A high-power, long-life sodium ion battery and its preparation method

By optimizing the positive and negative electrode structures of sodium-ion batteries, using small-particle NaFePO4 with a specific ratio of positive electrode binder and conductive agent, and combining polymer solute and electrolyte design, the problem of low working efficiency of sodium-ion batteries at high power density is solved, and the effects of fast charging and discharging and long life are achieved.

CN119944043BActive Publication Date: 2025-09-16FUJIAN SHIJI HUANA NEW ENERGY TECHNOLOGY GROUP CO LTD
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Patent Information

Application Number
CN202510106026.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-01-23
Publication Date
2025-09-16
Estimated Expiration
2045-01-23

AI Technical Summary

Technical Problem

Existing sodium-ion batteries have low operating efficiency and slow charging speed at high power density, making it difficult to meet the needs of high-performance energy storage systems.

Method used

Small-particle NaFePO4 is mixed with a specific proportion of positive electrode binder and conductive agent to form a positive electrode with a stable structure and rich micropores. It is combined with an appropriate amount of polymer solute and conductive agent, and the binding force between the current collector and the positive electrode slurry is enhanced through heat treatment. Specific electrolyte and negative electrode binder are used to accelerate the insertion and extraction of sodium ions, optimize the negative electrode structure, and add N-phthalylglycine to promote electrolyte wetting and water repellency.

Benefits of technology

It improves the working efficiency and charge and discharge speed of sodium-ion batteries at high power density, extends the cycle life and power density of the battery, and improves the charging speed and capacity retention rate of the battery.

✦ Generated by Eureka AI based on patent content.

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Patent Text Reader

Abstract

The present application relates to the field of electrochemical energy storage technology, and specifically discloses a high-power, long-life sodium-ion battery and its preparation method. The preparation method of the sodium-ion battery comprises: mixing NaFePO4 with a positive electrode binder and a positive electrode conductor to obtain a positive electrode slurry; the particle size D50 of NaFePO4 is 0.5~1μm; coating the positive electrode slurry on the positive electrode current collector and drying to obtain a positive electrode sheet; the mass proportion of the polymer solute in the positive electrode binder is 10~15%; mixing hard carbon with a negative electrode binder and a negative electrode conductor to obtain a negative electrode slurry; coating the negative electrode slurry on the negative electrode current collector and drying to obtain a negative electrode sheet; soaking the positive electrode sheet, the negative electrode sheet and the diaphragm in the electrolyte and encapsulating them into a sodium-ion battery. The small particle size of NaFePO4 increases the sodium ion deintercalation speed, and the low concentration and high total amount of the positive electrode binder are conducive to the formation of multiple micropores, promoting the migration of sodium ions, and making the battery have higher power and cycle life.
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Description

Technical Field

[0001] The present application relates to the field of electrochemical energy storage technology, and in particular to a high-power, long-life sodium ion battery and a preparation method thereof. Background Art

[0002] With the rapid development of the new energy industry, the demand for high-efficiency energy storage devices is growing. Currently, the mainstream energy storage technology on the market is still lithium-ion batteries, but lithium resources are limited and prices fluctuate significantly, prompting the industry to seek alternatives. Sodium-ion batteries have attracted much attention due to their abundant resources and low costs, but early sodium-ion batteries generally suffered from poor cycle stability and rate performance. With technological advances, sodium-ion batteries have greatly improved in capacity and cycle life. However, at present, sodium-ion batteries have low operating efficiency at high power density and slow charging speeds, making it difficult to meet the needs of high-performance energy storage systems. Summary of the Invention

[0003] In view of the fact that the current sodium-ion batteries have low working efficiency and slow charging speed at high power density, which makes it difficult to meet the needs of high-performance energy storage systems, this application proposes the following technical solutions.

[0004] A method for preparing a high-power and long-life sodium ion battery comprises the following steps.

