CN115403028A - Preparation method of negative electrode material, negative electrode material and sodium ion battery - Google Patents
Preparation method of negative electrode material, negative electrode material and sodium ion battery Download PDFInfo
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- CN115403028A CN115403028A CN202211248066.3A CN202211248066A CN115403028A CN 115403028 A CN115403028 A CN 115403028A CN 202211248066 A CN202211248066 A CN 202211248066A CN 115403028 A CN115403028 A CN 115403028A
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- hydrochloric acid
- dilute hydrochloric
- negative electrode
- coal powder
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000003245 coal Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000000137 annealing Methods 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 29
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 20
- 230000001603 reducing effect Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 239000002817 coal dust Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 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 abstract description 26
- 229910052708 sodium Inorganic materials 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012535 impurity Substances 0.000 description 9
- 239000002194 amorphous carbon material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000007600 charging Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- -1 uniformly stirring Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000006467 substitution reaction 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
Abstract
The invention discloses an amorphous carbon negative electrode material, a preparation method thereof and a sodium ion battery, wherein the method comprises the following steps: mixing and stirring the coal powder and a dilute hydrochloric acid solution, separating, washing and drying to obtain dried coal powder; annealing the dried coal powder in a reducing atmosphere to obtain an amorphous carbon negative electrode material; wherein the concentration of the dilute hydrochloric acid solution is more than or equal to 0.5mol/L, and the annealing temperature is lower than 600 ℃. The preparation method is simple and easy to implement, is beneficial to large-scale preparation, has the advantages of less pollution in the treatment process and low price, and the obtained amorphous carbon cathode material has excellent sodium storage performance and is beneficial to increasing the energy density of the whole battery.
Description
Technical Field
The invention relates to the technical field of batteries, and relates to a negative electrode material, a preparation method thereof and a sodium ion battery.
Background
With the rapid development of social economy, the energy crisis is becoming more serious, and the rapid development of renewable energy sources becomes a consensus all over the world. However, renewable energy sources are random and unstable, requiring reasonable collocation and use of energy storage systems. In view of abundant sodium resource reserves and low cost, the sodium ion battery has excellent application prospect in the field of large-scale energy storage. Because the sodium ion battery has an energy storage principle similar to that of the lithium ion battery, most of the electrode materials of the lithium ion battery can be applied to the sodium ion battery. However, the sodium storage activity of the graphite cathode commonly used in lithium ion batteries is very low. Therefore, the search for suitable anode materials has become a key technical point for the development of sodium ion batteries (Energy environ. Sci.2021,14, 2244).
Among the negative electrode materials of sodium ion batteries, carbon-based negative electrode materials are widely researched due to the fact that the preparation process is simple and the microstructure is easy to regulate and control. The carbon-based anode material mainly comprises: graphite negative electrode materials, hard carbon negative electrode materials and amorphous carbon negative electrode materials. Because sodium ions cannot exist between graphite layers stably, the actual capacity of the graphite cathode material in the sodium ion battery is often low, and stable sodium ion storage can be realized only by means of solvent co-intercalation or preparation of expanded graphite. The hard carbon-based negative electrode material refers to a carbon material that is still difficult to graphitize at high temperature, and exhibits a stable sodium storage platform at 0.1V and thus has a high reversible sodium storage capacity (adv. Energy mater.2019, 1903176). The amorphous carbon negative electrode material can store sodium through chemical adsorption and micropores, and also has higher reversible sodium storage capacity.
Disclosure of Invention
The invention aims to provide a negative electrode material, a preparation method thereof and a sodium-ion battery.
In a first aspect, the present invention provides a method for preparing an anode material, which is characterized by comprising the following steps:
mixing, separating, washing and drying the coal powder and a dilute hydrochloric acid solution to obtain dried coal powder;
annealing the dried coal powder in a mixed atmosphere of reducing gas and inert gas to obtain an amorphous carbon negative electrode material;
wherein the concentration of the dilute hydrochloric acid solution is more than or equal to 0.5mol/L.
