A method for ultrafast synthesis of sodium battery carbon anode materials

Abstract

The application discloses a method for synthesizing a carbon negative electrode material of a sodium battery in an ultrafast mode, and belongs to the technical field of sodium battery negative electrode materials. The method uses an ultrafast pulse laser method, adopts various carbon precursors and additives, and can synthesize a carbon negative electrode of a sodium battery with ideal performance in an ultra-short time. The process and material design are simple and efficient. Through laser pulse preparation and carbon material design, different types of carbon precursors can be prepared into carbon negative electrodes with high initial efficiency and high performance in an ultra-short time. The process can realize the flow production and the standardized production of high-performance sodium battery carbon negative electrode materials under different carbon precursor conditions, and is beneficial to the rapid development of sodium batteries.

Description

Technical Field

[0001] This invention relates to a technology in the field of sodium-ion battery manufacturing, specifically a method for ultrafast synthesis of carbon anode materials for sodium batteries. Background Technology

[0002] Sodium-ion batteries possess advantages such as abundant sodium resources, long cycle life, and low maintenance costs. They can not only compensate for the shortcomings of lithium-ion batteries and alleviate lithium resource shortages, but also replace environmentally unfriendly lead-acid batteries, ensuring national energy security and sustainable social development. They have broad application prospects in the field of grid energy storage. Developing low-cost, high-performance carbon anode materials is key to realizing the commercial application of sodium-ion batteries.

[0003] However, current sodium-ion battery carbon anode materials prepared using traditional high-temperature pyrolysis methods and carbon precursors suffer from numerous problems, such as easy graphitization, low initial efficiency, and high cost, which have hindered their application in sodium-ion battery carbon anode materials. This is mainly due to the slow heating, low energy intensity, and large energy loss inherent in traditional preparation methods. Furthermore, different carbon precursors have different compositions, resulting in significant variations in the electrochemical performance of carbon materials obtained through traditional methods, making it difficult to achieve standardized and streamlined production of high-performance carbon anode materials. Therefore, further innovation in preparation methods and material design is still needed for high-performance carbon anodes. Summary of the Invention

[0004] To address the aforementioned shortcomings of current technologies, this invention provides a method for ultrafast synthesis of sodium battery carbon anode materials, which has advantages such as short synthesis time, high speed, and high product performance.

[0005] This invention is achieved through the following technical solution:

[0006] A method for ultrafast synthesis of sodium battery carbon anode material involves using carbon precursor and additives as raw materials, mixing them thoroughly, and then preparing the sodium battery carbon anode material in 1-10 minutes using an ultrafast pulsed laser method under an inert atmosphere.

[0007] Furthermore:

[0008] The carbon precursor is selected from any one or more of starch, sucrose, lignocellulose, bamboo, phenolic resin, polyethylene, polystyrene, polytetrafluoroethylene, polyvinyl chloride resin, graphene, asphalt, petroleum coke, anthracite, and mesophase asphalt. Preferably, the carbon precursor combination is a combination of two materials in a ratio of 1:10 to 1:1.

[0009] The additive is selected from any one of sodium salt, strong acid, and lithium salt, and its mass fraction is 2%-30% of the total mass of carbon precursor, preferably 10-15%.

[0010] The sodium salt is selected from any one or more of the following: sodium chloride, sodium sulfate, sodium thiosulfate, sodium carbonate, sodium fluoride, sodium nitrate, sodium phosphate, sodium acetate, sodium citrate, sodium malate, sodium trifluoromethanesulfonate, sodium difluorosulfonamide, sodium difluoromethanesulfonamide, sodium difluorophosphate, sodium hexafluorophosphate, disodium ethylenediaminetetraacetate, and sodium peroxide.

[0011] The strong acid is selected from any one or more of the following: sulfuric acid, nitric acid, hydrochloric acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, benzoic acid, salicylic acid, caffeic acid, lactic acid, pyruvic acid, acetoacetic acid, β-hydroxybutyric acid, oxaloacetic acid, glutaric acid, and adipic acid.

