CN116239099A - Negative electrode active material of sodium ion battery, and preparation method and application thereof - Google Patents
Negative electrode active material of sodium ion battery, and preparation method and application thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 128
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000006183 anode active material Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims description 39
- 239000000571 coke Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 239000005539 carbonized material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 238000009656 pre-carbonization Methods 0.000 abstract description 17
- 238000005245 sintering Methods 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 10
- 230000002441 reversible effect Effects 0.000 abstract description 10
- 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 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 239000011229 interlayer Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a sodium ion battery negative electrode active material, a preparation method and application thereof, and belongs to the technical field of sodium ion battery materials. According to the preparation method of the sodium ion battery anode active material, the semi-coke powder is subjected to pre-carbonization treatment and high-temperature sintering treatment in sequence, so that the preparation method has the advantages of simplicity in operation, environment friendliness, high efficiency, few byproducts and high yield, is easy to realize large-scale production, has good technical economy, and solves the problem that the existing sodium ion battery anode carbon material cannot achieve the effects of hard carbon yield, reversible capacity, first-week coulomb efficiency and the like. The negative electrode active material prepared by the preparation method of the negative electrode active material of the sodium ion battery has the advantages of large carbon microcrystalline interlayer spacing and rich and high reversible defect sites; the assembled sodium ion battery has excellent sodium storage performance such as large reversible capacity, high first-week coulomb efficiency and the like.
Description
Technical Field
The invention relates to a sodium ion battery negative electrode active material, a preparation method and application thereof, and belongs to the technical field of sodium ion battery materials.
Background
The lithium ion battery has the characteristics of high energy, high voltage, low self discharge, high energy conversion efficiency, excellent cycle performance and the like, has larger application advantages in the energy storage field, and accounts for 86.3% of the total electrochemical energy storage. However, the lithium resource reserves are limited, and the bottleneck of the resource end gradually appears with the great increase of the battery demand in the fields of new energy automobiles and the like. Sodium resources are abundant in reserves, wide in distribution and simple in extraction. Sodium ion batteries are receiving increasing attention in the battery field as alternatives to lithium ion batteries. In the core performance of the battery, the energy density interval of the sodium ion battery and the lithium iron phosphate battery have an overlapping range. The main advantages of sodium ion batteries compared to lithium ion batteries are: (1) the current collector material is cheaper; (2) better interfacial ion diffusion capability; (3) higher ionic conductivity; (4) the low-temperature performance is more excellent; (5) the safety performance is better.
The negative electrode material is one of the key factors determining the performance of the sodium ion battery. Graphite is a common negative electrode material for lithium ion batteries, but has proven to be unsuitable for sodium storage due to its small carbon crystallite spacing (0.3354 nm). At present, the anode active material of the sodium ion battery is mainly made of hard carbon, and precursors for preparing the hard carbon mainly comprise biomass, resin, asphalt, anthracite and the like. The biomass and resin-based hard carbon have the problems of high cost, low yield, large specific surface area and the like, and the irreversible capacity is high in the first-week charge and discharge process. The asphalt-based carbon material has the problems of low capacity, high cost and the like. The carbon microcrystalline layer spacing of the smokeless coal-based hard carbon is smaller, and the capacity is lower. Therefore, the preparation of a carbonaceous anode carbon material for sodium ion batteries by using the above-mentioned precursors is difficult to achieve in terms of product yield, reversible capacity, first-week coulombic efficiency and the like, and there is an urgent need to find new carbonaceous anode material precursors. Semi-coke is an important large-scale coal chemical product, the semi-coke yield in 2021 is about 6000 ten thousand tons in China, and semi-coke blocks (> 3 mm) are mainly applied to the fields of metallurgy, chemical industry, clean fuel, formed coke, adsorbent and the like. In the process of semi coke production, transportation and use, the produced semi coke powder (< 3 mm) accounts for about 6% of the total semi coke yield. At present, due to the lack of an efficient comprehensive utilization way, a large amount of semi-coke powder is backlogged, which occupies land and causes environmental pollution. It is worth noting that the semi-coke has the characteristics of high fixed carbon content, low ash content, low volatile matter and the like, and has potential advantages in the field of hard carbon preparation for sodium ion batteries. The Chinese patent document CN 115124021A discloses a preparation method of a hard carbon material of a nitrogen-oxygen double-doping process modified semi-coke system, which specifically comprises the following steps: weighing semi-coke blocks and crushing; performing ultrasonic dispersion on the obtained semi coke powder; weighing nitrogen source powder; mixing semi-coke powder and nitrogen source powder to obtain mixed powder; placing the mixed powder into a high-temperature tube furnace, introducing an oxygen-containing atmosphere into the high-temperature furnace, heating, preserving heat and pre-oxidizing; introducing inert gas, heating, preserving heat, and cooling to room temperature to obtain the hard carbon material. According to the method, the efficiency and the content of nitrogen atom doping can be improved through pre-oxidation, the electronic conductivity is improved, the surface wettability is improved, the pore structure is optimized, defects are introduced, more active sites are provided for sodium storage, and therefore the first effect and the specific capacity of the semi-coke-based hard carbon material are improved, but the preparation process is complicated because pre-oxidation and nitrogen doping treatment are required for preparing the hard carbon material.
