium ion batteries. Organic electrodes are affected by the principle of like dissolves like and are easily soluble in organic electrolytes, resulting in poor cycle stability. In addition, low intrinsic conductivity greatly limits the actual capacity and energy density of organic electrodes. Organic electrodes with low capacity and poor cycle stability hinder their application in deep-sea energy storage batteries. Therefore, it is of great significance to further optimize organic electrodes to adapt to the more harsh deep-sea environment.
[0004] Among the existing optimization strategies, polymerization is considered to be an effective way to solve the problem of organic electrode dissolution, but polymerization will lead to the introduction of a large number of inactive functional groups, reduce the proportion of redox active groups, and further compress the capacity. The composite of organic materials with highly conductive carbon nanotubes / graphene can greatly improve the conductivity of organic electrodes, but the manufacture of organic electrodes composited with carbon nanotubes / graphene usually requires strict synthesis control and cumbersome operations, with low yield and high cost. These strategies are not conducive to the development and production of high-capacity and long-cycle-life organic electrodes. Summary of the invention
[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for preparing a high-energy and durable organic electrode and a deep-sea energy storage battery thereof. The method uses a low-cost organic material 2,2'-bipyridine-4,4'-dicarboxylic acid (BDA) as an active material, combined with a simple and scalable high-energy ball milling method after modification, to anchor BDA in a conductive network composed of polyvinylidene fluoride (PVDF) and conductive carbon black (Super P), namely a BDA organic electrode. The modification method of the organic electrode of the present invention has a simple process and high feasibility, and can mass-produce high-energy and durable organic electrodes, and realize the practical application of high-performance potassium ion batteries; the use of the organic electrode for the application of low-cost distributed energy storage systems facing the ocean has immeasurable scientific significance and broad practical application prospects.
[0006] To achieve the above purpose, the technical solution designed by the present invention is as follows:
[0007] The present invention provides a method for preparing a high-energy and durable organic electrode, comprising the following steps:
[0008] (1) adding 2,2'-bipyridine-4,4'-dicarboxylic acid, conductive carbon black and polyvinylidene fluoride into a quartz mortar, mixing and grinding to obtain a black mixed material 1, wherein the mass ratio of 2,2'-bipyridine-4,4'-dicarboxylic acid, conductive carbon black and polyvinylidene fluoride is 1:0.8:0.2;
[0009] (2) The black mixed material 1 was added into a glass bottle containing steel balls with particle sizes of 3 mm, 4 mm and 5 mm, and the glass bottle was placed in a planetary ball mill for pre-grinding to obtain a black mixed material 2; the number ratio of the steel balls with particle sizes of 3 mm, 4 mm and 5 mm was 3:2:1, and the capacity of the glass bottle was 5-10 mL; the speed of the pre-grinding treatment was 200-400 rpm, and the time was 5-10 min;
[0010] (3) Adding N-methylpyrrolidone into the glass bottle containing the black mixed material 2, placing the glass bottle in a planetary ball mill for ball milling to obtain a mixed slurry;
[0011] (4) Pour the mixed slurry onto the copper foil and apply it with a scraper to obtain a wet electrode sheet;
[0012] (5) The wet electrode sheet is placed in a vacuum oven and dried to obtain a high-energy and durable organic electrode.
[0013] Furthermore, in the step (3), the mass volume ratio of the black mixture 2 and N-methylpyrrolidone is 1:0.005-0.008; the rotation speed of the ball milling treatment is 200-400 rpm, and the time is 10-12 h.
[0014] Furthermore, the mass volume ratio of the black mixture 2 and N-methylpyrrolidone is 1:0.005.
[0015] Furthermore, in the step (4), the electrode sheet load after the blade coating is maintained at 1.2-1.5 mg / cm 2 .
[0016] Furthermore, in step (5), the temperature of the vacuum oven is 100-110° C., and the drying time is 8-12 hours.
[0017] The present invention also provides a high-energy and durable organic electrode prepared by the preparation method, wherein the organic electrode uses 2,2'-bipyridine-4,4'-dicarboxylic acid as an active material, a conductive network composed of polyvinylidene fluoride and conductive carbon black, and is prepared by a high-energy ball milling method; wherein the organic electrode is flat and smooth, and the 2,2'-bipyridine-4,4'-dicarboxylic acid active material is uniformly distributed in the conductive network.
