CN116654897A - Preparation method and application of hard carbon anode material of sodium ion battery - Google Patents
Preparation method and application of hard carbon anode material of sodium ion battery Download PDFInfo
- Publication number
- CN116654897A CN116654897A CN202310704643.3A CN202310704643A CN116654897A CN 116654897 A CN116654897 A CN 116654897A CN 202310704643 A CN202310704643 A CN 202310704643A CN 116654897 A CN116654897 A CN 116654897A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- sodium ion
- solid waste
- ion battery
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 37
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 32
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010405 anode material Substances 0.000 title claims description 7
- 239000010426 asphalt Substances 0.000 claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000012216 screening Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002910 solid waste Substances 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004380 ashing Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000003607 modifier Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000010902 straw Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 244000061456 Solanum tuberosum Species 0.000 claims description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 244000020551 Helianthus annuus Species 0.000 claims description 2
- 235000003222 Helianthus annuus Nutrition 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 240000007316 Xerochrysum bracteatum Species 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 238000003801 milling Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method and application of a hard carbon negative electrode material of a sodium ion battery. Firstly, uniformly mixing agricultural solid waste powder and oxidized asphalt, carbonizing at a high temperature, grinding and crushing by using a wheel, and screening by using an ultrasonic vibration screen; adding a substance containing a boron-containing alkali metal compound to carry out ashing, adding dilute hydrochloric acid into an ashed product as a modifier to carry out reaction, then washing, filtering and drying to obtain a final product, adding oxidized asphalt in the high-temperature carbonization process, improving the first efficiency, crushing by using wheel milling, and carrying out low structural damage on a hard carbon negative electrode.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method and application of a hard carbon negative electrode material of a sodium ion battery.
Background
The new energy automobile, electric energy storage and clean energy storage industries are rapidly developed. At present, the new energy automobile and the energy storage device mainly take lithium ion batteries, and the lithium ion batteries are rapidly developed and applied on a large scale, so that the lithium demand and the cost of raw materials of the lithium ion batteries are rapidly increased, and the huge demand of the lithium ion batteries can not be met soon. And the lithium resource reserves in China are limited, and the requirement of lithium ion batteries on lithium can be met only through import.
Compared with lithium element, the abundance of sodium element in the same main group in crust is 420 times of that of the sodium element in crust, and the sodium content reserve in China is rich without dependence on foreign import. Therefore, sodium ion batteries are not two alternatives to lithium ion batteries.
Graphite is the most used negative electrode material with the most mature technology in the current lithium ion battery, but because the radius of sodium ions is larger than that of lithium ions, the sodium ions can generate larger volume expansion after being intercalated into the graphite, so that the battery has extremely poor energy density and cycle performance. Therefore, research and development of a negative electrode material dedicated to sodium ion batteries is needed.
The development of negative electrode materials with such characteristics is mainly focused on hard carbon, soft carbon, tin-based materials, etc., among which hard carbon materials with low voltage plateau are considered as the negative electrode materials of sodium ion batteries closest to practical application.
The preparation method of the existing hard carbon anode material of the sodium ion battery mainly comprises the following two steps: 1. pyrolyzing the organic resin at high temperature; after pyrolysis, the modification is carried out by liquid phase coating, and the solvent used for the liquid phase coating is also an organic solvent. 2. Pyrolyzing petroleum asphalt at high temperature; the petroleum asphalt is oxidized and modified by concentrated sulfuric acid or hydrogen peroxide, and the following problems exist in the above technology: 1) The reaction conditions are harsh, a large amount of organic volatile matters can be generated in the high-temperature treatment process of the preparation raw materials, the environmental pollution is serious, and the cost pressure is high in the aspect of environmental protection. 2) The preparation process of the polymer material is complex, and the cost of raw materials is high. 3) The prepared hard carbon negative electrode material of the sodium ion battery has the defects of large specific surface area, low tap density, low initial efficiency, high ash content, poor rate capability and the like.