[0012] The lithium salt is selected from any one or more of lithium carbonate, lithium hydroxide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium boron trifluoride, lithium bis(trifluoromethanesulfonyl)imide, lithium dioxalate borate, and lithium difluorooxalate borate.

[0013] The thorough mixing is achieved by, but not limited to, grinding or ball milling, preferably ball milling, for a time of 3-20 hours.

[0014] The ultrafast pulsed laser method described above has a heating temperature of 400-1800℃ and a heating time of 1-10 min.

[0015] The ultrafast pulsed laser method described above uses a laser wavelength of 500nm-1200nm.

[0016] The inert atmosphere described herein uses nitrogen or argon as the gas.

[0017] The carbon anode materials prepared by the above method in this invention can achieve a carbon yield of over 60%.

[0018] The present invention also provides an application of the carbon anode material prepared above in a sodium-ion battery.

[0019] The carbon anode material prepared by this invention, when applied to sodium-ion batteries, showed that its first-cycle coulombic efficiency could reach over 90%, and its specific capacity reached 350 mAh g. -1 The stable cycle capacity retention rate reaches over 98%.

[0020] The beneficial effects of this invention are as follows:

[0021] This invention discloses a method for ultrafast synthesis of sodium-ion battery carbon anode materials. Utilizing an ultrafast pulsed laser method and employing various carbon precursors and additives, it enables the synthesis of sodium-ion battery carbon anode materials with ideal performance in an ultra-short time. This process and material design are simple and efficient. Through laser pulse preparation and carbon material design, different types of carbon precursors can be prepared into high-efficiency, high-performance carbon anodes in an ultra-short time. This allows for the streamlined and standardized production of high-performance sodium-ion battery carbon anode materials under different carbon precursor conditions, which is beneficial to the rapid development of sodium-ion batteries.

[0022] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Attached Figure Description

[0023] Figure 1 Scanning electron microscope (SEM) images of the carbon anode materials prepared in Example 1 and Comparative Example 1.

[0024] Figure 2 Transmission electron microscopy (TEM) images of the carbon anode materials prepared in Example 1 and Comparative Example 1.

[0025] Figure 3 The images show the XRD patterns of the carbon anode materials prepared in Example 1 and Comparative Example 1.

[0026] Figure 4 The discharge specific capacity and first-cycle coulombic efficiency of the carbon anode materials prepared in Example 1 and Comparative Example 1 are compared.

[0027] Figure 5 This serves as a comparison of the cycle performance of the carbon anode materials prepared in Example 1 and Comparative Example 1. Detailed Implementation

[0028] Example 1

[0029] A method for ultrafast synthesis of carbon anode materials for sodium batteries includes the following steps:

[0030] (1) Take 100g of mesophase pitch, add 10wt% polyethylene resin, and ball mill for 10h to mix thoroughly.

[0031] (2) Add 10wt% sodium peroxide and ball mill for 10 hours to mix thoroughly;

[0032] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a pulsed laser device (laser wavelength 500nm-1200nm, energy density 1-500J / cm). 2 In the pulse width 3ps, frequency 1-10MHz, the maximum temperature is set to 1200℃ and burned for 5min.

[0033] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0034] carbon precursor Sodium peroxide Ball grinding time Burning temperature Burning time Carbon production quality 110g 11g 20h 1200℃ 5min 90g .

[0035] Comparative Example 1

[0036] A method for preparing a carbon anode material for sodium batteries includes the following steps:

[0037] (1) Take 100g of mesophase pitch, add 10wt% polyethylene resin, and ball mill for 10h to mix thoroughly.

[0038] (2) Add 10wt% sodium peroxide and ball mill for 10 hours to mix thoroughly;

[0039] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a conventional heating tube furnace, with the maximum temperature set at 1200℃ and the calcination time at 12h.

