CN118343749A - Negative electrode material of sodium ion battery and preparation method thereof - Google Patents
Negative electrode material of sodium ion battery and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 48
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 99
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007873 sieving Methods 0.000 claims abstract description 20
- 239000003077 lignite Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims description 21
- 238000005087 graphitization Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000005347 demagnetization Effects 0.000 claims 1
- 229910021385 hard carbon Inorganic materials 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007833 carbon precursor Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode material of a sodium ion battery and a preparation method thereof. The method comprises the following steps: crushing raw lignite for the first time; graphitizing the materials after primary crushing; sieving and demagnetizing the graphitized material; ball milling is carried out on the materials subjected to sieving and demagnetizing; drying the ball-milled material; scattering the dried materials; sieving and demagnetizing the scattered materials to obtain the negative electrode material of the sodium ion battery. The material used by the invention has low cost, wide sources, high capacity and high first week coulomb efficiency, higher cost performance and simple preparation method and process, and is suitable for commercial application.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a negative electrode material of a sodium ion battery and a preparation method thereof.
Background
Sodium ion batteries are receiving attention as a new battery technology. The development and application of high-performance and low-cost negative electrode materials are important preconditions for the commercialization of sodium ion batteries. Graphite is widely used as a negative electrode material in lithium batteries, but graphite is difficult to use as a negative electrode in sodium ion batteries due to thermodynamic reasons and its inherent structure.
At present, the prior art adopts coal and hard carbon precursors as raw materials to prepare a sodium ion battery anode material, and the main design concept is that the sodium ion battery anode material is obtained by directly carrying out high-temperature pyrolysis on the coal as the raw materials under inert atmosphere or carrying out high-temperature pyrolysis on the coal and hard carbon precursors as the raw materials under inert atmosphere after adding solvents, mechanically mixing and drying the mixture, and then carrying out high-temperature pyrolysis under the inert atmosphere.
The sodium ion battery cathode material prepared by the method adopts coal as a raw material, the coal is used as a soft carbon precursor, the capacity of the carbon material obtained by high-temperature pyrolysis is low and is mostly lower than 250mAh/g, the initial cycle coulomb efficiency is about 80%, and the sodium ion battery cathode material with higher capacity is difficult to obtain by high-temperature pyrolysis even after the sodium ion battery cathode material is mixed with a hard carbon precursor. And the hard carbon precursor is simply adopted as a raw material for high-temperature pyrolysis, so that the anode material with high capacity (more than 280 mAh/g) and high first-week coulomb efficiency (more than 85%) can be obtained, but the cost is high, and the large-scale industrialized production is difficult. The common negative electrode material of the sodium ion battery which can be commercialized on a large scale is generally hard carbon, but the prepared hard carbon material has poor electrochemical performance, the capacity is generally less than 280mAh/g, the first-week coulomb efficiency is generally less than 80%, and the first-week coulomb efficiency and the capacity are difficult to simultaneously consider.
Disclosure of Invention
The sodium ion battery anode material and the preparation method thereof provided by the invention have the advantages that the used material is low in cost and wide in source, meanwhile, the material has high capacity and high first-week coulomb efficiency, the cost performance is high, the preparation method is simple in process, and the method is suitable for commercial application.
In a first aspect, the present invention provides a method for preparing a negative electrode material of a sodium ion battery, the method comprising:
Crushing raw lignite for the first time;
Graphitizing the materials after primary crushing;
sieving and demagnetizing the graphitized material;
ball milling is carried out on the materials subjected to sieving and demagnetizing;
Drying the ball-milled material;
scattering the dried materials;
Sieving and demagnetizing the scattered materials to obtain the negative electrode material of the sodium ion battery.
Optionally, the primary crushing of the raw lignite comprises:
Carrying out jaw breaking or hammer breaking pretreatment on raw lignite to obtain a coarsely crushed material;
the coarsely crushed materials are crushed for the first time, and the granularity is controlled to be 10-20 mu m.
Optionally, graphitizing the material after primary pulverization includes:
charging the materials after primary crushing into a graphitization furnace;
heating, preserving heat and cooling according to a normal graphitization temperature curve;
and discharging the materials layer by layer in the sequence from top to bottom.