[0005] NaFePO4 is uniformly mixed with a positive electrode binder and a positive electrode conductor in a mass ratio of 10:(2-3):(0.5-1.5) to obtain a positive electrode slurry; the particle size D50 of the NaFePO4 is 0.5-1 μm; the positive electrode slurry is coated on a positive electrode current collector, and a positive electrode sheet is obtained after drying and curing; wherein the positive electrode binder includes a polymer solute and a solvent, and the mass proportion of the polymer solute in the positive electrode binder is 10-15%.

[0006] The hard carbon is mixed evenly with a negative electrode binder and a negative electrode conductor to obtain a negative electrode slurry; the negative electrode slurry is coated on a negative electrode current collector, and dried and solidified to obtain a negative electrode sheet.

[0007] The positive electrode sheet, the negative electrode sheet and the separator are immersed in an electrolyte and packaged into a sodium ion battery.

[0008] By adopting the above technical solution, using small-particle NaFePO4, its specific surface area is large and the sodium ions are fully exposed. Applying it to sodium-ion batteries is beneficial to increase the speed of sodium ion extraction and back-insertion into the positive electrode, thereby increasing the ability to output large currents in a short time and improving the working efficiency of sodium-ion batteries at high power density. When the sodium-ion battery is charging, sodium ions are extracted from the positive electrode, and the positive electrode potential increases. At the same time, the sodium ions further migrate to the negative electrode surface in the electrolyte and are embedded in the negative electrode active material hard carbon. In this process, electrons flow from the positive electrode to the negative electrode through the external circuit, causing the negative electrode potential to decrease, thereby increasing the voltage difference between the positive and negative electrodes and realizing the charging of the sodium-ion battery. This solution increases the speed of sodium ions extraction and back-insertion into the positive electrode, thereby increasing the charge and discharge speed. After the positive current collector is dried and solidified, the solvent of the positive electrode binder is evaporated, and more micropores are obtained. These micropores are conducive to the penetration of the electrolyte, thereby promoting the migration of sodium ions. The mass ratio of NaFePO4 to the positive electrode binder and the positive electrode conductive agent is 10:(2-3):(0.5-1.5), and the mass proportion of the polymer solute in the positive electrode binder is 10-15%. This lower concentration and higher total amount of positive electrode binder can not only have a good adhesion effect on NaFePO4 after drying, reducing the powdering and cracking of the positive electrode material on the positive electrode sheet, but also facilitate the formation of more micropores after drying, which is conducive to the infiltration of the electrolyte and promotes the migration of sodium ions. The above design makes the sodium ion migration resistance small and the migration speed fast, so that the sodium ion battery has a higher power and cycle life.

[0009] A preferred solution of the preparation method of the high-power and long-life sodium ion battery is that the polymer solute is polyvinylidene fluoride; and the molecular weight of the polyvinylidene fluoride is 500,000 to 1,000,000.

[0010] By adopting the above technical solution, small-particle NaFePO4 and large-molecule polyvinylidene fluoride cooperate with each other, and the large-molecule polyvinylidene fluoride is dispersed in the NaFePO4 to form more gaps, which is conducive to the formation of more micropores after the solvent dries. In addition, polyvinylidene fluoride is uncharged, has low adsorption force for sodium ions, and has little binding effect on sodium ions. Sodium ions can easily leave the positive electrode and enter the electrolyte, all of which together improve the charging and discharging speed.

[0011] A preferred embodiment of the preparation method of the high-power and long-life sodium-ion battery is that before coating the positive electrode slurry on the positive electrode current collector, the positive electrode current collector is first heated to a temperature above the melting point and below the boiling point of the polymer solute, and the heating temperature is lower than the melting point of the positive electrode current collector, and then the positive electrode slurry is coated on the positive electrode current collector.

[0012] By adopting the above technical solution, the polymer solute melts on the surface of the positive electrode current collector at the contact surface between the positive electrode slurry and the positive electrode current collector, thereby enhancing the mutual bonding force, reducing the contact resistance between the positive electrode material and the positive electrode current collector, and improving the power density and charging speed of the battery.