In the method of the present invention, the reducing gas means a gas having reducing properties, specifically, a gas capable of reducing oxygen-containing groups in the pulverized coal at a high temperature. In some embodiments of the invention, the elevated temperature is 300-500 ℃.
In the method of the present invention, the concentration of the dilute hydrochloric acid may be, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.3mol/L, 1.5mol/L, 1.7mol/L, 1.8mol/L, 2mol/L, 2.1mol/L/2.2mol/L, 2.3mol/L, 2.4mol/L, 2.5mol/L, or the like.
In some embodiments of the invention, the annealing temperature is 300-500 ℃.
The inventor finds that, in general, an amorphous carbon material is prepared from a common biomass material or an organic material, in such a method, although the amorphous carbon material obtained by carbonizing at a lower temperature has good sodium ion diffusion kinetics and exhibits excellent rate sodium storage performance, due to the lower calcination temperature, more heteroatoms exist, so that the coulomb efficiency of the first ring is not high, and the energy density of the whole battery needs to be further improved.
The method uses the coal powder as a raw material for preparing the amorphous carbon material, and the coal is cleaned by using the dilute hydrochloric acid with a certain concentration, so that the impurity content in the coal can be reduced, and meanwhile, the residual chlorine element can reversibly absorb/desorb sodium ions during sodium storage, so that the sodium storage capacity is increased. By utilizing the mixed atmosphere of the reducing gas and the inert gas to carry out annealing treatment, the safety in the high-temperature treatment process is ensured, meanwhile, the reducing gas can reduce oxygen-containing groups in coal at high temperature, the irreversible reaction in the sodium storage process is reduced, the first-circle coulomb efficiency of the sodium ion battery is improved, and the reversible sodium storage capacity is further increased.
In the method, the concentration of the dilute hydrochloric acid is not suitable to be too low, and if the concentration is too low, impurity metal elements are remained, and the sodium storage capacity is reduced.
In the method of the present invention, the annealing temperature is not suitable to be too high, and if the annealing temperature is too high, part of carbon chains in the coal may be decomposed, so as to reduce the retention rate of carbon, which affects the electrochemical performance of the final sodium battery, and even may cause excessive reaction between the coal and reducing gas, such as excessive reaction between the coal and hydrogen to produce alkane, and excessive reaction between the coal and chlorine to produce halogenated hydrocarbon.
Meanwhile, when the common biomass material or the organic material is used as a raw material to prepare the amorphous carbon material, a large amount of harmful gas is generated in the treatment process, and the air environment is polluted. The method of the invention uses the coal powder as the raw material for preparing the amorphous carbon material, and has the advantages of less pollution and low cost in the treatment process.
The preparation method is simple and easy to implement, large-scale preparation is facilitated, and the obtained amorphous carbon cathode material has excellent sodium storage performance and is beneficial to increasing the energy density of the full-cell.
Preferably, the concentration of the dilute hydrochloric acid solution is 0.5-2.5 mol/L.
Preferably, the mass ratio of the pulverized coal to the dilute hydrochloric acid solution is 1 (10-100), such as 1.
Preferably, the carbon content of the coal dust is 80 to 90wt%, such as 80wt%, 82wt%, 85wt%, 88wt%, or 90wt%, etc.; an average particle diameter of 5 to 20 μm, for example, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 μm; the specific surface area is less than 10m 2 In g, e.g. 9m 2 /g、8m 2 /g、7m 2 /g、5m 2 G or 4m 2 (iv)/g, etc.; the tap density is greater than 0.7g/mL, e.g., 0.8g/mL, 0.9g/mL, 1g/mL, 1.2g/mL, 1.3g/mL, or 1.5g/mL, etc.