[0018] The present invention also provides a deep-sea energy storage battery, which comprises a high-energy and durable organic electrode prepared by the preparation method.
[0019] Principle of the present invention:
[0020] 1. The organic electrode of the present invention induces and strengthens the weak interaction force between BDA molecules, and improves the problem of high solubility and poor cycle stability of BDA in potassium ion organic electrolyte. At the same time, after high-energy ball milling, the BDA block is reduced in size and tightly wrapped by a dense conductive network, which increases the contact area and conductivity between the electrolyte, greatly improves the density and utilization of active sites, and further improves the actual capacity. The unique ball milling process can achieve uniform dispersion of organic active materials in the conductive network composed of PVDF and Super P, shortening the ion diffusion path, improving electronic conductivity, and stimulating the anti-dissolution effect of weak interaction forces between molecules, thereby improving the actual capacity and cycle stability of organic electrodes used in potassium ion batteries.
[0021] 2. The present invention uses three small steel balls with different particle sizes of 3 mm, 4 mm, and 5 mm as ball milling media, and limits the steel balls to a volume space of 5 to 10 mL. First, compared with traditional large-particle-size ball milling media, the ball milling efficiency of mixed-particle-size ball milling media is more prominent. This is because a large number of smaller-particle-size ball milling media will perform high-frequency extrusion and collision on the ball milling material, and more efficiently convert the kinetic energy of the ball milling media into the ball milling material. Secondly, the kinetic energy given to the steel balls in a small space can be limited to a reasonable range, and the chemical properties of the organic materials will not be destroyed while ensuring effective collision with the organic materials.
[0022] Beneficial effects of the present invention:
[0023] 1. The present invention uses 2,2'-bipyridine-4,4'-dicarboxylic acid (BDA) as the active material, combined with a modified simple and scalable high-energy ball milling method, to anchor the BDA block in a conductive network composed of polyvinylidene fluoride (PVDF) and conductive carbon black (Super P), thereby reducing the size of the active material, shortening the ion diffusion path, improving the electronic conductivity, and stimulating the anti-dissolution effect of weak intermolecular forces, thereby improving the actual capacity and cycle stability of organic electrodes used in potassium ion batteries.
[0024] 2. The present invention is different from the traditional high-energy ball milling method, which achieves the purpose of synthesis or production by applying excessive energy to the mixture. In the traditional high-energy ball milling method for preparing organic materials, the molecular activity and weak intermolecular forces are easily destroyed during the high-speed, high-frequency and high-energy ball milling collision process, which damages the energy density and cycle stability of the organic electrode. The present invention creatively confines the organic active materials, conductive agents and binders to a smaller space, selects small-sized steel balls, and gives the organic molecules appropriate energy, which greatly improves the electrochemical activity of the organic materials without destroying the molecular activity and weak intermolecular forces.