Disclosure of Invention
The invention aims to provide a preparation method of a sodium ion battery anode active material, which can solve the problem of complex preparation process when the sodium ion battery anode active material is prepared by adopting semi-coke at present.
A second object of the present invention is to provide a negative active material for a sodium ion battery.
The third object of the invention is to provide an application of the negative electrode active material of the sodium ion battery in preparing the sodium ion battery.
In order to achieve the above purpose, the preparation method of the sodium ion battery anode active material of the invention adopts the following technical scheme:
the preparation method of the negative electrode active material of the sodium ion battery comprises the following steps:
(1) Heating the semi-coke powder to 700-1000 ℃ in an inert atmosphere, preserving heat or not, and cooling to obtain a pre-carbonized material;
(2) And heating the pre-carbonized material to 1300-1600 ℃ in an inert atmosphere, preserving heat or not, and cooling to obtain the sodium ion battery anode active material.
According to the preparation method of the sodium ion battery anode active material, the semi-coke powder is subjected to pre-carbonization treatment and high-temperature sintering treatment respectively, so that the preparation method has the advantages of simplicity in operation, environment friendliness, high efficiency, few byproducts and high yield, is easy to realize large-scale production, has good technical economy, and solves the problem that the existing sodium ion battery anode carbon material cannot achieve the effects of hard carbon yield, reversible capacity, first-week coulomb efficiency and the like. The negative electrode active material prepared by the preparation method of the negative electrode active material of the sodium ion battery has the advantages of large carbon microcrystalline layer spacing and rich reversible defect sites, and the assembled sodium ion battery has the advantages of large reversible capacity, high first-week coulomb efficiency and the like. Meanwhile, the invention provides a brand new idea for the high added value comprehensive utilization of the semi coke; the method can change waste into valuable for the semi coke powder which is difficult to use, and has higher social benefit, economic benefit and environmental benefit.
The effect of the pre-carbonization treatment in the hard carbon preparation process is mainly shown as follows: (1) the microstructure characteristic of the hard carbon is optimized, and the sodium storage characteristic is enhanced; (2) volatile matters in the semi-coke are reduced, and for a high-temperature carbonization link, the efficiency can be improved, and the energy consumption can be reduced; (3) the volatile matters in the semi-coke are reduced, and the service life of a high-temperature furnace with high price used in a high-temperature carbonization link is prolonged, because the primary/secondary pyrolysis products generated in the semi-coke heat treatment process influence the service life of key parts of the high-temperature furnace; (4) volatile matters in the semi-coke are reduced, and the operation safety of the high-temperature furnace is improved. Thus, the volatiles of the high temperature furnace feed should be controlled at a lower level.
Preferably, in the step (1), the heating rate of the heating is 1-10 ℃/min. The temperature rising rate of the room temperature to the temperature adopted by the pre-carbonization treatment is controlled to be 1-10 ℃/min, and the effect of indirectly regulating and controlling the microstructure characteristics of the hard carbon is achieved. Preferably, in step (1), the time of the incubation is not more than 3 hours. Further preferably, in the step (1), the time for the heat preservation is 1 to 3 hours. Too short pre-carbonization treatment time can cause imperfect development of hard carbon microcrystals, too long pre-carbonization treatment time can cause high energy consumption and low efficiency.