[0013] A preferred solution for the preparation method of the high-power and long-life sodium-ion battery is that the electrolyte is an aqueous electrolyte; and the negative electrode binder is a polymer material with a negative surface charge in water.

[0014] By adopting the above technical solution, the negative electrode binder has an attractive effect on sodium ions, thereby increasing the speed at which sodium ions are embedded in the negative electrode during charging, thereby increasing the charging speed.

[0015] A preferred solution of the preparation method of the high-power and long-life sodium ion battery is that the negative electrode binder is a carboxymethyl cellulose solution or a hydroxyethyl cellulose solution.

[0016] By adopting the above technical solution, these celluloses contain groups such as uronic acid groups and polar hydroxyl groups. These groups are usually negatively charged on the surface in water. These groups will adsorb positive charges, such as sodium ions, in aqueous solution, accelerating the embedding of sodium ions into the negative electrode.

[0017] A preferred embodiment of the method for preparing a high-power, long-life sodium-ion battery is as follows: the mass concentration of the polymer material in the negative electrode binder is 0.5-1%, and the hard carbon, the negative electrode binder, and the negative electrode conductive agent are mixed in a mass ratio of 8:(0.5-1.5):(0.5-1.5).

[0018] By adopting the above technical solution, the negative electrode binder with a lower proportion and lower concentration is not easy to clog the nanopore structure of the hard carbon, thereby protecting the hard carbon's good ability to store sodium ions, maintaining the hard carbon's high reversible specific capacity, and improving the battery's cycle performance.

[0019] A preferred embodiment of the preparation method of the high-power and long-life sodium-ion battery is that the raw materials for preparing the positive electrode slurry also include N-phthalylglycine; NaFePO4 is uniformly mixed with the positive electrode binder, the positive electrode conductor, and N-phthalylglycine in a mass ratio of 10:(2-3):(0.5-1.5):(0.1-0.2) to obtain the positive electrode slurry.

[0020] By adopting the above technical solution, N-phthaloylglycine is doped into the positive electrode. The hydrophilic carboxyl group in N-phthaloylglycine promotes the wetting of the electrolyte on the microporous surface of the positive electrode. The benzene heterocycle has a water-repellent effect, which reduces excessive penetration of water into the bonding structure, reduces the damage to the positive electrode structure caused by battery charging and discharging, and improves the battery's cycle capacity retention rate and power density.

[0021] A preferred embodiment of the preparation method of the high-power and long-life sodium-ion battery is that the positive electrode conductive agent is acetylene black, carbon nanotubes or Ketjen black; the negative electrode conductive agent is acetylene black, carbon nanotubes or Ketjen black; the D50 particle size of the acetylene black is 30 to 45 nm; the D50 length of the carbon nanotubes is 10 to 30 μm; and the D50 particle size of the Ketjen black is 20 to 100 nm.

[0022] By adopting the above technical solution, the acetylene black, carbon nanotubes or Ketjen black of this size has good conductivity and stability.

[0023] A preferred solution for the preparation method of the high-power, long-life sodium-ion battery is as follows: the solute of the electrolyte is NaPF6, and the solvent is a mixture of monomethyl acrylate, ethylene glycol dimethyl ether, and methanol; the concentration of NaPF6 in the electrolyte is 0.5M to 1.5M; and hydroquinone monomethyl ether is further added to the electrolyte, and the mass concentration of the hydroquinone monomethyl ether in the electrolyte is 0.05 to 0.15%.

[0024] By adopting the above technical solution, hydroquinone monomethyl ether can effectively inhibit the oxidative decomposition of the electrolyte under high voltage, thereby improving the cycle life of the battery.

[0025] A high-power and long-life sodium ion battery is prepared according to the above preparation method.

[0026] By adopting the above technical solution, the sodium ions of the battery can quickly detach from the positive electrode during charging, thereby increasing its power. The cycle life of the battery can be improved by designing a suitable raw material ratio and adding N-phthalylglycine.