[0040] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0041] carbon precursor Sodium peroxide Ball grinding time Burning temperature roasting time Carbon production quality 110g 11g 20h 1200℃ 12h 50g .

[0042] Product structure:

[0043] like Figures 1-3 As shown, the carbon anode materials prepared in Example 1 and Comparative Example 1 were compared by scanning electron microscopy, transmission electron microscopy, and XRD, respectively. It can be found that the carbon anode material prepared by laser pulse in Example 1 has fewer graphite layers and a lower degree of graphitization compared with the carbon anode material prepared by conventional process in Comparative Example 1.

[0044] Performance testing:

[0045] Preparation of sodium battery carbon electrode: The carbon anode material of sodium battery prepared above is weighed with carbon black, binder (PVDF) and carbon anode material in a mass ratio of 1:1:8, and then thoroughly mixed and ground. Then N-methylpyrrolidone (NMP) is added and ground together to make the carbon black and binder uniformly mixed. Aluminum foil is used as the current collector, and the slurry is uniformly coated on the surface of the current collector using a coating tool to prepare the sodium battery carbon electrode.

[0046] Sodium-ion half-cell assembly: Using sodium foil as the negative electrode, a sodium battery carbon electrode as the positive electrode, glass fiber as the separator, and 1.0M NaPF6 / Diglyme as the electrolyte, a sodium-ion half-cell is assembled. Assembly is performed in an argon atmosphere glove box with H2O < 0.1 ppm and O2 < 0.1 ppm. The assembly process is as follows: 1. Stack the negative electrode shell, spring sheet, gasket, and negative electrode sheet in that order; 2. Add electrolyte to the negative electrode sheet, place the separator, add electrolyte again, then place the carbon electrode sheet, and finally attach the positive electrode shell; 3. Compact the battery using a sealing machine under a pressure of 750 Psi to complete the assembly.

[0047] The assembled sodium-ion half-cells were then subjected to charge-discharge capacity and cycle performance tests, as detailed below:

[0048] Test conditions: Constant current charge and discharge measurements of the battery were recorded on a Blue Electric testing instrument at 25℃. The charge and discharge voltage ranges of the half-cell were 0.1C (1C = 300mAh g). -1 ), 0.01-2.5V.

[0049] Charge / discharge capacity test:

[0050] Install the test battery on the test instrument and place it in a test environment of (25±1)℃. Set the following program: let it stand for 8 hours; discharge it to 0V with a constant current of 0.1C; let it stand for 5 minutes; then charge it to 2.5V with a constant current of 0.1C; repeat the above charge and discharge steps 5 to 10 times.

[0051] Cyclic performance testing:

[0052] Install the test battery on the test instrument and place it in a test environment of (25±1)℃. Set the following procedure: let it stand for 8 hours; discharge it to 0V with a constant current of 0.1C; let it stand for 5 minutes; then charge it to 2.5V with a constant current of 0.1C; repeat the above charge and discharge steps.

[0053] like Figure 4 As shown, the carbon anode material prepared in Example 1 achieved a first-cycle coulombic efficiency of 91%, while the carbon anode material prepared in Comparative Example 1 only achieved a first-cycle coulombic efficiency of 75%. Figure 5 It can be seen that the carbon anode material obtained in Example 1 has a significantly higher discharge capacity than that in Comparative Example 1, and its capacity retention rate reaches 99% after 100 cycles.

[0054] Example 2

[0055] A method for ultrafast synthesis of carbon anode materials for sodium batteries includes the following steps:

[0056] (1) Take 100g of petroleum coke, crush it, add 10wt% polyvinyl chloride resin, and ball mill for 10h to mix thoroughly.

[0057] (2) Add 10wt% sodium acetate and ball mill for 10 hours to mix thoroughly;

[0058] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a pulsed laser device (laser wavelength 500nm-1200nm, 1-500J / cm). 2 In the 3ps, 1-10MHz mode, the maximum temperature was set to 1000℃ and burned for 4 minutes.