Preferably, in the step (2), the heating rate of the heating is 1-5 ℃/min. The temperature rising rate of the room temperature to the temperature adopted by the high-temperature sintering treatment is controlled to be 1-5 ℃/min, and the method has the function of directly regulating and controlling the microstructure characteristics of the hard carbon.
Preferably, the incubation time is no more than 6 hours. Further preferably, in the step (2), the time of the heat preservation is 2 to 6 hours. The high-temperature sintering treatment time is too short, which can cause imperfect development of hard carbon microcrystals, and the high-temperature sintering treatment time is too long, which can cause large energy consumption and low efficiency and can negatively affect optimization of hard carbon defect characteristics.
Preferably, the semi-coke powder has an ash content of less than 1%. The ash content of the semi-coke powder is less than 1%, which is favorable for reducing the ash content of hard carbon products and further is favorable for enhancing the sodium storage characteristic of the hard carbon.
Preferably, the semi-coke powder has a particle size of not less than 400 mesh. The granularity of the semi-coke powder is not less than 400 meshes, which is beneficial to enhancing the sodium storage characteristic of hard carbon products.
Preferably, in the step (1), the temperature rising rate from the room temperature to the temperature adopted for the pre-carbonization treatment is 2-10 ℃/min.
Preferably, in the step (2), the temperature rising rate from the room temperature to the temperature used for the high temperature sintering treatment is 3 to 5 ℃/min.
Preferably, the semi-coke powder is prepared by a process comprising the steps of: crushing semi-coke to obtain semi-coke particles, carrying out acid washing and deashing treatment on the semi-coke particles, washing with water until washing liquid is neutral, and drying to obtain semi-coke powder; the granularity of the semi-coke particles is not less than 400 meshes.
It is understood that in the present invention, the particle size of the powder is not less than 400 mesh means that the powder can pass through a 400 mesh sieve; the particle size of the particles is not less than 400 mesh, meaning that the particles pass through a 400 mesh screen.
Preferably, the acid washing and deashing treatment is to sequentially adopt hydrochloric acid and hydrofluoric acid to carry out acid washing and deashing on the semi-coke particles. Compared with other pickling and deashing treatment technologies, the semi-coke particles are sequentially subjected to pickling and deashing by adopting hydrochloric acid and hydrofluoric acid, and the method has the beneficial effect that the deashing effect is more remarkable.
Preferably, the inert atmospheres used in step (1) and step (2) are each independently selected from nitrogen and/or argon.
The invention has no limit to the production place of the semi-coke, and the semi-coke can be used in places such as Xinjiang, inner Mongolia, shaanxi and the like. The semi-coke used in the invention refers to a solid product obtained by dry distillation of brown coal, long flame coal, non-caking coal or weak caking coal with low deterioration degree at about 600 ℃, and the hard carbon material with higher carbon microcrystalline interlayer spacing and rich sodium storage active sites can be obtained by high-temperature carbonization without oxidation and nitrogen doping treatment.
The technical scheme adopted by the negative electrode active material of the sodium ion battery is as follows:
the sodium ion battery anode active material prepared by the preparation method of the sodium ion battery anode active material.
The sodium ion battery anode active material has the advantages of large carbon microcrystalline layer spacing, rich reversible defect sites, large reversible capacity, high first-week coulomb efficiency and the like.
The application of the negative electrode active material of the sodium ion battery in preparing the sodium ion battery adopts the following technical scheme:
the application of the sodium ion battery anode active material prepared by the preparation method of the sodium ion battery anode active material in the preparation of sodium ion batteries.
The sodium ion battery anode active material prepared by the preparation method of the sodium ion battery anode active material is used for preparing the sodium ion battery, so that the prepared sodium ion battery has larger reversible capacity and higher first-week coulomb efficiency.
Preferably, the negative electrode of the sodium ion battery comprises a current collector and a negative electrode active material layer positioned on the surface of the current collector, wherein the negative electrode active material layer is prepared from the negative electrode active material of the sodium ion battery, the conductive agent and the binder.
Preferably, the conductive agent is acetylene black, and the binder is polyvinylidene fluoride.