[0027] In summary, the high-power and long-life sodium ion battery and its preparation method of the present application have the following beneficial effects: by designing the ratio of NaFePO4 to the positive electrode binder and the positive electrode conductor, a positive electrode with a stable structure and rich in micropores is formed, which is conducive to the penetration of the electrolyte into the positive electrode and the formation of a thicker SEI film during the first charge and discharge, thereby facilitating the rapid detachment and embedding of sodium ions into the electrode, improving the cycle stability and service life of the positive electrode, and thus improving the rate performance and power density of the battery. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments are described clearly and completely below. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. Based on the following embodiments, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0029] Example 1

[0030] In this embodiment, a high-power and long-life sodium ion battery is prepared by the following steps.

[0031] Preparation of positive electrode slurry: NaFePO4 is evenly mixed with a positive electrode binder and a positive electrode conductor in a mass ratio of 10:2.5:1 to obtain a positive electrode slurry. Among them, the particle size D50 of NaFePO4 is 0.8μm. The positive electrode binder includes a polymer solute and a solvent. The polymer solute is polyvinylidene fluoride. DMF (tetrahydrofuran) is used as the solvent. The mass proportion of polyvinylidene fluoride in the positive electrode binder is 12%, and complete dissolution is achieved by heating. The molecular weight of polyvinylidene fluoride is 700,000. The positive electrode conductor is acetylene black, and the D50 particle size of acetylene black is 38nm.

[0032] Prepare the positive electrode sheet: Apply the positive electrode slurry to the positive electrode current collector, dry and solidify it to obtain the positive electrode sheet. The positive electrode current collector is a 0.1 mm thick aluminum foil. The positive electrode slurry is applied to a thickness of 50 μm on the positive electrode current collector.

[0033] Preparation of negative electrode slurry: Hard carbon, a negative electrode binder, and a negative electrode conductive agent were uniformly mixed in a mass ratio of 8:1:1 to obtain a negative electrode slurry. The hard carbon had a D50 particle size of 46 nm. The negative electrode binder was an aqueous solution of carboxymethyl cellulose, which accounted for 0.7% by mass of the negative electrode binder. The negative electrode conductive agent was carbon nanotubes, with a D50 length of 22 μm.

[0034] Prepare the negative electrode sheet: Apply the negative electrode slurry to the negative electrode current collector, bake at 155°C for 1 hour, and dry and solidify to obtain the negative electrode sheet. The negative electrode slurry is applied to a thickness of 50 μm on the negative electrode current collector, which is 0.1 mm thick aluminum foil.

[0035] Prepare the electrolyte: the solute of the electrolyte is NaPF6, and the solvent is a mixture of monomethyl acrylate, ethylene glycol dimethyl ether and methanol in a volume ratio of 1:1:1; the concentration of NaPF6 in the electrolyte is 1M; hydroquinone monomethyl ether is also added to the electrolyte, and the mass concentration of hydroquinone monomethyl ether in the electrolyte is 0.1%.

[0036] Prepare the battery: Immerse the positive electrode sheet, negative electrode sheet and polyethylene separator in the electrolyte and encapsulate them into a sodium ion battery.

[0037] Example 2

[0038] In this embodiment, a high-power and long-life sodium ion battery is prepared by the following steps.

[0039] Preparation of positive electrode slurry: NaFePO4 is evenly mixed with a positive electrode binder and a positive electrode conductor in a mass ratio of 10:2:1.5 to obtain a positive electrode slurry. Among them, the particle size D50 of NaFePO4 is 0.5μm. The positive electrode binder includes a polymer solute and a solvent. The polymer solute is polyvinylidene fluoride. DMF (tetrahydrofuran) is used as the solvent. The mass proportion of polyvinylidene fluoride in the positive electrode binder is 10%, and complete dissolution is achieved by heating. The molecular weight of polyvinylidene fluoride is 500,000. The positive electrode conductor is acetylene black, and the D50 particle size of acetylene black is 38nm.