The coal powder with the carbon content of 80-90 wt% is selected, so that on one hand, the main body of the material is ensured to be carbon element, and on the other hand, the material also has more oxygen-containing groups and can be converted into sodium storage active sites in subsequent treatment. The average grain diameter is 5-20 mu m, and the specific surface area is less than 10m 2 The pulverized coal with the tap density of more than 0.7g/mL has better processing performances of homogenization, coating, rolling and the like, is convenient for the subsequent preparation of the sodium-ion battery cell, and is beneficial to improving the compaction density.
As a preferred technical solution of the method of the present invention, the mixing of the pulverized coal and the dilute hydrochloric acid solution is accompanied by stirring, and the stirring time is preferably 2 to 12 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 11 hours, or 12 hours.
Preferably, the separation mode is centrifugation, and the washing mode is water washing.
Preferably, the separation and washing are performed sequentially 1 to 3 times, such as 1, 2 or 3 times. Here, the number of times is one cycle of separation and washing performed in this order.
Preferably, the drying temperature is 60 to 120 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like; the drying time is 2 to 12 hours, such as 2 hours, 3 hours, 4 hours, 6 hours, 7 hours, 8 hours, 10 hours or 12 hours and the like.
In a preferred embodiment of the method of the present invention, the volume ratio of the reducing gas is 1 to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or the like, based on the total volume of the mixed atmosphere.
In some preferred embodiments of the present invention, the reducing gas is hydrogen.
In some preferred embodiments of the invention, the reducing gas is chlorine.
The method takes hydrogen or chlorine as reducing gas for preparing the amorphous carbon material, and the hydrogen or chlorine reacts with coal to prepare the amorphous carbon when the amorphous carbon material is annealed at a certain temperature (for example, 300-500 ℃), so that oxygen-containing groups in the coal can be reduced, and other impurity elements cannot be introduced; when chlorine is used as reducing gas, the chlorine can also replace oxygen, and the introduced chlorine can reversibly absorb/desorb sodium ions during sodium storage, so that the sodium storage capacity is increased.
Preferably, the inert gas includes at least one of helium, argon, and neon. In some embodiments of the invention, argon is used as the inert gas.
Preferably, the aeration rate of the mixed gas of the inert gas and the reducing gas is 10 to 100mL/min, for example, 10mL/min, 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min or 100mL/min.
The annealing temperature is preferably 300 to 500 ℃, and may be, for example, 300 ℃, 330 ℃, 350 ℃, 375 ℃, 400 ℃, 425 ℃, 450 ℃, 470 ℃, 500 ℃ or the like, preferably 400 to 500 ℃.
The heat preservation time of the annealing treatment is preferably 4 to 12 hours, such as 4 hours, 6 hours, 8 hours, 10 hours, 12 hours and the like, and preferably 4 to 8 hours.
In some preferred embodiments of the invention, the annealing temperature is 400-500 ℃, and the holding time of the annealing treatment is 4-8 h. The proper annealing temperature and the heat preservation time can better ensure the full reduction of the oxygen-containing group, and further improve the reversible capacity.
Preferably, the temperature increase rate of the annealing treatment is 1 to 10 ℃/min, for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, or 10 ℃/min, etc., preferably 1 to 5 ℃/min.
It will be appreciated by those skilled in the art that the annealing process includes a cooling step. Illustratively, it may be naturally cooled to room temperature.
As a preferred technical scheme of the method, the method comprises the following steps:
s1: adding coal powder into a dilute hydrochloric acid solution, wherein the mass ratio of the coal powder to the dilute hydrochloric acid solution is 1 (10-100), the concentration of dilute hydrochloric acid is 0.5-2.5 mol/L, mixing and stirring for 2-12 h, then centrifugally washing for 1-3 times, and drying for 2-12 h at the temperature of 60-120 ℃;
s2: and flatly paving the dried coal powder in a crucible, then sending the crucible into a tubular furnace, annealing in the mixed atmosphere of argon and hydrogen, wherein the volume ratio of hydrogen in the mixed atmosphere of argon and hydrogen is 1-10%, the ventilation speed is 10-100 mL/min, during annealing, heating the tubular furnace from room temperature to 400-500 ℃ at the heating speed of 1-10 ℃/min, then preserving heat for 4-8 h, and naturally cooling to room temperature after the annealing is finished, thus obtaining the amorphous carbon cathode material.