[0025] 3. The present invention has the characteristics of cheap raw materials, green and environmentally friendly process, high yield, large output, and excellent electrochemical performance of the product. This method provides a universal optimization strategy for improving the energy density and cycle durability of organic active materials. In the industry background where large-scale energy storage devices require excellent performance, safety and reliability, high-energy and durable organic electrodes have the potential for large-scale application. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is a scanning electron microscope image of the BDA organic electrode prepared in Example 1;
[0027] Figure 2 XRD comparison diagram of BDA organic electrode and BDA powder prepared in Example 1;
[0028] Figure 3 This is a comparison diagram of infrared spectra of the BDA organic electrode and BDA powder prepared in Example 1;
[0029] Figure 4 This is the Raman spectrum of the BDA organic electrode prepared in Example 1;
[0030] Figure 5 This is a transmission electron microscopy image of the BDA organic electrode prepared in Example 1;
[0031] Figure 6 Schematic diagram of the intermolecular weak forces of the BDA powder prepared in Example 1;
[0032] Figure 7 The button-type potassium ion battery assembled with the BDA organic electrode prepared in Example 1 and the button-type battery assembled with the BDA electrode prepared without ball milling treatment were tested at 100 mA g -1 Cycle comparison diagram under low current density;
[0033] Figure 8 The button-type potassium ion battery assembled with the BDA organic electrode prepared in Example 1 and the button-type battery assembled with the BDA electrode prepared without ball milling treatment were tested at 1000 mA g -1 Cycle comparison diagram under high current density;
[0034] Fig. 9 A comparison chart of the rate performance of a button-type potassium ion battery assembled with a BDA organic electrode prepared in Example 1 and a button-type battery assembled with a BDA electrode prepared without ball milling treatment;
[0035] Fig.10 The in-situ infrared spectrum of the button-type potassium ion battery assembled with the BDA organic electrode prepared in Example 1;
[0036] Fig.11 The in-situ Raman spectrum of the button-type potassium ion battery assembled with the BDA organic electrode prepared in Example 1;
[0037] Fig.12 This is the in-situ XRD pattern of the button-type potassium ion battery assembled with the BDA organic electrode prepared in Example 1. DETAILED DESCRIPTION
[0038] The present invention is further described in detail below in conjunction with specific embodiments so that those skilled in the art can understand.
[0039] Example 1
[0040] A method for preparing high-energy and long-lasting organic electrodes
[0041] This method uses 2,2'-bipyridine-4,4'-dicarboxylic acid (BDA) as the active material, combined with a modified simple and scalable high-energy ball milling method, to anchor the BDA block in a conductive network composed of polyvinylidene fluoride (PVDF) and conductive carbon black (Super P) to obtain a BDA organic electrode; the specific steps are as follows:
[0042] 1) Add 500 mg of 2,2'-bipyridine-4,4'-dicarboxylic acid, 400 mg of conductive carbon black, and 100 mg of polyvinylidene fluoride into a quartz mortar and grind thoroughly for 10 min until a black mixture with no obvious white powder is obtained;
[0043] 2) adding the black mixed material obtained in step 1) into a glass bottle with a capacity of 5-10 mL and containing steel balls, placing the glass bottle in a planetary ball mill for ball milling for 10 minutes at a speed of 300 revolutions per minute to obtain a uniformly mixed black mixed material; wherein the steel balls in the glass bottle have different particle sizes, namely 3 mm, 4 mm, and 5 mm, and the number ratio is 3:2:1;
[0044] 3) Add 5 ml of N-methylpyrrolidone into the glass bottle containing the uniformly mixed black mixture obtained in step 2), and place the glass bottle in a planetary ball mill for ball milling for 12 hours at a ball milling speed of 350 revolutions per minute to obtain a mixed slurry;
[0045] 4) Pour the mixed slurry obtained in step 3) onto the copper foil and apply it with a scraper to obtain a flat and uniform wet electrode sheet. The electrode sheet load is maintained at 1.2-1.5 mg / cm 2 ;
[0046] 5) The wet electrode sheet obtained in step 4) is placed in a vacuum oven and dried overnight at 110° C. in a vacuum environment to obtain a high-energy and durable BDA organic electrode.
[0047] The performance of the prepared BDA organic electrode and BDA powder were analyzed.
[0048] Figure 1 The scanning electron microscope images of the BDA organic electrode and BDA powder show that the BDA organic electrode prepared by the present invention is successfully and evenly dispersed in the conductive network composed of polyvinylidene fluoride (PVDF) and conductive carbon black (Super P), which is conducive to establishing a fast ion / electron transmission path, improving the utilization rate of organic active groups, and stimulating the potential weak interaction between molecules of organic materials, which plays a significant role in improving the actual capacity and cycle stability of the organic electrode.
[0049] Figure 2 This is the XRD comparison diagram of BDA organic electrode and BDA powder, showing that their molecular crystal structures are exactly the same.
[0050] Figure 3 This is a comparison of the infrared spectra of BDA organic electrode and BDA powder, showing that there is no obvious change in the functional groups of the two.
[0051] Figure 4 This is the Raman spectrum of the BDA organic electrode, showing that the Raman signals from the pyridine ring and carboxylic acid group are very strong.