[0040] Prepare the positive electrode sheet: Apply the positive electrode slurry to the positive electrode current collector, dry and solidify it to obtain the positive electrode sheet. The positive electrode current collector is a 0.1 mm thick aluminum foil. The positive electrode slurry is applied to a thickness of 50 μm on the positive electrode current collector.

[0041] Preparation of negative electrode slurry: Hard carbon, a negative electrode binder, and a negative electrode conductive agent were uniformly mixed in a mass ratio of 8:1:1 to obtain a negative electrode slurry. The hard carbon had a D50 particle size of 46 nm. The negative electrode binder was an aqueous solution of carboxymethyl cellulose, with the mass fraction of carboxymethyl cellulose in the negative electrode binder being 0.5%. The negative electrode conductive agent was carbon nanotubes, with a D50 length of 22 μm.

[0042] Prepare the negative electrode sheet: Apply the negative electrode slurry to the negative electrode current collector, bake at 155°C for 1 hour, and dry and solidify to obtain the negative electrode sheet. The negative electrode slurry is applied to a thickness of 50 μm on the negative electrode current collector, which is 0.1 mm thick aluminum foil.

[0043] Prepare the electrolyte: the solute of the electrolyte is NaPF6, and the solvent is a mixture of monomethyl acrylate, ethylene glycol dimethyl ether and methanol in a volume ratio of 1:1:1; the concentration of NaPF6 in the electrolyte is 1M; hydroquinone monomethyl ether is also added to the electrolyte, and the mass concentration of hydroquinone monomethyl ether in the electrolyte is 0.1%.

[0044] Prepare the battery: Immerse the positive electrode sheet, negative electrode sheet and polyethylene separator in the electrolyte and encapsulate them into a sodium ion battery.

[0045] Example 3

[0046] In this embodiment, a high-power and long-life sodium ion battery is prepared by the following steps.

[0047] Preparation of positive electrode slurry: NaFePO4 is evenly mixed with a positive electrode binder and a positive electrode conductor in a mass ratio of 10:3:0.5 to obtain a positive electrode slurry. Among them, the particle size D50 of NaFePO4 is 1μm. The positive electrode binder includes a polymer solute and a solvent. The polymer solute is polyvinylidene fluoride. DMF (tetrahydrofuran) is used as the solvent. The mass proportion of polyvinylidene fluoride in the positive electrode binder is 15%, and complete dissolution is achieved by heating. The molecular weight of polyvinylidene fluoride is 1 million. The positive electrode conductor is acetylene black, and the D50 particle size of acetylene black is 38nm.

[0048] Prepare the positive electrode sheet: Apply the positive electrode slurry to the positive electrode current collector, dry and solidify it to obtain the positive electrode sheet. The positive electrode current collector is a 0.1 mm thick aluminum foil. The positive electrode slurry is applied to a thickness of 50 μm on the positive electrode current collector.

[0049] Preparation of negative electrode slurry: Hard carbon, a negative electrode binder, and a negative electrode conductive agent were uniformly mixed in a mass ratio of 8:1:1 to obtain a negative electrode slurry. The hard carbon had a D50 particle size of 46 nm. The negative electrode binder was an aqueous solution of hydroxyethyl cellulose, with the mass fraction of hydroxyethyl cellulose in the negative electrode binder being 1%. The negative electrode conductive agent was carbon nanotubes, with a D50 length of 22 μm.

[0050] Prepare the negative electrode sheet: Apply the negative electrode slurry to the negative electrode current collector, bake at 155°C for 1 hour, and dry and solidify to obtain the negative electrode sheet. The negative electrode slurry is applied to a thickness of 50 μm on the negative electrode current collector, which is 0.1 mm thick aluminum foil.