[0059] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0060] carbon precursor Sodium acetate Ball grinding time Burning temperature Burning time Carbon production quality 110g 11g 20h 1000℃ 4min 100g .

[0061] Comparative Example 2

[0062] A method for preparing a carbon anode material for sodium batteries includes the following steps:

[0063] (1) Take 100g of petroleum coke, crush it, add 10wt% polyvinyl chloride resin, and ball mill for 10h to mix thoroughly.

[0064] (2) Add 10wt% sodium acetate and ball mill for 10 hours to mix thoroughly;

[0065] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a conventional heating tube furnace, with the maximum temperature set at 1200℃ and the calcination time at 12h.

[0066] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0067] carbon precursor Sodium acetate Ball grinding time Burning temperature roasting time Carbon production quality 110g 11g 20h 1200℃ 12h 55g .

[0068] Example 3

[0069] A method for ultrafast synthesis of carbon anode materials for sodium batteries includes the following steps:

[0070] (1) Take 100g of bamboo, crush it, add 10wt% anthracite, and ball mill for 10h to mix thoroughly;

[0071] (2) Add 10wt% sodium nitrate and ball mill again for 10h to mix thoroughly to obtain a mixed precursor;

[0072] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a pulsed laser device (laser wavelength 500nm-1200nm, 1-500J / cm). 2 In the 3ps, 1-10MHz mode, the maximum temperature was set to 1400℃ and burned for 6 minutes.

[0073] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0074] carbon precursor Sodium hydroxide Ball grinding time Burning temperature Burning time Carbon production quality 110g 11g 20h 1400℃ 7min 100g .

[0075] Comparative Example 3

[0076] A method for preparing a carbon anode material for sodium batteries includes the following steps:

[0077] (1) Take 100g of bamboo, crush it, add 10wt% anthracite, and ball mill for 10h to mix thoroughly;

[0078] (2) Add 10wt% sodium nitrate and ball mill again for 10h to mix thoroughly to obtain a mixed precursor;

[0079] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a conventional heating tube furnace, with the maximum temperature set at 1600℃ and the calcination time at 12h.

[0080] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0081] carbon precursor Sodium acetate Ball grinding time Burning temperature roasting time Carbon production quality 110g 11g 20h 1600℃ 12h 40g .

[0082] Example 4

[0083] A method for ultrafast synthesis of carbon anode materials for sodium batteries includes the following steps:

[0084] (1) Take 100g of phenolic resin, crush it, add 10wt% petroleum coke, and ball mill for 10h to mix thoroughly.

[0085] (2) Add 10wt% sodium fluoride and ball mill for 10h to mix thoroughly;

[0086] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a pulsed laser device (laser wavelength 500nm-1200nm, 1-500J / cm). 2 In the 3ps, 1-10MHz mode, the maximum temperature was set to 1600℃ and burned for 10 minutes.

[0087] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0088] carbon precursor Sodium fluoride Ball grinding time Burning temperature Burning time Carbon production quality 110g 11g 20h 1600℃ 10min 90g .

[0089] Example 5

[0090] A method for ultrafast synthesis of carbon anode materials for sodium batteries includes the following steps:

[0091] (1) Take 100g of lignocellulose, add 20wt% asphalt, and ball mill for 15h to mix thoroughly;

[0092] (2) Add 10wt% sodium hydroxide and ball mill again for 10h to mix thoroughly to obtain a mixed precursor;

[0093] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a pulsed laser device (laser wavelength 500nm-1200nm, 500W, 3ps, 1MHz-10 MHz), and the maximum temperature was set to 1100℃ for 5min.

[0094] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0095] carbon precursor Sodium hydroxide Ball grinding time Burning temperature Burning time Carbon production quality 120g 12g 25h 1100℃ 5min 100g .