As another preferred technical solution of the method of the present invention, the method comprises the steps of:
s1: adding coal powder into a dilute hydrochloric acid solution, wherein the mass ratio of the coal powder to the dilute hydrochloric acid solution is 1 (10-100), the concentration of dilute hydrochloric acid is 0.5-2.5 mol/L, mixing and stirring for 2-12 h, then centrifugally washing for 1-3 times, and drying for 2-12 h at the temperature of 60-120 ℃;
s2: and flatly paving the dried coal powder in a crucible, then sending the crucible into a tubular furnace, and carrying out annealing treatment in the mixed atmosphere of argon and chlorine, wherein the volume ratio of the chlorine in the mixed atmosphere of argon and chlorine is 1-10%, the ventilation speed is 10-100 mL/min, during the annealing treatment, the tubular furnace is heated to 400-500 ℃ from the room temperature at the heating speed of 1-10 ℃/min, then the temperature is kept for 4-8 h, and after the annealing treatment is finished, the tubular furnace is naturally cooled to the room temperature, so that the amorphous carbon cathode material can be obtained.
In a second aspect, the present invention provides an anode material prepared by the method of the first aspect. In some embodiments, the anode material is in an amorphous state and has an oxygen content of less than 1wt%. The amorphous carbon cathode material has low oxygen content, can reduce the irreversible reaction in the sodium storage process,
in a third aspect, the present invention provides a sodium ion battery, comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode comprises the negative electrode material of the second aspect.
The positive electrode active material in the positive electrode may be any conventionally known material capable of reversibly intercalating and deintercalating sodium ions, which is known to those skilled in the art and can be used in sodium ion batteries. In some embodiments of the present invention, the positive electrode active material in the positive electrode is prussian white.
Preferably, the chemical formula of the Prussian white is Na 2 MnFe(CN) 6 。
The invention adopts the amorphous carbon cathode material to prepare the cathode, adopts Prussian white to prepare the anode, constructs a novel sodium ion battery, and has excellent electrochemical performance.
The method for preparing the positive electrode and the negative electrode is not particularly limited, and those skilled in the art can prepare the negative electrode by referring to the method disclosed in the prior art, and the method for preparing the negative electrode includes, by way of example and not limitation: and grinding and mixing the amorphous carbon negative electrode material (which can be called coal-derived amorphous carbon), CMC, SBR and KS-6 according to a certain mass ratio, adding deionized water, uniformly stirring, coating on a copper foil, and drying to obtain the negative electrode.
Preferably, the mass ratio of the amorphous carbon negative electrode material to the CMC, the SBR and the KS-6 is 94:2:2:2; adding deionized water in an amount which is 0.5-2 times the mass of the solid powder; the drying temperature is 80-180 ℃.
In one embodiment, a method of preparing a positive electrode includes: na is mixed with 2 MnFe(CN) 6 The composite material is prepared by grinding and mixing CMC, SBR and conductive carbon black according to a certain mass ratio, adding deionized water, uniformly stirring, coating on an aluminum foil, and drying to obtain a positive electrode.
Preferably, na 2 MnFe(CN) 6 And the mass ratio of CMC, SBR and KS-6 is 92:2:2:4; adding deionized water in an amount which is 0.5-2 times the mass of the solid powder; the drying temperature is 80-180 ℃.