[0051] Prepare the electrolyte: the solute of the electrolyte is NaPF6, and the solvent is a mixture of monomethyl acrylate, ethylene glycol dimethyl ether and methanol in a volume ratio of 1:1:1; the concentration of NaPF6 in the electrolyte is 1M; hydroquinone monomethyl ether is also added to the electrolyte, and the mass concentration of hydroquinone monomethyl ether in the electrolyte is 0.1%.

[0052] Prepare the battery: Immerse the positive electrode sheet, negative electrode sheet and polyethylene separator in the electrolyte and encapsulate them into a sodium ion battery.

[0053] Example 4

[0054] This embodiment adopts the technical scheme substantially the same as that of Example 1 to prepare a sodium ion battery, the only difference being that before the positive electrode slurry is coated on the positive electrode current collector, the positive electrode current collector is first heated to 200° C., and then the positive electrode slurry is coated on the positive electrode current collector.

[0055] Example 5

[0056] This example uses substantially the same technical solution as Example 1 to prepare a sodium ion battery, with the only difference being that the raw materials for preparing the positive electrode slurry also include N-phthalylglycine (melting point 198°C). NaFePO4 is uniformly mixed with a positive electrode binder, a positive electrode conductor, and N-phthalylglycine in a mass ratio of 10:2:0.5:0.2 to obtain a positive electrode slurry.

[0057] Example 6

[0058] This example uses substantially the same technical solution as Example 1 to prepare a sodium-ion battery, with the only difference being that the raw materials for preparing the positive electrode slurry also include N-phthalylglycine (melting point 198°C). NaFePO4 is uniformly mixed with a positive electrode binder, a positive electrode conductor, and N-phthalylglycine in a mass ratio of 10:3:1.5:0.1 to obtain a positive electrode slurry.

[0059] Comparative Example 1

[0060] In this comparative example, a sodium ion battery was prepared using a technical solution substantially similar to that of Example 1, with the only difference being that the particle size D50 of NaFePO4 was 0.2 μm.

[0061] Comparative Example 2

[0062] In this comparative example, a sodium ion battery was prepared using a technical solution substantially similar to that of Example 1, with the only difference being that the particle size D50 of NaFePO4 was 2 μm.

[0063] Comparative Example 3

[0064] This comparative example adopts a technical solution substantially the same as that of Example 1 to prepare a sodium ion battery, the only difference being that, when preparing the positive electrode slurry, NaFePO4 is uniformly mixed with the positive electrode binder and the positive electrode conductor in a mass ratio of 10:1:1, and the mass proportion of polyvinylidene fluoride in the positive electrode binder is 30%.

[0065] The positive and negative electrode sheets prepared in the above embodiments and comparative examples were of the same size, and other components in the battery were also the same. The following electrical performance tests were performed.

[0066] Test Example 1

[0067] 1. Test capacity retention under the same conditions:

[0068] Table 1 Number of charge and discharge cycles at 5C and capacity retention at 45°C

[0069]

[0070]

[0071] The sodium ion batteries prepared in Examples 1-6 have good capacity retention and long cycle life under high-power charge and discharge conditions. The NaFePO4 particle size of Comparative Example 1 is too small, resulting in a decrease in the strength retention of the positive electrode structure, which reduces the cycle capacity of the battery. The NaFePO4 particle size of Comparative Example 2 is too large, resulting in a smaller specific surface area, which makes the positive electrode structure less regular and the strength also decreases, causing the cycle capacity of the battery to decrease. The concentration of polyvinylidene fluoride in the positive electrode binder of Comparative Example 3 is large, and the overall amount of positive electrode binder used is small, which reduces the uniformity of the dispersion of polyvinylidene fluoride, weakens the adhesion to other materials, and causes the positive electrode structure strength to decrease, thereby causing the cycle capacity of the battery to decrease.