[0096] Example 6

[0097] A method for ultrafast synthesis of carbon anode materials for sodium batteries includes the following steps:

[0098] (1) Take 100g of starch, add 20wt% sucrose, and ball mill for 10 hours to mix thoroughly;

[0099] (2) Add 10wt% sodium phosphate and ball mill again for 10h to mix thoroughly to obtain a mixed precursor;

[0100] (3) Under a nitrogen inert gas atmosphere, the obtained mixed precursor was placed in a pulsed laser device (laser wavelength 500nm-1200nm, 1-500J / cm). 2 In the 3ps, 1-10MHz mode, the maximum temperature was set to 500℃ and burned for 2 minutes.

[0101] The experimental data for the carbon materials prepared according to the above examples are as follows, under normal chemical laboratory conditions:

[0102] carbon precursor Sodium phosphate Ball grinding time Burning temperature Burning time Carbon production quality 120g 12g 20h 500℃ 2min 84g .

[0103] The sodium battery carbon anode materials prepared in Examples 1-6 and Comparative Examples 1-3 of this invention were assembled into sodium-ion half-cells according to the aforementioned method, and their performance was tested respectively, as shown in Table 1.

[0104] Table 1

[0105]

[0106] Summarize:

[0107] Compared with existing technologies, the present invention provides a method for ultrafast synthesis of sodium battery carbon anode materials. This method utilizes an ultrafast pulsed laser method, employing various carbon precursors and additives to synthesize high-performance sodium battery carbon anodes in an ultra-short time. The process and material design are simple and efficient. Through laser pulse preparation and carbon material design, different types of carbon precursors can be prepared into high-efficiency, high-performance carbon anodes in an ultra-short time. This enables the standardized and streamlined production of high-performance sodium battery carbon anode materials under different carbon precursor conditions, which is beneficial to the rapid development of sodium batteries. Compared with current preparation methods, this method offers advantages such as shorter preparation time, higher speed, and higher product performance.

[0108] The above-described specific implementations can be partially adjusted by those skilled in the art in different ways without departing from the principles and purpose of the present invention. The scope of protection of the present invention is defined by the claims and is not limited to the above-described specific implementations. All implementation schemes within the scope of the claims are bound by the present invention.

Claims

1. A method for ultrafast synthesis of sodium battery carbon anode material, comprising: using carbon precursor and additives as raw materials, thoroughly mixing them, and then using an ultrafast pulsed laser method in an inert atmosphere to prepare sodium battery carbon anode material within 1-10 minutes; The carbon precursor is selected from any one or more of starch, sucrose, lignocellulose, bamboo, phenolic resin, polyethylene, polystyrene, polytetrafluoroethylene, polyvinyl chloride resin, graphene, asphalt, petroleum coke, anthracite, and mesophase asphalt. The additive is a sodium salt, and its mass fraction is 2%-30% of the total mass of the carbon precursor. The ultrafast pulsed laser method described herein has a heating temperature of 400-1800℃, a heating time of 1-10 min, and a laser wavelength of 500nm-1200nm.

2. The method for ultrafast synthesis of sodium battery carbon anode material according to claim 1, characterized in that: The sodium salt is selected from any one or more of sodium chloride, sodium sulfate, sodium thiosulfate, sodium carbonate, sodium fluoride, sodium nitrate, sodium phosphate, sodium acetate, sodium citrate, sodium malate, sodium trifluoromethanesulfonate, sodium difluorosulfonamide, sodium difluoromethanesulfonamide, sodium difluorophosphate, sodium hexafluorophosphate, disodium ethylenediaminetetraacetate, and sodium peroxide.

3. The method for ultrafast synthesis of sodium battery carbon anode material according to claim 1, characterized in that: The thorough mixing is achieved by grinding or ball milling for 3-20 hours.

4. The method for ultrafast synthesis of sodium battery carbon anode material according to claim 1, characterized in that: The inert atmosphere described herein uses nitrogen or argon as the gas.

5. A sodium battery carbon anode material prepared by the method according to any one of claims 1-4.

6. The application of the sodium battery carbon anode material according to claim 5 in a sodium-ion battery.

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