Disclosure of Invention
The invention aims to solve the technical defects of strong pollution and high cost of the raw materials for producing the hard carbon negative electrode material of the existing sodium ion battery, and finally prepare the hard carbon negative electrode material of the sodium ion battery with good electrical property.
In order to achieve the above purpose, the invention adopts the following technical scheme,
the preparation method of the hard carbon negative electrode material of the sodium ion battery mainly comprises the following steps:
(1) Uniformly mixing agricultural solid waste powder and oxidized asphalt, and then carrying out high-temperature carbonization coating modification to obtain a modified product, wherein the use amount of the oxidized asphalt accounts for 10% -20% of the mass of the agricultural solid waste powder, the high-temperature carbonization is carried out in a protection gas tube furnace, the carbonization temperature is 800-1000 ℃, and the carbonization time is 1-5h (preferably 2h carbonization at 850-900 ℃);
(2) Crushing the modified product obtained in the step (1) in a wheel mill, and then screening and grading in an ultrasonic vibration screen to obtain undersize;
(3) Uniformly mixing the undersize with a substance A containing a boron-containing alkali metal compound (preferably, the undersize and the substance A have the mass of 1 (3-6)), ashing for 1-3 hours at 900-1000 ℃ under the condition of protective gas to obtain an ashed product (preferably, ashing for 2 hours at 900 ℃), adding dilute hydrochloric acid with the concentration of 50-150ml/L into the ashed product as a modifier for reaction, and then washing, filtering and drying to obtain the final product of the hard carbon anode material of the sodium ion battery, wherein the mass ratio of the undersize to the substance A is 1: (2-4);
further, the particle size control conditions of the agricultural solid waste powder in the step (1) are as follows:
d10 =4-6 μm, d50=12-14 μm, d90 < 30 μm, particle size distribution K value=1.6-2.0;
further, in the step (1), the agricultural solid waste powder is obtained by cleaning, drying, cutting, crushing and screening the agricultural solid waste into the agricultural solid waste powder, wherein the crushing is performed in a crusher, and the rotation speed of a main machine is that: 12000r/min, and pulverizing time of 30s-60s; the screening time is 5-10 minutes, and the diameter of the sieve holes is 250-325 meshes.
Still further, the agricultural solid waste is potato straw, corn straw, and/or sunflower straw.
Further, the substance A is a boron-containing alkali metal compound or a mixture of the boron-containing alkali metal compound and the alkali metal compound, and further, the substance A is borax or the mass ratio is 2: 8-4: 6 sodium carbonate and borax.
Further, the pulverizing conditions in the step (2) are as follows: the spiral rotating speed is 8-25r/min; grinding for 8-10 minutes; the screening conditions are as follows: the intensity of ultrasonic wave is 20-80%, the amplitude is 1-3mm, and the screening time is 6-10 minutes;
further, the ratio of the undersize to the dilute hydrochloric acid in the step (3) is 1mg: (10-30) mL, preferably; 1mg: (15-20) mL.
Further, the washing in the step (3) is performed by using ultrapure deionized water, the ion conductivity of the ultrapure deionized water is controlled to be 1-1.5 mu omega/cm, and the washing is controlled until the pH value of the filtrate is more than 6;
further, the drying in the step (3) is performed in a vacuum freeze dryer for 2-4 hours at a freeze drying temperature of-20 ℃ to-40 ℃ and a vacuum pressure: 60-100Pa.
Further, the asphalt oxide is coal asphalt-based asphalt oxide or petroleum asphalt-based asphalt oxide;
the invention also provides application of the hard carbon negative electrode material of the sodium ion battery, which is obtained by the preparation method, in preparation of the sodium ion battery.