[0052] Figure 5This is a transmission electron microscope image of the BDA organic electrode, showing that the spacing of the BDA organic material on the (110) crystal plane is 3.42Å, with significant π stacking characteristics.
[0053] Figure 6 Schematic diagram of the weak intermolecular forces of BDA powder, showing that BDA organic materials have potential cyclic stability properties.
[0054] The above results all indicate that the method for preparing a high-energy and durable organic electrode of the present invention can perfectly preserve the structure and active functional groups of the organic material.
[0055] Example 2
[0056] The button-type potassium ion battery is assembled using the high-energy and durable BDA organic electrode obtained in Example 1, and the specific steps are as follows:
[0057] The BDA organic electrode prepared by the present invention is used as the negative electrode of the potassium ion battery. The electrode sheet is made by punching a copper foil into a round sheet with a diameter of 10 mm. The mass loading of the punched electrode sheet is 1.2-1.5 mg cm -2 CR2016 button cells were assembled in an argon glove box. Potassium metal sheets and glass fiber filter paper (GF / A) were used as counter electrodes and separators, respectively. The potassium ion electrolyte was 2.5 M KFSI dissolved in triethyl phosphate (TEP, 100%).
[0058] 1. In this embodiment, a high-energy and long-lasting BDA organic electrode and a BDA electrode prepared without ball milling treatment are respectively assembled with a potassium metal electrode sheet into a button-type potassium ion battery.
[0059] Two button-type potassium ion batteries at 100 mA g -1 The comparison results of the cycling performance at low current density are as follows Figure 7 Shown: BDA organic electrode provides 327 mAh g -1 The initial discharge capacity is 293 mAh g after 80 cycles. -1 The initial discharge capacity of the BDA electrode without ball milling was only 275 mAh g -1 It is proved that compared with the BDA electrode without ball milling treatment, the BDA organic electrode prepared by the present invention has higher actual capacity and cycle performance.
[0060] High-energy and long-lasting BDA organic electrodes and BDA electrodes prepared without ball milling were assembled with potassium metal electrodes to form button-type potassium ion batteries at 1000 mA g -1 Comparison of cycling performance at high current density Figure 8 Shown: BDA organic electrode provides 177 mAh g-1 The initial discharge capacity is 210 mAh g after 700 cycles. -1 The initial discharge capacity of the BDA electrode without ball milling treatment was only 139 mAh g -1 , and after 80 cycles, the capacity decayed significantly. This once again proves that the BDA organic electrode prepared by the present invention has excellent cycle stability and the actual capacity is also greatly improved.
[0061] 2. High-energy and long-lasting BDA organic electrodes and BDA electrodes prepared without ball milling treatment were assembled with potassium metal electrode sheets into button-type potassium ion batteries.
[0062] Comparison of rate performance of two button-type potassium ion batteries Fig. 9 As shown: When the current density is increased from 50 mA g -1 Gradually increase to 100, 200, 500, 1000 mA g -1 When the specific capacities of BDA organic electrode 1 are 400, 320, 282, 210, and 154 mAh g -1 , while the specific capacities of the BDA electrode without ball milling treatment were 340, 260, 227, 155, and 103 mAh g -1 This indicates that the BDA organic electrode prepared by the present invention has excellent rate performance.
[0063] 3. In-situ infrared spectroscopy test results of button-type potassium ion batteries prepared with high energy and long-lasting BDA organic electrodes Fig.10 As shown: These active functional groups exhibit reversible changes during the battery electrochemical cycle, indicating that the BDA organic electrode undergoes stable cyclic changes during potassium ion coordination and no damage to the active functional groups occurs.
[0064] 4. In-situ Raman spectroscopy test results of button-type potassium ion batteries prepared with high energy and long-lasting BDA organic electrodes Fig.11 As shown: The carbonyl and imine groups show periodic enhancement and weakening in the battery electrochemical reaction, further confirming the stability of the BDA organic electrode in the cycle, and the efficient coordination reaction gives it a simple electron / ion storage mechanism, which helps to stabilize and reliable the energy storage process.