The method for assembling the sodium ion battery is not limited in the present invention, and those skilled in the art can prepare the sodium ion battery by referring to the conventional assembly method, but preferably, the battery is assembled so that the positive electrode active material supporting amount is 1 to 3 times (for example, 1 time, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.8 times, 2 times, 2.2 times, 2.5 times, 2.7 times, or 3 times) the negative electrode active material supporting amount, and the electrolyte solute is NaClO 4 The solvent is a mixed solution of PC, EC and DEC, the electrolyte additive is VC, FEC and PS, and the diaphragm is a glass fiber diaphragm or a polymer diaphragm.
The invention has the following beneficial effects:
(1) The method uses the coal powder as a raw material for preparing the amorphous carbon material, and the coal is cleaned by using the dilute hydrochloric acid with a certain concentration, so that the impurity content can be reduced, and meanwhile, the residual chlorine element can reversibly absorb/desorb sodium ions during sodium storage, and the sodium storage capacity is increased. By annealing treatment in the mixed atmosphere of reducing gas and inert gas, oxygen-containing groups in coal can be safely reduced at high temperature, irreversible reaction in the sodium storage process is reduced, the coulomb efficiency of the first circle of the sodium-ion battery is improved, and the reversible sodium storage capacity is further increased.
(2) The preparation method is simple and easy to implement, is beneficial to large-scale preparation, has the advantages of less pollution in the treatment process and low price, and the obtained amorphous carbon cathode material has excellent sodium storage performance and is beneficial to increasing the energy density of the whole battery.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments.
The coal powder adopted by the embodiment of the invention has the following properties: the carbon content of the coal powder is 80-90 wt%, the average grain diameter is 5-20 mu m, and the specific surface area is less than 10m 2 (iv) g, tap density greater than 0.7g/mL.
Example 1
The embodiment provides a preparation method of an anode material, which comprises the following steps:
step 1), adding 1g of coal powder into 50g of dilute hydrochloric acid solution, mixing and stirring for 4h, then centrifugally washing for 2 times, and drying for 6h at 80 ℃.
And 2) flatly paving the dried coal powder in a crucible, then sending the crucible into a tube furnace, and annealing in an argon-hydrogen (hydrogen volume ratio is 5%) mixed atmosphere at the aeration speed of 20mL/min. During annealing treatment, the temperature of the tubular furnace is raised from room temperature to 500 ℃ at the temperature raising speed of 5 ℃/min, then the temperature is kept for 4h, and after the annealing treatment is finished, the tubular furnace is naturally cooled to room temperature, so that the amorphous carbon cathode material, namely the coal-derived amorphous carbon, can be obtained.
The embodiment also provides a sodium ion battery, and the amorphous carbon negative electrode material prepared by the method is used as an active substance of a negative electrode. The preparation method of the sodium-ion battery comprises the following steps:
mixing the coal-derived amorphous carbon, CMC, SBR and KS-6 in a mass ratio of 94:2:2:2 grinding and mixing for 30min, then adding deionized water with the mass being 1 time that of the mixture, stirring for 2h, uniformly stirring, coating the mixture on a copper foil, and drying the copper foil at 140 ℃ to obtain the cathode.
Mixing Na 2 MnFe(CN) 6 CMC, SBR and conductive carbon black, wherein the mass ratio of the components is 92:2:2:4 grinding and mixing for 30min, then adding deionized water with the mass of 1 time, stirring for 2h, uniformly stirring, coating on an aluminum foil, and drying at 140 ℃ to obtain the anode.
Assembling the sodium ion battery by using the cathode and the anode, wherein the loading capacity of the active substance of the anode is 2 times of that of the cathode; the solute of the electrolyte is NaClO 4 The electrolyte solvent is a mixed solution of PC, EC, and DEC, the volume ratio of PC, EC, and DEC is 1; the diaphragm is a glass fiber diaphragm; and (4) after the battery is packaged, standing for 24 hours, and testing the reversible capacity, the first-circle coulombic efficiency and the rate capability of the battery.