Optionally, the heating, heat preservation and cooling according to the normal graphitization temperature curve comprises:
Continuously powering the graphitization furnace for 80-90 hours to enable the temperature to reach 2800-3000 ℃;
keeping the graphitization furnace at the constant temperature of 2800-3000 ℃ for 10-15 hours;
air cooling for 5-8 days, water cooling for 5-8 days, and cooling to below 50-60 ℃.
Optionally, the sieving and demagnetizing the graphitized material comprises:
sequentially packing graphitized materials, and marking;
sieving with 50-150 mesh sieve;
the materials on the sieve and the demagnetizing materials are collected separately.
Optionally, the ball milling treatment of the material after sieving and demagnetizing comprises:
Pouring materials within 100g into a ball milling tank;
weighing grinding balls according to a ball-material ratio of 8-20 times, and placing the grinding balls into a ball milling tank;
Adding secondary pure water into the ball milling tank, wherein the volume of the water accounts for 1/2-2/3 of that of the whole ball milling tank;
Ball milling is carried out.
Optionally, the drying the ball-milled material comprises:
cleaning the inside of the electrothermal blowing drying oven;
placing the ball-milled material and the grinding balls into a tray of an oven, wherein the temperature of the oven is set to 105-110 ℃ and the time is set to 24-30 hours.
Optionally, the scattering the dried material includes:
when the temperature of the dried material is reduced to room temperature, the material and the grinding balls are put into a self-sealing bag together;
Manually kneading and uniformly mixing;
The materials and the grinding balls are screened by a 20-60 mesh sieve, and the grinding balls and the materials are separated.
Optionally, the sieving and demagnetizing the scattered material to obtain the sodium ion battery anode material comprises:
And (5) after the scattered materials are visually examined to be free of foreign matters, sieving the materials through a 325-mesh sieve to obtain the negative electrode material of the sodium ion battery.
In a second aspect, the invention provides a sodium ion battery anode material, which is prepared by adopting the preparation method of the sodium ion battery anode material.
The sodium ion battery anode material and the preparation method thereof provided by the embodiment of the invention have the advantages that the used raw material lignite is low in cost and wide in source, the prepared anode material is applied to sodium ion batteries, has high capacity and high first-week coulomb efficiency, the cost performance is high, and the preparation method is simple in process and suitable for commercial application.
Drawings
FIG. 1 is a flow chart of a method for preparing a negative electrode material for a sodium ion battery according to an embodiment of the present invention;
Fig. 2 and fig. 3 are microscopic morphology diagrams of a negative electrode material of a sodium ion battery according to an embodiment of the present invention;
Fig. 4 is an XRD test chart of the negative electrode material of the sodium ion battery provided by the embodiment of the invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a preparation method of a sodium ion battery anode material, as shown in fig. 1, comprising the following steps:
s11, crushing the raw lignite for the first time.
Before crushing, firstly, primarily checking raw material lignite, determining the moisture, ash content, volatile matters and sulfur content of the raw material lignite, and determining whether drying treatment is required according to detection indexes, specifically, when the moisture content of the raw material lignite is more than 2 percent, drying treatment is required; and then carrying out jaw breaking or hammer breaking pretreatment on the raw lignite to obtain a coarsely crushed material.
Then, the material after coarse crushing is crushed for the first time, and the granularity is controlled to be 10-20 mu m.
S12, graphitizing the material after primary crushing.
Firstly, checking the graphitization furnace before charging to ensure that the graphitization furnace can normally run, detecting the loose packing density of the materials before charging to determine the charging amount, and charging the materials after primary crushing into a crucible and then charging into the furnace.
Then, heating, heat preservation and cooling are carried out according to a normal graphitization temperature curve, and the specific steps are as follows:
Continuously powering the graphitization furnace for 80-90 hours to enable the temperature to reach 2800-3000 ℃; then keeping the graphitization furnace at the constant temperature of 2800-3000 ℃ for 10-15 hours; then air cooling is carried out for 5-8 days, water cooling is carried out for 5-8 days, cooling is carried out, and then discharging is carried out layer by layer according to the sequence from top to bottom.
Wherein, when discharging after cooling, discharging is carried out at the temperature of 50-60 ℃ generally, so as to prevent the rebound of temperature and the oxidation of hard carbon materials.