[0065] 5. In-situ XRD test results of button-type potassium ion batteries prepared with high energy and long-lasting BDA organic electrodes Fig.12 As shown: the diffraction peak does not change during the battery electrochemical cycle, indicating that the BDA organic electrode maintains a stable crystal structure during the coordination reaction of large-sized potassium ions. This further proves that the BDA organic electrode prepared by the present invention has excellent structural stability, explaining its excellent electrochemical performance.
[0066] In summary, due to the unique ball milling process, the BDA organic electrode produced by the present invention is anchored in a conductive network composed of polyvinylidene fluoride (PVDF) and conductive carbon black (Super P) compared with the BDA electrode that has not been ball milled. The organic electrode induces and strengthens the weak interaction between BDA molecules, improving the problem of high solubility and poor cycle stability of BDA in potassium ion organic electrolytes. At the same time, after high-energy ball milling, the BDA block is reduced in size and tightly wrapped by a dense conductive network, which increases the contact area and conductivity between the electrolyte, greatly improves the active site density and utilization rate, and thus improves the actual capacity and cycle stability of the organic electrode used in potassium ion batteries. It shows that the high-energy and durable organic electrode prepared by the present invention has the potential to prepare deep-sea energy storage batteries.
[0067] Example 3
[0068] A method for preparing a high-energy and durable organic electrode, the specific steps are as follows:
[0069] 1) Add 500 mg of 2,2'-bipyridine-4,4'-dicarboxylic acid, 400 mg of conductive carbon black, and 100 mg of polyvinylidene fluoride into a quartz mortar and grind thoroughly for 15 min until a black mixture with no obvious white powder is obtained;
[0070] 2) Add the black mixed material obtained in step 1) into a glass bottle with a capacity of 5-10 mL and containing steel balls, and place the glass bottle in a planetary ball mill for 5 minutes at a ball milling speed of 300 revolutions per minute for pre-grinding to obtain a uniformly mixed black mixed material; wherein the steel balls in the glass bottle have different particle sizes, namely 3 mm, 4 mm, and 5 mm, and the number ratio is 3:2:1;
[0071] 3) Add 5 ml of N-methylpyrrolidone into the glass bottle containing the uniformly mixed black mixture obtained in step 2), and place the glass bottle in a planetary ball mill for 10 hours at a ball milling speed of 350 revolutions per minute to obtain a mixed slurry;
[0072] 4) Pour the mixed slurry obtained in step 3) onto the copper foil and apply it with a scraper to obtain a flat and uniform wet electrode sheet. The electrode sheet load is maintained at 1.2-1.5 mg / cm 2 ;
[0073] 5) The wet electrode sheet obtained in step 4) is placed in a vacuum oven and dried overnight at 110° C. in a vacuum environment to obtain a high-energy and durable BDA organic electrode.
[0074] Example 4
[0075] A method for preparing a high-energy and durable organic electrode, the specific steps are as follows:
[0076] 1) Add 500 mg of 2,2'-bipyridine-4,4'-dicarboxylic acid, 400 mg of conductive carbon black, and 100 mg of polyvinylidene fluoride into a quartz mortar and grind thoroughly for 12 min until a black mixture with no obvious white powder is obtained;
[0077] 2) Add the black mixed material obtained in step 1) into a glass bottle with a capacity of 5-10 mL and containing steel balls, and place the glass bottle in a planetary ball mill for 10 minutes at a ball milling speed of 200 revolutions per minute for pre-grinding to obtain a uniformly mixed black mixed material; wherein the steel balls in the glass bottle have different particle sizes, namely 3 mm, 4 mm, and 5 mm, and the number ratio is 3:2:1;
[0078] 3) Add 5 ml of N-methylpyrrolidone into the glass bottle containing the uniformly mixed black mixture obtained in step 2), and place the glass bottle in a planetary ball mill for 12 hours at a ball milling speed of 300 revolutions per minute to obtain a mixed slurry;
[0079] 4) Pour the mixed slurry obtained in step 3) onto the copper foil and apply it with a scraper to obtain a flat and uniform wet electrode sheet. The electrode sheet load is maintained at 1.2-1.5 mg / cm 2 ;
[0080] 5) The wet electrode sheet obtained in step 4) is placed in a vacuum oven and dried overnight at 110° C. in a vacuum environment to obtain a high-energy and durable BDA organic electrode.