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
1. the agricultural solid waste is used as the raw material for preparing the hard carbon cathode, so that the source is wide, the reserves are rich, the cost is low, and the pollution is low;
2. adding oxidized asphalt in the high-temperature carbonization process, filling residual carbon carbonized by the oxidized asphalt into micropores of a hard carbon anode precursor and coating the micropores on the surface of the hard carbon anode precursor, so that the specific surface area of the hard carbon anode can be reduced, the surface is coated, modified and modified, the reversible lithium consumption in the charge and discharge process is reduced, and the first efficiency is finally improved; the unoxidized carbon fiber spinning pitch added in the prior art can form a graphite-like structure after carbonization, and sodium ions have insufficient capacity in the graphite structure and have low first efficiency;
3. the hard carbon anode precursor carbonized at high temperature is crushed by using wheel milling, so that compared with the mechanical mill used in the prior art, the structural damage to materials is small, the proportion of the crushed material micro powder is small, the particle size distribution K value is small, the particle size distribution is narrow, and the tap density is large; meanwhile, compared with a single-pure vibrating screen used in the prior art, the vibrating screen with ultrasonic waves is fast in screening efficiency and high in yield;
4. and ashing the carbonized material by using a boron-containing alkali metal compound, and then treating the carbonized material by using dilute hydrochloric acid, wherein the boron-containing alkali metal compound can convert silicate ash in biomass hard carbon into alkali metal silicate in the ashing process, and then the alkali metal silicate is removed by acidification of the dilute hydrochloric acid. In the prior art, concentrated sulfuric acid or aqua regia is usually selected for ash removal, and the two are strong acidic substances, and the reaction conditions are severe, so that the requirements on reaction equipment and operation are high, and the practicability is poor. In addition, the main constituent elements of the boron element and the hard carbon cathode are in the same period and are in adjacent positions, the chemical properties are similar, and the boron element is doped into a hard carbon lattice in a heteroatom form to form a defective solid solution, so that lattice defects of the hard carbon lattice are increased, the surface density of a fermi state is increased, the hard carbon material is in an electron-rich state, and the conductivity and the multiplying power performance of the hard carbon material are improved. Therefore, the addition of the boron-containing alkali metal compound can both reduce ash in the hard carbon anode and play a role in improving its rate capability.
5. The filtered matters are dehydrated by using a freeze-drying technology, the water in the filtered matters is frozen into a solid state in a vacuum state in the freeze-drying mode, and then the solid state is dehydrated after sublimating into water vapor.
Drawings
Fig. 1 to 3 are charge and discharge graphs after the negative electrode materials of comparative examples and examples 1 to 2 were prepared into button cells, respectively, in the test examples.
Fig. 4 is a scanning electron micrograph of example 2.
Detailed Description
The technical scheme of the invention is described below through specific examples.
In the following examples and comparative examples:
washing in the step (3) by ultrapure deionized water, wherein the ionic conductivity is controlled to be 1-1.5 mu omega/cm, the mass ratio of water to the to-be-washed is controlled to be 10/1-2/1, and the washing is carried out until the pH value of the filtrate is more than 6;
the purity of the nitrogen is 99.5%, and the flow rate of the nitrogen is 150-200ml/min.
Example 1 a method for preparing a hard carbon negative electrode material of a sodium ion battery comprises the following steps:
(1) Cleaning and drying potato straw, cutting into blocks with length of 1-2cm, pulverizing in a Chinese herbal medicine pulverizer, sieving, and rotating at the speed of main machine during pulverizing: 12000r/min, pulverizing time 60s, sieving in a vibrating sieve for 8 min with sieve mesh diameter 300 mesh, sieving product D10 of 4.64 μm, D50 of 12.8 μm, D90 of 28.45 μm, and particle size distribution coefficient k value (D90-D10)/D50 of 1.86.
(2) Uniformly mixing the obtained undersize and coal tar pitch-based asphalt at a mass ratio of 100:12, carbonizing the undersize and coal tar pitch-based asphalt in a tube furnace filled with nitrogen at 850 ℃ for 2 hours, treating the carbonized product in a wheel mill for 10 minutes, and sieving the carbonized product by using a vibrating screen with ultrasonic waves, wherein the grinding conditions are as follows: 1. the spiral rotating speed is 12r/min; 2. grinding time is 10 minutes; the screening conditions are as follows: ultrasonic intensity: 50%, amplitude: 3mm, screening time is 8 minutes;
(3) And (3) mixing the screened undersize product obtained in the step (2) with borax in a ratio of 1/3, ashing for 1.5 hours at a muffle furnace and 900 ℃, adding 50mL/L of diluted hydrochloric acid into the rest product, stirring and reacting for 4 hours at a temperature of 80 ℃ and a rotating speed of 80r/min, washing the obtained reaction product with ultrapure deionized water, filtering, and then performing freeze-vacuum drying in a freeze dryer for 2 hours (the freeze-drying temperature is minus 30 ℃ and the freeze-drying pressure is 80 Pa) to obtain the hard carbon negative electrode material of the sodium ion battery.