Preferably, the mass ratio of the sodium ion battery anode active material, the conductive agent and the binder is 90:5:5.
Drawings
Fig. 1 is an XRD pattern of the negative active material of the sodium ion battery prepared in example 1 of experimental example 1;
fig. 2 is an XRD pattern of the negative active material of the sodium ion battery prepared in example 2 of experimental example 1;
fig. 3 is an XRD pattern of the negative active material of the sodium ion battery prepared in example 3 of experimental example 1;
fig. 4 is an XRD pattern of the negative active material of the sodium ion battery prepared in example 4 of experimental example 1;
fig. 5 is an XRD pattern of the negative active material of the sodium ion battery prepared in example 5 of experimental example 1;
fig. 6 is a schematic diagram of a first-week charge-discharge curve of a sodium-ion battery assembled from the negative active material of the sodium-ion battery prepared in example 1 of experimental example 2; in fig. 6, red lines represent charge curves, and black lines represent discharge curves;
fig. 7 is a schematic diagram of a first-week charge-discharge curve of a sodium-ion battery assembled from the negative electrode active material of the sodium-ion battery prepared in example 2 of experimental example 2; in fig. 7, red lines represent charge curves, and black lines represent discharge curves;
fig. 8 is a schematic diagram of a first-week charge-discharge curve of a sodium-ion battery assembled from the negative active material of the sodium-ion battery prepared in example 3 of experimental example 2; in fig. 8, red lines represent charge curves, and black lines represent discharge curves;
fig. 9 is a schematic diagram of a first-week charge-discharge curve of a sodium-ion battery assembled from the negative active material of the sodium-ion battery prepared in example 4 of experimental example 2; in fig. 9, red lines represent charge curves, and black lines represent discharge curves;
fig. 10 is a schematic diagram of a first-week charge-discharge curve of a sodium-ion battery assembled from the negative active material of the sodium-ion battery prepared in example 5 of experimental example 2; in fig. 10, red lines represent charge curves, and black lines represent discharge curves.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The ash content in examples 1 to 6 and comparative examples 1 to 7 of the present invention was measured in accordance with the specification of the standard GB/T1429-2009 "method for measuring ash content of carbon material".
1. The specific examples of the preparation method of the sodium ion battery anode active material of the invention are as follows:
example 1
The preparation method of the sodium ion battery anode active material of the embodiment specifically comprises the following steps:
(1) Preparing semi-coke powder: crushing a certain amount of semi-coke with a production area of Xinjiang into 400 meshes, sequentially carrying out deashing treatment by using dilute hydrochloric acid (mass fraction is 10%) and dilute hydrofluoric acid (mass fraction is 10%), washing by using deionized water until a washing solution is neutral, and drying to obtain semi-coke powder (ash content is less than 1% and granularity is not less than 400 meshes);
(2) Pre-carbonization treatment: placing the semi-coke powder into a tube furnace, heating to 800 ℃ in an inert atmosphere (nitrogen) at a heating rate of 5 ℃/min, preserving heat for 1h, and then cooling to room temperature to obtain a pre-carbonized material;
(3) High-temperature sintering treatment: and (3) placing the pre-carbonized material in a high-temperature furnace, heating to 1400 ℃ in an inert atmosphere (nitrogen) at a heating rate of 1 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain the sodium ion battery anode active material.
Example 2
The preparation method of the sodium ion battery anode active material of the embodiment specifically comprises the following steps:
(1) Preparing semi-coke powder: crushing a certain amount of semi-coke with an inner Mongolia production area to 400 meshes, sequentially carrying out deashing treatment by using dilute hydrochloric acid (mass fraction is 10%) and dilute hydrofluoric acid (mass fraction is 10%), washing by using deionized water until a washing solution is neutral, and drying to obtain semi-coke powder (ash content is less than 1% and granularity is not less than 400 meshes);
(2) Pre-carbonization treatment: placing the semi-coke powder into a tube furnace, heating to 900 ℃ in an inert atmosphere (nitrogen) at a heating rate of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain a pre-carbonized material;
(3) High-temperature sintering treatment: and (3) placing the pre-carbonized material in a high-temperature furnace, heating to 1300 ℃ in an inert atmosphere (argon) at a heating rate of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain the sodium ion battery anode active material.