[0072] 2. Test power density under the same conditions:

[0073] Table 2 Power density test data

[0074] Power density / (kW / kg) Example 1 6.53 Example 2 6.29 Example 3 6.41 Example 4 6.76 Example 5 6.84 Example 6 6.95 Comparative Example 1 6.08 Comparative Example 2 5.87 Comparative Example 3 5.95

[0075] The batteries prepared in Examples 1-6 have a high power density. The raw materials used to prepare the positive electrode slurries in Examples 5 and 6 also include N-phthalylglycine. The hydrophilic carboxyl groups in N-phthalylglycine promote the wetting of the electrolyte on the microporous surface of the positive electrode, increasing the rate at which sodium ions leave and re-embed into the positive electrode. The benzene heterocycle has a water-repellent effect, reducing excessive water penetration into the bonding structure, reducing damage to the positive electrode structure during battery charging and discharging, and improving the battery's power density.

[0076] The NaFePO4 particle size of Comparative Example 1 is too small. Although it increases the specific surface area, the holes formed are also small, which is not conducive to the infiltration of the electrolyte and the formation of a thicker SEI film, thereby reducing the sodium ion migration rate and reducing the power density. The NaFePO4 particle size of Comparative Example 2 is too large, which makes the specific surface area of ​​NaFePO4 smaller, reduces the amount of sodium ions released, reduces the rate of sodium ion release, and reduces the power density. The polyvinylidene fluoride concentration of Comparative Example 3 is large, and the overall amount of positive electrode binder is small, that is, the amount of solvent is reduced, the space occupied by the solvent is reduced, and the holes formed after the solvent evaporates are reduced, which is not conducive to the infiltration of the electrolyte and the formation of a thicker SEI film, thereby reducing the migration efficiency of the effective sodium ions and reducing the power density of the battery.

[0077] 3. Test charging speed under the same conditions

[0078] Table 3 Charging speed test

[0079]

[0080] The batteries prepared in Examples 1-6 had a relatively fast charging speed. Example 4 had the fastest charging speed because the positive electrode current collector was heated to 200°C before the positive electrode slurry was applied to the positive electrode current collector, which reduced the contact resistance and thus increased the charging speed.

[0081] The NaFePO4 particle size in Comparative Example 1 is too small. Although the specific surface area is increased, the pores formed are also small, which is not conducive to the infiltration of the electrolyte and the formation of a thicker SEI film, which reduces the sodium ion migration rate and the charging speed. The NaFePO4 particle size in Comparative Example 2 is too large, which makes the specific surface area of ​​NaFePO4 smaller, reduces the amount of sodium ions released, and reduces the rate of sodium ion release, which reduces its charging speed. The positive electrode of Comparative Example 3 has few pores, which is not conducive to the infiltration of the electrolyte and the formation of a thicker SEI film, which reduces the migration efficiency of effective sodium ions and thus reduces the charging speed of the battery.

[0082] The present application controls the NaFePO4 particle size to be moderately small, increases its specific surface area, increases the amount and rate of sodium ion release, controls the positive electrode binder with a larger molecular weight, is conducive to creating more and larger pores, is conducive to the penetration of the electrolyte, and thus is conducive to the migration of sodium ions. In addition, it also controls the addition of a larger volume but lower concentration of positive electrode binder, on the one hand, promotes the dispersion of polymer solutes in NaFePO4 particles, on the other hand, increases the amount of solvent so that the evaporation of the solvent can form more pores, which is conducive to the penetration of the electrolyte, improves the sodium ion mobility, and improves the cycle performance, power performance and charging speed of the battery. The present application also heats the current collector to above the melting point and outside the boiling point of the polymer solute, so that after the positive electrode slurry is coated on the current collector, the polymer solute melts on the current collector, increases the contact area, reduces the contact resistance, and thus improves the power density and charging speed of the battery. The present application also adds N-phthaloylglycine to the positive electrode slurry. The hydrophilic carboxyl group in N-phthaloylglycine promotes the wetting effect of the electrolyte on the microporous surface of the positive electrode, increases the speed at which sodium ions leave the positive electrode and re-embed into the positive electrode, and the benzene heterocycle has a water-repellent effect, reduces excessive penetration of water into the bonding structure, reduces the damage to the positive electrode structure caused by battery charging and discharging, and improves the power density and cycle life of the battery.