(1) Reversible capacity and first turn coulombic efficiency test
Charging the sodium ion battery to 3.8V at 0.5C at room temperature (25 ℃), then converting to constant voltage charging (3.8V), stopping when the current is less than 0.02C, standing for 5min, discharging to 1.5V at 0.5C, standing for 5min, and circularly charging, standing, discharging and standing for 3 times; obtaining the reversible capacity of the sodium-ion battery according to the third discharge capacity; first cycle coulombic efficiency (%) = first cycle discharge capacity/first cycle charge capacity.
(2) Rate capability test
Charging the sodium ion battery to 3.8V at the temperature of 0.5 ℃ at room temperature (25 ℃), then converting to constant voltage charging (3.8V), stopping when the current is less than 0.02 ℃, standing for 5min, discharging to 1.5V at the temperature of 0.5 ℃, standing for 5min, and circularly charging, standing, discharging and standing for 5 times; then changing the charging current and the discharging current into 1C, 2C and 3C in turn, repeating the charging and discharging process, and respectively cycling 'charging-standing-discharging-standing' for 5 times. And recording the discharge capacity of the whole circulation process to obtain the rate capability of the sodium-ion battery.
The sodium ion batteries were prepared in the same manner as in example 1 and were tested for reversible capacity, first-turn coulombic efficiency, and rate capability, and the test results of all examples and comparative examples are shown in table 1.
Example 2
The embodiment provides a preparation method of an anode material, which comprises the following steps:
step 1), adding 1g of coal powder into 50g of dilute hydrochloric acid solution, mixing and stirring for 4h, then centrifugally washing for 2 times, and drying for 6h at 80 ℃.
And 2) flatly paving the dried coal powder in a crucible, then sending the crucible into a tube furnace, and annealing in an argon-hydrogen (hydrogen volume ratio is 5%) mixed atmosphere at an aeration speed of 20mL/min. During annealing treatment, the temperature of the tubular furnace is raised from room temperature to 380 ℃ at the temperature raising speed of 5 ℃/min, then the temperature is kept for 6h, and after the annealing treatment is finished, the tubular furnace is naturally cooled to the room temperature, so that the amorphous carbon cathode material, namely the coal-derived amorphous carbon, can be obtained.
Example 3
The embodiment provides a preparation method of an anode material, which comprises the following steps:
step 1), adding 1g of coal powder into 50g of dilute hydrochloric acid solution, mixing and stirring for 4h, then centrifugally washing for 2 times, and drying for 6h at 80 ℃.
And 2) flatly paving the dried coal powder in a crucible, then sending the crucible into a tube furnace, and annealing in an argon-hydrogen (hydrogen volume ratio is 5%) mixed atmosphere at the aeration speed of 20mL/min. During annealing treatment, the temperature of the tubular furnace is raised from room temperature to 500 ℃ at the heating rate of 5 ℃/min, then the temperature is kept for 1.5h, and after the annealing treatment is finished, the tubular furnace is naturally cooled to the room temperature, so that the amorphous carbon cathode material, namely the coal-derived amorphous carbon, can be obtained.
Example 4
This example differs from example 1 in that the concentration of dilute hydrochloric acid is 2.5mol/L.
Example 5
This example differs from example 1 in that the annealing temperature was 275 ℃.
Example 6
The present example is different from example 1 in that the mass ratio of pulverized coal to dilute hydrochloric acid solution is 1.
Example 7
The difference from example 1 is that chlorine is used instead of hydrogen.
Comparative example 1
This comparative example differs from example 1 in that the concentration of dilute hydrochloric acid is 0.02mol/L.
Comparative example 2
This comparative example differs from example 1 in that dilute hydrochloric acid was replaced with dilute sulfuric acid and the concentration of hydrogen ions was the same as in example 1.
Comparative example 3
This comparative example is different from example 1 in that the mixed atmosphere of argon and hydrogen was replaced with an air atmosphere.