Graphitizing the material after primary crushing has the following effects:
The internal main structure of lignite is continuously raised along with graphitization temperature, cracks are generated along the two-phase interface of mineral distribution, and local atomic arrangement is gradually ordered to generate isotropic polycrystalline structure graphite. The micro carbon spheres are separated out from the surface and cracks of the lignite from 2000 ℃, and the volume of the carbon spheres is continuously increased along with the continuous increase of the temperature until the granularity reaches about 100 microns, so that the micro carbon spheres are combined and broken. Continuously heating to 3000 ℃ to form anisotropic lamellar wrinkled graphite crystals;
the quartz decomposed from the primary quartz and clay minerals in the lignite reacts with carbon at 1800 ℃ to generate graphitized intermediate product silicon carbide, and the product is decomposed at 2600 ℃ to generate straight graphite sheets with extremely high regularity. Therefore, amorphous carbon in different chemical environments in raw coal can be converted into graphite, but the microstructure of the crystal is not the same.
Carbon-based materials are attractive as negative electrode materials for sodium ion batteries due to their good cost effectiveness and electrochemical stability. Generally, as the heat treatment temperature increases, the degree of graphitization increases, so that the surface area and porosity of the hard carbon decrease, and the defect content decreases. The surface area, porosity and defect content of hard carbon are important factors affecting their electrochemical properties, including reversible capacity, operating voltage and initial coulombic efficiency, all improved upon graphitization.
S13, sieving and demagnetizing the graphitized material.
Sequentially packing graphitized materials, and marking; then sieving with a 50-150 mesh sieve; the materials on the sieve and the demagnetizing materials are collected separately.
S14, ball milling is carried out on the materials subjected to screening and demagnetizing.
Ball milling is carried out by adopting a planetary ball mill by adopting a wet method, and the medium is water. The method comprises the following steps:
pouring the weighed materials into a ball mill tank, wherein the weight of the materials is recommended to be less than 100 g; weighing grinding balls according to a ball-material ratio of 8-20 times, and placing the grinding balls into a ball milling tank; adding secondary pure water into the ball milling tank, wherein the volume of the water accounts for about 1/2-2/3 of the whole ball milling tank; ball milling is carried out.
And S15, drying the ball-milled material.
Firstly, cleaning the inside of an electrothermal blowing drying oven; then, placing the ball-milled material and the grinding balls into a tray of an oven, wherein the temperature of the oven is set to 105-110 ℃ and the time is set to 24-30 hours.
S16, scattering the dried materials.
When the temperature of the dried material is reduced to room temperature, the material and the grinding balls are put into a self-sealing bag together; then manually kneading and evenly mixing; and then the materials and the grinding balls are screened by a 20-60-mesh sieve together, and the grinding balls and the materials are separated.
S17, sieving and demagnetizing the scattered materials to obtain the negative electrode material of the sodium ion battery.
After the separated materials are visually inspected to be free of foreign matters, the materials are sieved by a 325-mesh sieve; because the materials are easy to agglomerate, the screening time is prolonged properly.
The following table shows conventional detection data of the negative electrode material of the sodium ion battery prepared by the preparation method.
The particle size is measured by a Markov 2000 laser particle size analyzer, the specific surface area is measured by a NOVE e-type specific surface area analyzer, and other moisture, ash and volatile matters are calculated after the materials are dried and burned by a conventional instrument box type high-temperature furnace and an electrothermal blowing drying box.
Influence of moisture on electrical properties:
Generally, the moisture content of the negative electrode material is required to be controlled below 0.5%, and the internal resistance of the battery is increased due to the moisture, so that the performance of the battery is affected, and meanwhile, when the moisture content is too high, the capacity of the battery is reduced, and the cruising ability of the battery is affected.
Effect of ash on electrical properties:
Generally, the ash content in the negative electrode material is required to be controlled below 0.5%, and the following two aspects are mainly presented:
(1) Capacitance, cycle performance and lifetime
Studies have shown that the higher the ash content, the lower the capacitance of the negative electrode material, and the cycle performance of the battery decreases. This is because ash reduces the conductivity and electrochemical reaction rate of the anode material, resulting in a decrease in capacitance, and at the same time, makes the chemical reaction process inside the battery more difficult, thereby affecting the cycle performance and life of the battery.
(2) Safety performance
Negative electrode materials with high ash content can also have an impact on the safety performance of the battery. The high ash content can lead to increased self-discharge and heat generation of the battery, and simultaneously increase the gas release amount of the battery, affecting the reliability and safety of the battery.
Effect of volatiles on electrical properties:
Generally, the high volatile content affects the safety performance of the battery, because the volatile content is inflammable and explosive, and easily causes fire explosion in the battery, and the volatile content of the hard carbon anode material is often controlled below 8%.