[0083] Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments, or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a high-power and long-life sodium-ion battery, characterized in that: include: NaFePO4 is uniformly mixed with a positive electrode binder and a positive electrode conductive agent in a mass ratio of 10:(2-3):(0.5-1.5) to obtain a positive electrode slurry; the particle size D50 of the NaFePO4 is 0.5-1 μm; the positive electrode slurry is coated on a positive electrode current collector, and dried and solidified to obtain a positive electrode sheet; wherein the positive electrode binder includes a polymer solute and a solvent, and the mass proportion of the polymer solute in the positive electrode binder is 10-15%; The hard carbon is mixed with a negative electrode binder and a negative electrode conductive agent to obtain a negative electrode slurry; the negative electrode slurry is coated on a negative electrode current collector, and dried and solidified to obtain a negative electrode sheet; The positive electrode sheet, the negative electrode sheet and the separator are immersed in an electrolyte and packaged into a sodium ion battery.

2. The method for preparing a high-power and long-life sodium-ion battery according to claim 1, wherein The polymer solute is polyvinylidene fluoride; the molecular weight of the polyvinylidene fluoride is 500,000 to 1,000,000.

3. The method for preparing a high-power and long-life sodium-ion battery according to claim 1, wherein: Before coating the positive electrode slurry on the positive electrode current collector, the positive electrode current collector is first heated to a temperature above the melting point and below the boiling point of the polymer solute, and the heating temperature is lower than the melting point of the positive electrode current collector, and then the positive electrode slurry is coated on the positive electrode current collector.

4. The method for preparing a high-power and long-life sodium-ion battery according to claim 1, wherein: The electrolyte is an aqueous electrolyte; the negative electrode binder is a polymer material with a negative surface charge in water.

5. The method for preparing a high-power and long-life sodium-ion battery according to claim 4, wherein: The negative electrode binder is a carboxymethyl cellulose solution or a hydroxyethyl cellulose solution.

6. The method for preparing a high-power and long-life sodium-ion battery according to claim 5, characterized in that: The mass concentration of the polymer material in the negative electrode binder is 0.5-1%. The hard carbon, the negative electrode binder, and the negative electrode conductive agent are mixed in a mass ratio of 8:(0.5-1.5):(0.5-1.5).

7. The method for preparing a high-power and long-life sodium-ion battery according to claim 1, wherein: The raw materials for preparing the positive electrode slurry also include N-phthalylglycine; NaFePO4 is evenly mixed with a positive electrode binder, a positive electrode conductor, and N-phthalylglycine in a mass ratio of 10: (2~3): (0.5~1.5): (0.1~0.2) to obtain the positive electrode slurry.

8. The method for preparing a high-power and long-life sodium-ion battery according to claim 1, wherein: The positive electrode conductive agent is acetylene black, carbon nanotubes or Ketjen black; the negative electrode conductive agent is acetylene black, carbon nanotubes or Ketjen black; the D50 particle size of the acetylene black is 30~45nm; the D50 length of the carbon nanotubes is 10~30μm; the D50 particle size of the Ketjen black is 20~100nm.

9. The method for preparing a high-power and long-life sodium-ion battery according to claim 1, wherein: The solute of the electrolyte is NaPF6, and the solvent is a mixture of monomethyl acrylate, ethylene glycol dimethyl ether and methanol; the concentration of NaPF6 in the electrolyte is 0.5M~1.5M; hydroquinone monomethyl ether is also added to the electrolyte, and the mass concentration of hydroquinone monomethyl ether in the electrolyte is 0.05~0.15%.

10. A high-power and long-life sodium ion battery, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.

Citation Information

Patent Citations

  • Sodium ion liquid battery doped with carbon nanotubes and preparation method thereof

    CN117855577A

  • Lithium ion battery and preparation method therefor

    WO2022268147A1