TABLE 1
| Reversible capacity (0.5C) | First turn coulomb efficiency | Reversible capacity (3C) | |
| Example 1 | 1.32Ah | 82.7％ | 0.794Ah |
| Example 2 | 1.26Ah | 81.6％ | 0.756Ah |
| Example 3 | 1.28Ah | 82.3％ | 0.783Ah |
| Example 4 | 1.33Ah | 82.8％ | 0.810Ah |
| Example 5 | 1.16Ah | 78.2％ | 0.649Ah |
| Example 6 | 1.30Ah | 82.2％ | 0.792Ah |
| Example 7 | 1.35Ah | 84.3％ | 0.851Ah |
| Comparative example 1 | 1.19Ah | 79.5％ | 0.732Ah |
| Comparative example 2 | 1.21Ah | 81.2％ | 0.725Ah |
| Comparative example 3 | / | / | / |
As can be seen from table 1, in the embodiment of the present invention, a proper amount of dilute hydrochloric acid is used to clean coal, so as to reduce the content of impurities in coal powder, increase reversible capacity of residual chlorine element during sodium storage, and then perform annealing treatment by using a mixed atmosphere of reducing gas and inert gas, so as to safely reduce oxygen-containing groups in coal at a high temperature, reduce irreversible reaction during sodium storage, and further improve reversible capacity, first-cycle coulombic efficiency, and rate capability of a sodium ion battery.
In the preparation method, the cathode material prepared by selecting the annealing temperature of 400-500 ℃ and the heat preservation time of 4-8 h is suitable for batteries and has better electrochemical performance; comparing the data of example 1 and example 2, it can be seen that the annealing temperature in example 2 is slightly lower, which results in that part of the oxygen-containing groups are not reduced and the reversible capacity is reduced; comparing the data of examples 1 and 3, it can be seen that the incubation time in example 3 is slightly shorter, resulting in relatively poorer reduction effect and a decrease in reversible capacity. In addition, the annealing temperature is not suitable to be too low, when the annealing temperature is lower than 300 ℃, the improvement effect of the electrochemical performance of the battery can be influenced, and the annealing temperature of example 5 is lower than 300 ℃, so that part of oxygen-containing groups are not reduced basically, the reversible capacity of the sodium-ion battery is low, and the coulomb efficiency of the first circle is relatively low.
In the preparation method of the invention, the hydrochloric acid concentration of 0.5-2.5 mol/L is selected, so that higher impurity removal effect and chloride ion adsorption effect can be realized, and the material cost is less increased at the same time, and as can be seen from examples 1-4, the reversible capacity and the first-turn coulomb efficiency of the battery are relatively higher. In addition, when the mass ratio of the hydrochloric acid to the coal is 1 (30-50), higher impurity removal effect can be realized, reversible capacity is increased, and material cost is increased less; in example 6, the amount of hydrochloric acid used was small, the effect of removing impurities was not good, and the reversible capacity was slightly reduced.
In example 7, the oxygen-containing group is reduced by using the chlorine-hydrogen mixed gas, so that a large amount of chlorine element is doped into the pulverized coal, and high reversible capacity and first-turn coulombic efficiency are obtained, and the rate capability is excellent.
In comparative example 1, the hydrochloric acid concentration was too low, the impurity removal effect was poor, and the reversible capacity and the first-turn coulombic efficiency were low.
Comparative example 2 was washed with dilute sulfuric acid, without the adsorption of chlorine to sodium ions, resulting in a lower reversible capacity.
Comparative example 3 annealing was performed using an air atmosphere, so that the pulverized coal was completely oxidized and no product was generated.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing an anode material, the method comprising the steps of:
mixing coal powder and a dilute hydrochloric acid solution, separating, washing and drying to obtain dried coal powder;
annealing the dried coal powder in a mixed atmosphere of reducing gas and inert gas to obtain an amorphous carbon negative electrode material;
wherein the concentration of the dilute hydrochloric acid solution is more than or equal to 0.5mol/L.