Example 2 a method for preparing a hard carbon negative electrode material of a sodium ion battery comprises the following steps:
(1) Undersize was prepared in the same manner as in step (1) of example 1.
(2) Uniformly mixing the obtained undersize and petroleum asphalt-based asphalt oxide in a mass ratio of 100:14, carbonizing the undersize and petroleum asphalt-based asphalt in a tube furnace filled with nitrogen at 900 ℃ for 2 hours, treating the carbonized product in a wheel mill for 10 minutes, and sieving the carbonized product by using a vibrating screen with ultrasonic waves, wherein the grinding conditions are as follows: 1. the spiral rotating speed is 20r/min; 2. grinding for 8 minutes; the screening conditions are as follows: ultrasonic intensity: 60%, amplitude: 2mm, screening time is 10 minutes;
(3) The undersize material and sodium carbonate/boric acid mixture (the mass ratio of sodium carbonate to boric acid is 2:8-4:6) after sieving in the step (2) are mixed according to the following ratio of 1:4, ashing for 1.5 hours at 900 ℃ in a muffle furnace, adding 50mL/L of dilute hydrochloric acid into the rest product, stirring and reacting for 4 hours at 80 ℃ and a rotating speed of 80r/min, washing the obtained reaction product with ultrapure deionized water, filtering, and then freezing and drying in a freeze dryer for 2 hours (the freeze drying temperature is minus 30 ℃ and the freeze drying pressure is 80 Pa) to obtain the hard carbon anode material of the sodium ion battery.
Note that: the concentration unit ml/L of hydrochloric acid is the volume ratio of concentrated hydrochloric acid with the mass concentration of 37% to water.
Comparative example a method for preparing a hard carbon negative electrode material of a sodium ion battery comprises the following steps:
(1) Step (1) is the same as in example 1;
(2) The undersize and carbon fiber spinning pitch obtained above are mixed according to the mass ratio of 100:12, carbonizing the mixture for 2 hours at 850 ℃ in a nitrogen tube atmosphere furnace after uniformly mixing, and screening the carbonized product by a vibrating screen after treating the carbonized product in a mechanical mill for 10 minutes;
(3) Adding the undersize product obtained in the step (2) into 50mL/L of dilute hydrochloric acid (the volume ratio of the undersize mass to the dilute hydrochloric acid is 10mg/200 mL), stirring at the constant temperature of 80 ℃ and the speed of 80r/min for reaction for 4 hours, washing and filtering the reaction product by ultrapure deionized water, drying at the constant temperature of 120 ℃ for 4 hours in a constant pressure state in a constant temperature blast drying box, and crushing and screening to obtain the hard carbon anode material of the sodium ion battery.
Test example:
the hard carbon negative electrode materials of sodium ion batteries prepared in examples 1-2 and comparative example were tested for various physical and chemical indexes (the results are shown in Table 1), and MnO was used 2 As a positive electrode active material, a button cell assembled into CR2430 using the hard carbon negative electrode materials of sodium ion cells prepared in comparative examples and examples 1-2, respectively, step (3) as a negative electrode active material was subjected to an electrical property test, and the results are shown in table 2.
Basic parameter setting for charge and discharge test:
1. first effect and gram Capacity test: 1. standing for 2 hours; 2. 0.1C discharge, cutoff voltage 0.01V; 3. discharging at 0.09-0.02C, and stopping at 0.005V; 4. standing for 15 minutes; 5. 0.1C, cut-off voltage 1.5V.