[0081] Example 5
[0082] A method for preparing a high-energy and durable organic electrode, the specific steps are as follows:
[0083] 1) Add 500 mg of 2,2'-bipyridine-4,4'-dicarboxylic acid, 400 mg of conductive carbon black, and 100 mg of polyvinylidene fluoride into a quartz mortar and grind thoroughly for 10 min until a black mixture with no obvious white powder is obtained;
[0084] 2) Add the black mixed material obtained in step 1) into a glass bottle with a capacity of 5-10 mL and containing steel balls, and place the glass bottle in a planetary ball mill for pre-milling at a speed of 350 revolutions per minute for 10 minutes to obtain a uniformly mixed black mixed material; wherein the steel balls in the glass bottle have different particle sizes, namely 3 mm, 4 mm, and 5 mm, and the number ratio is 3:2:1;
[0085] 3) Add 5 ml of N-methylpyrrolidone into the glass bottle containing the uniformly mixed black mixture obtained in step 2), and place the glass bottle in a planetary ball mill for 12 hours at a ball milling speed of 400 revolutions per minute to obtain a mixed slurry;
[0086] 4) Pour the mixed slurry obtained in step 3) onto the copper foil and apply it with a scraper to obtain a flat and uniform wet electrode sheet. The electrode sheet load is maintained at 1.2-1.5 mg / cm 2 ;
[0087] 5) The wet electrode sheet obtained in step 4) is placed in a vacuum oven and dried overnight at 110° C. in a vacuum environment to obtain a high-energy and durable BDA organic electrode.
[0088] Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of them. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all belong to the protection scope of the present invention.
Claims
1. A method for preparing a high-energy and durable organic electrode, characterized in that: The following steps are involved: (1) adding 2,2'-bipyridine-4,4'-dicarboxylic acid, conductive carbon black and polyvinylidene fluoride into a quartz mortar, mixing and grinding to obtain a black mixed material 1, wherein the mass ratio of 2,2'-bipyridine-4,4'-dicarboxylic acid, conductive carbon black and polyvinylidene fluoride is 1:0.8:0.2; (2) adding the black mixed material 1 into a glass bottle containing steel balls with particle sizes of 3 mm, 4 mm and 5 mm, and placing the glass bottle in a planetary ball mill for pre-grinding to obtain a black mixed material 2; the number ratio of the steel balls with particle sizes of 3 mm, 4 mm and 5 mm is 3:2:1, and the capacity of the glass bottle is 5 to 10 mL; the rotation speed of the pre-grinding treatment is 200 to 400 rpm, and the time is 5 to 10 min; (3) adding N-methylpyrrolidone into the glass bottle containing the black mixed material 2, placing the glass bottle in a planetary ball mill for ball milling to obtain a mixed slurry; The mass volume ratio of black mixture 2 and N-methylpyrrolidone is 1:0.005; The ball milling process is performed at a speed of 200 to 400 rpm for 10 to 12 h. (4) pouring the mixed slurry onto copper foil and coating it with a scraper to obtain a wet electrode sheet; (5) The wet electrode sheet is placed in a vacuum oven and dried to obtain a high-energy and long-lasting organic electrode.
2. The preparation method according to claim 1, characterized in that: In the step (4), the electrode sheet load after the blade coating is maintained at 1.2 to 1.5 mg / cm 2 .
3. The preparation method according to claim 1, characterized in that: In the step (5), the temperature of the vacuum oven is 100 to 110° C., and the drying time is 8 to 12 hours.
4. A high-energy and durable organic electrode prepared by the preparation method of claim 1, characterized in that: The organic electrode uses 2,2'-bipyridine-4,4'-dicarboxylic acid as an active material, and a conductive network composed of polyvinylidene fluoride and conductive carbon black, and is manufactured by a high-energy ball milling method; wherein the organic electrode is flat and smooth, and the 2,2'-bipyridine-4,4'-dicarboxylic acid active material is uniformly distributed in the conductive network.
5. A deep-sea energy storage battery, characterized in that: The battery comprises a high-energy and long-lasting organic electrode prepared by the preparation method as claimed in claim 1.