2. The method according to claim 1, characterized in that the concentration of the dilute hydrochloric acid solution is 0.5-2.5 mol/L;
preferably, the mass ratio of the coal powder to the dilute hydrochloric acid solution is 1 (10-100), and more preferably 1 (30-50).
3. The method according to claim 1 or 2, wherein the coal dust has a carbon content of 80 to 90wt%, an average particle diameter of 5 to 20 μm, and a specific surface area of less than 10m 2 (iv)/g, tap density greater than 0.7g/mL.
4. The method according to any one of claims 1 to 3, wherein the mixing of the coal dust and the dilute hydrochloric acid solution is accompanied by stirring, and the stirring time is preferably 2 to 12 hours;
preferably, the separation mode is centrifugation, and the washing is water washing;
preferably, the separation and washing are sequentially performed 1 to 3 times;
preferably, the drying temperature is 60-120 ℃, and the drying time is 2-12 h.
5. The method according to any one of claims 1 to 4, wherein the volume of the reducing gas is 1 to 10% based on the total volume of the mixed atmosphere;
preferably, the reducing gas is selected from hydrogen or chlorine;
preferably, the inert gas includes at least one of helium, argon, and neon;
preferably, the aeration rate of the mixed atmosphere of the inert gas and the reducing gas is 10 to 100mL/min.
6. The method according to any one of claims 1 to 5, wherein the annealing is carried out at a temperature of 300 to 500 ℃, preferably 400 to 500 ℃;
preferably, the heat preservation time of the annealing treatment is 4-12 h, preferably 4-8 h;
preferably, the temperature increase rate of the annealing treatment is 1 to 10 ℃/min, more preferably 1 to 5 ℃/min.
7. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
s1: adding coal powder into a dilute hydrochloric acid solution, wherein the mass ratio of the coal powder to the dilute hydrochloric acid solution is 1 (10-100), the concentration of dilute hydrochloric acid is 0.5-2.5 mol/L, mixing and stirring for 2-12 h, then centrifugally washing for 1-3 times, and drying for 2-12 h at the temperature of 60-120 ℃;
s2: spreading the dried coal powder in a crucible, then sending the crucible into a tubular furnace, annealing in the mixed atmosphere of argon and hydrogen, wherein the volume ratio of hydrogen in the mixed atmosphere of argon and hydrogen is 1-10%, the ventilation speed is 10-100 mL/min, during the annealing, the tubular furnace is heated to 400-500 ℃ from the room temperature at the heating speed of 1-10 ℃/min, then preserving the heat for 4-8 h, and after the annealing is finished, naturally cooling to the room temperature to obtain the amorphous carbon cathode material.
8. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
s1: adding coal powder into a dilute hydrochloric acid solution, wherein the mass ratio of the coal powder to the dilute hydrochloric acid solution is 1 (10-100), the concentration of dilute hydrochloric acid is 0.5-2.5 mol/L, mixing and stirring for 2-12 h, then centrifugally washing for 1-3 times, and drying for 2-12 h at the temperature of 60-120 ℃;
s2: and flatly paving the dried coal powder in a crucible, then sending the crucible into a tubular furnace, and carrying out annealing treatment in the mixed atmosphere of argon and chlorine, wherein the volume ratio of the chlorine in the mixed atmosphere of argon and chlorine is 1-10%, the ventilation speed is 10-100 mL/min, during the annealing treatment, the tubular furnace is heated to 400-500 ℃ from the room temperature at the heating speed of 1-10 ℃/min, then the temperature is kept for 4-8 h, and after the annealing treatment is finished, the tubular furnace is naturally cooled to the room temperature, so that the amorphous carbon cathode material can be obtained.
9. A negative electrode material prepared according to any of claims 1 to 8, wherein the negative electrode material is amorphous and has an oxygen content of less than 1wt%.
10. A sodium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode comprises the negative electrode material of claim 9;
preferably, the positive electrode active material in the positive electrode is prussian white;
preferably, the chemical formula of the Prussian white is Na 2 MnFe(CN) 6 。
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