2. Multiplying power test: firstly, setting charge and discharge for 1 time according to first effect and gram capacity test parameters, then charging and discharging for 1 time at 0.2C, and stopping voltage: 0.005V-1.5V, and standing for 15 minutes; charging and discharging for 1 time at 0.5C, and keeping for 15 minutes at the cut-off voltage of 0.005-1.5V; charging and discharging for 1 time at 1C, and standing for 15 minutes at a cut-off voltage of 0.005-1.5V.
3. And (3) testing the cycle performance: and (3) carrying out charge and discharge for 100 times according to the multiplying power test parameter setting, namely, carrying out charge and discharge circulation for 100 times at 1C, and standing for 15 minutes at a cutoff voltage of 0.005-1.5V.
TABLE 1
TABLE 2
Note that: the screening time refers to the time when the oversize material is no longer being screened, and is specifically indicated in table 1: after the carbonized product is treated in the wheel milling for 10 minutes, a vibrating screen with ultrasonic waves is used; the mesh number of the screen used was 250 mesh, and the screen diameter was 30cm.
The proportion of the micro powder is the mass ratio of the materials with the granularity smaller than 1 micron in the product after grinding and crushing by a wheel to the total amount;
the ash content is detected by adopting a weight method, and the specific conditions are as follows: after weighing 1g of a negative electrode material sample and heating at 900 ℃ for 2 hours, the mass of the rest accounts for the percentage of the total mass of the weighed material.
The yield refers to: screening yield when using a belt ultrasonic vibration screen or a vibrating screen in step (2).
Claims (10)
1. A preparation method of a hard carbon negative electrode material of a sodium ion battery comprises the following steps:
(1) Uniformly mixing agricultural solid waste powder and oxidized asphalt, and then carrying out high-temperature carbonization to obtain a modified product, wherein the use amount of the oxidized asphalt is 10% -20% of the mass of the agricultural solid waste powder, the high-temperature carbonization is carried out in a tube furnace which is communicated with a protective gas, the carbonization temperature is 800-1000 ℃, and the carbonization time is 1-5 hours;
(2) Crushing the modified product obtained in the step (1) in a wheel mill, and then screening and grading in an ultrasonic vibration screen to obtain undersize;
(3) Uniformly mixing the undersize material with a substance A containing a boron-containing alkali metal compound, ashing for 1-3 hours at 900-1000 ℃ under the condition of protective gas to obtain an ashed product, adding dilute hydrochloric acid with the concentration of 50-150ml/L into the ashed product as a modifier for reaction, and then washing, filtering and drying to obtain the final product of the sodium ion battery hard carbon anode material, wherein the mass ratio of the undersize material to the substance A is 1: (2-4).
2. The method according to claim 1, wherein the particle size control conditions of the agricultural solid waste powder in the step (1) are as follows: d10 =4-6 μm, d50=12-14 μm, d90 < 30 μm, particle size distribution K value=1.6-2.0.
3. The method according to claim 2, wherein the agricultural solid waste powder in the step (1) is obtained by washing, drying, cutting, crushing, and sieving agricultural solid waste into agricultural solid waste powder, the crushing is performed in a pulverizer, and the rotation speed of a main machine is: 12000r/min, and pulverizing time of 30s-60s; the screening time is 5-10 minutes, and the diameter of the sieve holes is 250-325 meshes.
4. A method of preparation according to claim 3, wherein the agricultural solid waste is potato straw, corn straw and/or sunflower straw.
5. The preparation method according to claim 1, wherein the substance a is a boron-containing alkali metal compound or a mixture of a boron-containing alkali metal compound and an alkali metal compound.
6. The method according to claim 1, wherein the pulverizing conditions in step (2) are: the spiral rotating speed is 8-25r/min; grinding for 8-10 minutes; the screening conditions are as follows: the intensity of ultrasonic wave is 20-80%, the amplitude is 1-3mm, and the screening time is 6-10 minutes.