Example 3
The preparation method of the sodium ion battery anode active material of the embodiment specifically comprises the following steps:
(1) Preparing semi-coke powder: crushing a certain amount of semi-coke with an inner Mongolia production area to 400 meshes, sequentially carrying out deashing treatment by using dilute hydrochloric acid (mass fraction is 10%) and dilute hydrofluoric acid (mass fraction is 10%), washing by using deionized water until a washing solution is neutral, and drying to obtain semi-coke powder (ash content is less than 1% and granularity is not less than 400 meshes);
(2) Pre-carbonization treatment: placing the semi-coke powder into a tube furnace, heating to 800 ℃ in an inert atmosphere (argon) at a heating rate of 5 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain a pre-carbonized material;
(3) High-temperature sintering treatment: and (3) placing the pre-carbonized material in a high-temperature furnace, heating to 1400 ℃ in an inert atmosphere (argon) at a heating rate of 5 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain the sodium ion battery anode active material.
Example 4
The preparation method of the sodium ion battery anode active material of the embodiment specifically comprises the following steps:
(1) Preparing semi-coke powder: crushing a certain amount of semi-coke with an inner Mongolia production area to 400 meshes, sequentially carrying out deashing treatment by using dilute hydrochloric acid (mass fraction is 10%) and dilute hydrofluoric acid (mass fraction is 10%), washing by using deionized water until a washing solution is neutral, and drying to obtain semi-coke powder (ash content is less than 1% and granularity is not less than 400 meshes);
(2) Pre-carbonization treatment: placing the semi-coke powder into a tube furnace, heating to 700 ℃ in an inert atmosphere (argon) at a heating rate of 1 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain a pre-carbonized material;
(3) High-temperature sintering treatment: and (3) placing the pre-carbonized material in a high-temperature furnace, heating to 1400 ℃ in an inert atmosphere (nitrogen) at a heating rate of 3 ℃/min, preserving heat for 6 hours, and then cooling to room temperature to obtain the sodium ion battery anode active material.
Example 5
The preparation method of the sodium ion battery anode active material of the embodiment specifically comprises the following steps:
(1) Preparing semi-coke powder: crushing a certain amount of semi-coke with a production area of Shaanxi into 400 meshes, sequentially carrying out deashing treatment by using dilute hydrochloric acid (mass fraction is 10%) and dilute hydrofluoric acid (mass fraction is 10%), washing by using deionized water until a washing solution is neutral, and drying to obtain semi-coke powder (ash content is less than 1% and granularity is not less than 400 meshes);
(2) Pre-carbonization treatment: placing the semi-coke powder into a tube furnace, heating to 700 ℃ in an inert atmosphere (nitrogen) at a heating rate of 2 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain a pre-carbonized material;
(3) High-temperature sintering treatment: and (3) placing the pre-carbonized material in a high-temperature furnace, heating to 1400 ℃ in an inert atmosphere (nitrogen) at a heating rate of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain the sodium ion battery anode active material.
Example 6
The preparation method of the sodium ion battery anode active material of the embodiment specifically comprises the following steps:
(1) Preparing semi-coke powder: crushing a certain amount of semi-coke with a production area of Xinjiang into 400 meshes, sequentially carrying out deashing treatment by using dilute hydrochloric acid (mass fraction is 10%) and dilute hydrofluoric acid (mass fraction is 10%), washing by using deionized water until a washing solution is neutral, and drying to obtain semi-coke powder (ash content is less than 1% and granularity is not less than 400 meshes);
(2) Pre-carbonization treatment: placing the semi-coke powder into a tube furnace, heating to 1000 ℃ in an inert atmosphere (argon) at a heating rate of 10 ℃/min, preserving heat for 3 hours, and then cooling to room temperature to obtain a pre-carbonized material;
(3) High-temperature sintering treatment: and (3) placing the pre-carbonized material in a high-temperature furnace, heating to 1600 ℃ in an inert atmosphere (argon) at a heating rate of 5 ℃/min, preserving heat for 4 hours, and then cooling to room temperature to obtain the sodium ion battery anode active material.
Comparative example 1
The preparation method of the negative electrode active material for a sodium ion battery of this comparative example differs from that of example 5 only in that in the preparation method of the negative electrode active material for a sodium ion battery of this comparative example, the temperature used for the pre-carbonization treatment in step (2) is 600 ℃.
Comparative example 2
The preparation method of the negative electrode active material for sodium-ion battery of this comparative example differs from that of example 6 only in that in the preparation method of the negative electrode active material for sodium-ion battery of this comparative example, the temperature adopted in the pre-carbonization treatment in step (2) is 1100 ℃.
Comparative example 3
The preparation method of the negative electrode active material for a sodium ion battery of this comparative example differs from that of example 2 only in that the temperature used for the high-temperature sintering treatment in step (3) is 1200 ℃.
Comparative example 4
The preparation method of the negative electrode active material for a sodium ion battery of this comparative example differs from that of example 6 only in that the temperature adopted in the high-temperature sintering treatment in step (3) is 1700 ℃.
Comparative example 5
The preparation method of the negative electrode active material for sodium-ion battery of this comparative example differs from the preparation method of the negative electrode active material for sodium-ion battery of example 5 only in that, in the preparation method of the negative electrode active material for sodium-ion battery of this comparative example, step (1) comprises the steps of: and crushing a certain amount of semi-coke of Shaanxi in a production area to 400 meshes to obtain semi-coke powder.
Comparative example 6
The preparation method of the negative electrode active material for a sodium-ion battery of this comparative example differs from the preparation method of the negative electrode active material for a sodium-ion battery of example 5 only in that in the preparation method of the negative electrode active material for a sodium-ion battery of this comparative example, step (2) is omitted.
Comparative example 7
The preparation method of the negative active material for a sodium ion battery of this comparative example differs from the preparation method of the negative active material for a sodium ion battery of example 5 only in that in the preparation method of the negative active material for a sodium ion battery of this comparative example, step (3) is omitted, and the time of the pre-carbonization treatment in step (2) is adjusted from 2 hours to 4 hours.
2. Specific examples of the negative electrode active material of the sodium ion battery of the invention are as follows:
the negative electrode active material of the sodium ion battery of the present embodiment is prepared by the preparation method of the negative electrode active material of any one of the sodium ion batteries of the embodiments 1 to 6.
3. Specific examples of the application of the negative electrode active material of the sodium ion battery in the preparation of the sodium ion battery are as follows:
the sodium ion battery anode active material prepared by the preparation method of the sodium ion battery anode active material in any one of the embodiments 1-6 is used for preparing a sodium ion battery.
Experimental example 1
To determine the carbon microcrystalline layer spacing of the negative electrode active materials of sodium ion batteries prepared in examples 1 to 6 and comparative examples 1 to 7, the negative electrode active materials of sodium ion batteries prepared in examples 1 to 6 and comparative examples 1 to 7 were characterized by an X-ray diffractometer, respectively, and the characterization results of the negative electrode active materials of sodium ion batteries prepared in examples 1 to 5 are shown in fig. 1 to 5. XRD patterns of the negative electrode active materials for sodium ion batteries prepared in examples 1 to 6 and comparative examples 3, 4 and 7 gave the carbon microcrystalline layer spacing of each negative electrode active material for sodium ion battery, and the results are shown in Table 1.
Table 1 carbon microcrystalline layer spacing of the negative electrode active materials for sodium ion batteries prepared in examples 1 to 6, comparative examples 3, 4, and 7
| Negative electrode active material | Carbon crystallite interlayer spacing (nm) | Negative electrode active material | Carbon crystallite interlayer spacing (nm) |
| Example 1 | 0.372 | Example 2 | 0.372 |
| Example 3 | 0.369 | Example 4 | 0.368 |
| Example 5 | 0.366 | Example 6 | 0.362 |
| Comparative example 3 | 0.376 | Comparative example 4 | 0.355 |
| Comparative example 7 | 0.380 | - | - |
As can be seen from Table 1, the type of semi-coke and the preparation process parameters (temperature, time, etc. of high-temperature sintering treatment and pre-carbonization treatment) have an important influence on the carbon microcrystalline layer spacing of the hard carbon produced.
Experimental example 2
To evaluate the electrochemical properties of the negative active materials for sodium-ion batteries prepared in examples 1 to 6 and comparative examples 1 to 7, the negative active materials for sodium-ion batteries prepared in examples 1 to 6 and comparative examples 1 to 7 were assembled into sodium-ion batteries, and then an electrochemical performance test was performed on a new multi-channel battery test system, with a potential interval of 0.01 to 2.0V.
The method for assembling the sodium ion battery comprises the following steps: uniformly mixing a sodium ion battery anode active material, acetylene black and polyvinylidene fluoride binder (PVDF) according to the mass ratio of 90:5:5, adding a proper amount of 1-methyl-2-pyrrolidone (NMP), grinding to paste slurry, coating the paste slurry on copper foil, drying at 80 ℃ for 12 hours in a vacuum drying box, cutting into a disc-shaped negative plate with the diameter of 12mm, using the sodium plate as a counter electrode, using glass fiber as a diaphragm, and assembling the battery in a glove box to obtain a CR2032 type button battery, wherein electrolyte adopted by the battery is NaPF with the concentration of 1mol/L 6 Solution, naPF 6 The solvent in the solution consists of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1. And before the electrochemical performance test, standing the assembled CR2032 button battery for more than 12 hours, and then performing the electrochemical performance test.
The first cycle charge and discharge curves of the sodium ion batteries assembled from the negative electrode active materials of the sodium ion batteries prepared in examples 1 to 5 are shown in fig. 6 to 10. The first week charge capacity and first week coulombic efficiency of each sodium ion cell are summarized in table 2.
Table 2 first week charge capacity and first week coulombic efficiency of sodium-ion batteries assembled from the negative active materials of sodium-ion batteries prepared in examples 1 to 6 and comparative examples 1 to 7
Claims (10)
1. The preparation method of the negative electrode active material of the sodium ion battery is characterized by comprising the following steps of:
(1) Heating the semi-coke powder to 700-1000 ℃ in an inert atmosphere, preserving heat or not, and cooling to obtain a pre-carbonized material;
(2) And heating the pre-carbonized material to 1300-1600 ℃ in an inert atmosphere, preserving heat or not, and cooling to obtain the sodium ion battery anode active material.
2. The method for producing a negative electrode active material for a sodium ion battery according to claim 1, wherein in the step (1), the heating rate of the heating is 1 to 10 ℃/min; the heat preservation time is not more than 3 hours.
3. The method for producing a negative electrode active material for a sodium ion battery according to claim 1, wherein in the step (2), the heating rate of the heating is 1 to 5 ℃/min; the heat preservation time is not longer than 6 hours.
4. The method for preparing a negative active material for a sodium ion battery according to claim 1, wherein ash content of the semi-coke powder is less than 1%.
5. The method for preparing a negative active material for a sodium ion battery according to claim 1, wherein the semi-coke powder has a particle size of not less than 400 mesh.
6. The method for preparing a negative active material for a sodium ion battery according to any one of claims 1 to 5, wherein the semi-coke powder is prepared by a method comprising the steps of: crushing semi-coke to obtain semi-coke particles, carrying out acid washing and deashing treatment on the semi-coke particles, washing with water until washing liquid is neutral, and drying to obtain semi-coke powder; the granularity of the semi-coke particles is not less than 400 meshes.
7. The method for preparing a negative electrode active material of a sodium ion battery according to claim 6, wherein the acid washing and deashing treatment is to sequentially adopt hydrochloric acid and hydrofluoric acid to carry out acid washing and deashing on semi-coke particles.
8. A negative active material for a sodium ion battery prepared by the method for preparing a negative active material for a sodium ion battery according to any one of claims 1 to 7.
9. Use of a sodium ion battery negative electrode active material prepared by the method for preparing a sodium ion battery negative electrode active material of any one of claims 1-7 in the preparation of a sodium ion battery.
10. The use according to claim 9, wherein the negative electrode of the sodium-ion battery comprises a current collector and a negative electrode active material layer on the surface of the current collector, the negative electrode active material layer being made of the sodium-ion battery negative electrode active material prepared by the method for preparing a negative electrode active material of a sodium-ion battery according to any one of claims 1 to 7, a conductive agent and a binder.
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