Influence of specific surface area on electrical properties:
The specific surface area of the battery material is one of the important references for battery performance. The larger the specific surface area of the battery material, the better the conductive properties, thermal conductive properties, and energy storage and discharge efficiency of the battery. However, the hard carbon negative electrode in the sodium ion battery has an influence on the initial effect of the battery, and the higher the surface area is, the lower the concentration gradient of the battery is, so that the initial effect of the battery is not favored. In addition, the hard carbon negative electrode with larger surface area can reduce the electrostatic capacity of the battery, thereby further reducing the initial efficiency. Therefore, in general, the specific surface area of the hard carbon anode is often controlled to be 2-8 m 2/g.
Influence of particle size on electrical properties:
(1) Influencing the energy density of the battery
The size of the particle size of the negative electrode material directly influences the energy density of the battery, and the smaller the particle size is, the higher the energy density of the battery is. This is because smaller particles of material can increase the specific surface area of the electrode, thereby increasing the reaction area between the electrode and the electrolyte, promoting the progress of the electrochemical reaction, and improving the battery performance.
(2) Influencing the cycle performance of the battery
The size of the negative electrode material also affects the cycle performance of the battery. Smaller material particles can form a tighter electrode structure, which is beneficial to ion transmission and electrochemical reaction, and improves the cycle performance and stability of the battery.
(3) Influencing electrode safety
The particle size of the negative electrode material also affects the safety of the electrode. Smaller particles of material can increase the specific surface area of the electrode, promoting the progress of the electrochemical reaction, but also tend to cause the internal structure of the electrode to become compact, thereby making it difficult to release internal heat and gases, causing the risk of overheating or even explosion of the battery.
Therefore, the D50 of the general hard carbon negative electrode material is usually controlled to 10.0 μm or less or 5.0 μm or less, and preferably D50 is 7.0.+ -. 1.5. Mu.m.
Influence of microelements on electrical properties:
The metallic elements of copper, nickel, iron, manganese and cobalt are all common trace elements in the cathode material of the battery, and mainly come from the self-carrying of the material and the introduction of the material on a production line in the preparation process. If the content is too high, a series of problems such as increase in production cost, acceleration of electrode aging, reduction in the number of circulations of the electrode, harm to the environment, and the like may be caused. In addition, nickel is a toxic element, so that the content thereof is more required to be controlled within a certain range. The main microelements are precisely controlled, and the aim is to ensure the quality and performance of the battery. Generally, the iron content is controlled below 100ppm, and the four elements of copper, nickel, manganese and cobalt are controlled below 10 ppm. The above detection data were measured by inductively coupled plasma emission spectrometer model ICP-6300 from Siemens.
According to the table, the ash content of the sodium ion battery anode material prepared by the preparation method is 0.266%, the moisture content is 0.281%, the volatile content is 0.893%, the specific surface area is 7.129m 2/g, the iron content is below 100ppm, and the contents of copper, nickel, manganese and cobalt are all below 10ppm, so that the requirements of the sodium ion battery anode material are met.
As shown in fig. 2 and 3, the microscopic morphology of the negative electrode material of the sodium ion battery prepared by the preparation method is shown.
The figure shows that the whole microstructure of the prepared anode material is characterized by single particle, uniform particle size, smooth particle surface, few defects such as sharp angles or local protrusions and cracks which can cause the degradation of the anode material, and further more excellent electrochemical performance.
Fig. 4 is an XRD (X-ray Diffraction) test chart of the negative electrode material of the sodium ion battery obtained by the above preparation method. The scanning mode is theta-2 theta and the step is 2 degrees/s measured by using an Shimadzu XRD-6100X-ray diffractometer. Abscissa: 2θ refers to the angle of 2θ diffraction, i.e., the angle between the extension of the incident X-ray and the reflected X-ray. The ordinate Intensity represents the number of photons collected. The peak intensity (sharp or short fingertip) represents the crystallinity and grain size. A certain crystal face corresponding to the ordinate of the XRD diffraction peak; the higher the peak relative to the standard spectrum, the more atoms of the array that make up such crystal planes are present in the crystalline material. The larger the diffraction peak intensity is, the better the crystallization degree is, the larger the crystal grains are, and the growth of the corresponding crystal faces is ordered. As can be seen from the graph, the XRD pattern of the coal-based carbon negative electrode material obtained by the application shows typical amorphous carbon characteristics, namely, a hump appears near 24 degrees 2 theta, the highest peak position obviously shifts to the low-angle direction, and the peak width span is larger. This shows that the average (002) crystal face layer spacing of the coal-based carbon anode material prepared by the application is larger, and the (002) crystal face size is smaller, which is beneficial to intercalation, diffusion and deintercalation of sodium ions.
The following table shows the test data of button cell batteries prepared from the negative electrode materials of sodium ion batteries obtained by the preparation method.
According to the table, the specific capacity of the prepared negative electrode material is more than 290mAh/g, and the first-week coulomb efficiency is more than 90 percent.
The preparation method of the sodium ion battery anode material provided by the embodiment of the invention has the characteristics that the used raw material lignite is low in cost and wide in source, the lignite is more in pores and rich in functional groups, phenolic hydroxyl groups are used as the main materials, and the reaction activity is high, the activation time is short and the like; the prepared negative electrode material is applied to sodium ion batteries, has high capacity and high first week coulombic efficiency, has higher cost performance, and is simple in preparation method and process and suitable for commercial application.
The embodiment of the invention also provides a sodium ion battery anode material, which is prepared by adopting the preparation method of the sodium ion battery anode material.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A method for preparing a negative electrode material of a sodium ion battery, which is characterized by comprising the following steps:
Crushing raw lignite for the first time;
Graphitizing the materials after primary crushing;
sieving and demagnetizing the graphitized material;
ball milling is carried out on the materials subjected to sieving and demagnetizing;
Drying the ball-milled material;
scattering the dried materials;
Sieving and demagnetizing the scattered materials to obtain the negative electrode material of the sodium ion battery.
2. The method of claim 1, wherein the primary crushing of the raw lignite comprises:
Carrying out jaw breaking or hammer breaking pretreatment on raw lignite to obtain a coarsely crushed material;
the coarsely crushed materials are crushed for the first time, and the granularity is controlled to be 10-20 mu m.
3. The method of claim 1, wherein graphitizing the once crushed material comprises:
charging the materials after primary crushing into a graphitization furnace;
heating, preserving heat and cooling according to a normal graphitization temperature curve;
and discharging the materials layer by layer in the sequence from top to bottom.
4. The method of claim 3, wherein said raising, maintaining and lowering the temperature according to the normal graphitization temperature profile comprises:
Continuously powering the graphitization furnace for 80-90 hours to enable the temperature to reach 2800-3000 ℃;
keeping the graphitization furnace at the constant temperature of 2800-3000 ℃ for 10-15 hours;
air cooling for 5-8 days, water cooling for 5-8 days, and cooling to below 50-60 ℃.
5. The method of claim 1, wherein screening the graphitized material for demagnetization comprises:
sequentially packing graphitized materials, and marking;
sieving with 50-150 mesh sieve;
the materials on the sieve and the demagnetizing materials are collected separately.
6. The method of claim 1, wherein ball milling the sifted demagnetized material comprises:
Pouring materials within 100g into a ball milling tank;
weighing grinding balls according to a ball-material ratio of 8-20 times, and placing the grinding balls into a ball milling tank;
Adding secondary pure water into the ball milling tank, wherein the volume of the water accounts for 1/2-2/3 of that of the whole ball milling tank;
Ball milling is carried out.
7. The method of claim 1, wherein drying the ball-milled material comprises:
cleaning the inside of the electrothermal blowing drying oven;
placing the ball-milled material and the grinding balls into a tray of an oven, wherein the temperature of the oven is set to 105-110 ℃ and the time is set to 24-30 hours.
8. The method of claim 1, wherein the breaking up the dried material comprises:
when the temperature of the dried material is reduced to room temperature, the material and the grinding balls are put into a self-sealing bag together;
Manually kneading and uniformly mixing;
The materials and the grinding balls are screened by a 20-60 mesh sieve, and the grinding balls and the materials are separated.
9. The method of claim 1, wherein the sieving and demagnetizing the scattered material to obtain the sodium ion battery anode material comprises:
And (5) after the scattered materials are visually examined to be free of foreign matters, sieving the materials through a 325-mesh sieve to obtain the negative electrode material of the sodium ion battery.
10. A negative electrode material for a sodium ion battery, wherein the negative electrode material for a sodium ion battery is prepared by the method according to any one of claims 1 to 9.
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