7. The process of claim 1, wherein the ratio of undersize to dilute hydrochloric acid in step (3) is 1mg: (10-30) mL.
8. The method according to claim 1, wherein the washing in the step (3) is performed by ultrapure deionized water, the ionic conductivity of the ultrapure deionized water is controlled to be 1-1.5 μΩ/cm, and the washing is controlled until the pH of the filtrate is more than 6; the drying in the step (3) is carried out in a vacuum freeze dryer for 2-4 hours at a freeze drying temperature of-20 ℃ to-40 ℃ and a vacuum pressure: 60-100Pa.
9. The method of claim 1, wherein the asphalt oxide is coal asphalt-based asphalt oxide or petroleum asphalt-based asphalt oxide.
10. Use of the hard carbon negative electrode material of the sodium ion battery obtained by the preparation method of any one of claims 1-9 in the preparation of the sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310704643.3A CN116654897A (en) | 2023-06-14 | 2023-06-14 | Preparation method and application of hard carbon anode material of sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310704643.3A CN116654897A (en) | 2023-06-14 | 2023-06-14 | Preparation method and application of hard carbon anode material of sodium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116654897A true CN116654897A (en) | 2023-08-29 |
Family
ID=87727737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310704643.3A Pending CN116654897A (en) | 2023-06-14 | 2023-06-14 | Preparation method and application of hard carbon anode material of sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116654897A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117342541A (en) * | 2023-12-05 | 2024-01-05 | 山东泰和科技股份有限公司 | Asphalt-derived carbon sodium ion battery anode material and preparation method and application thereof |
-
2023
- 2023-06-14 CN CN202310704643.3A patent/CN116654897A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117342541A (en) * | 2023-12-05 | 2024-01-05 | 山东泰和科技股份有限公司 | Asphalt-derived carbon sodium ion battery anode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103214245B (en) | Carbon/carbon composite microsphere material, production method and lithium ion battery | |
| CN103682350B (en) | Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material | |
| CN109796003B (en) | Coal-based hard carbon surface oxygen functional group directional regulation and control method for sodium storage cathode | |
| CN109921018A (en) | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material | |
| CN111224078A (en) | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode | |
| CN106169582B (en) | A kind of natural needle coke composite graphite negative electrode material production method | |
| CN110504430A (en) | A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof | |
| CN114171738A (en) | Graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN107611396B (en) | Sulfur-asphalt-based/graphene composite material and preparation method and application thereof | |
| CN103840161A (en) | Method for preparing lithium battery negative electrode material, and lithium battery negative electrode sheet | |
| CN116654897A (en) | Preparation method and application of hard carbon anode material of sodium ion battery | |
| CN114335522A (en) | Coal-based carbon negative electrode material, preparation method and application thereof, and battery containing coal-based carbon negative electrode material | |
| CN113307254A (en) | Method for preparing three-dimensional porous graphene sheet by using low-temperature double-salt compound and application | |
| CN113880068A (en) | Hard carbon composite material and preparation method and application thereof | |
| CN111320161A (en) | Preparation method and application of asphalt-based carbon nanosheet | |
| CN110510595A (en) | A kind of preparation method of the N/S codope porous carbon for lithium-sulfur cell | |
| KR100960139B1 (en) | Negative active material for lithium secondary battery, method of preparing thereof, and lithium secondary battery comprising the same | |
| CN110061197B (en) | Coal-based battery negative electrode material and preparation method and application thereof | |
| CN116724411A (en) | Method for preparing hard carbon anode material by using fiber biomass, product and application thereof | |
| CN111613794A (en) | Modified graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN110061198B (en) | Silicon-carbon composite negative electrode material and preparation method and application thereof | |
| CN114314581B (en) | Preparation method of artificial graphite negative electrode material and lithium ion battery | |
| CN115285969A (en) | Biomass-derived nitrogen-doped hard carbon material and preparation method and application thereof | |
| CN111892051B (en) | Biomass graded porous carbon for capacitor electrode material and preparation method thereof | |
| CN111204731B (en) | Preparation method of hard carbon negative electrode material of sodium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |