CN114890404A - Preparation method of bamboo charcoal capable of being produced in large scale and application of bamboo charcoal in sodium ion battery - Google Patents
Preparation method of bamboo charcoal capable of being produced in large scale and application of bamboo charcoal in sodium ion battery Download PDFInfo
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- CN114890404A CN114890404A CN202210603395.9A CN202210603395A CN114890404A CN 114890404 A CN114890404 A CN 114890404A CN 202210603395 A CN202210603395 A CN 202210603395A CN 114890404 A CN114890404 A CN 114890404A
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 79
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 79
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 79
- 241001330002 Bambuseae Species 0.000 title claims abstract description 71
- 239000011425 bamboo Substances 0.000 title claims abstract description 71
- 239000003610 charcoal Substances 0.000 title claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 241000209128 Bambusa Species 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 229910021385 hard carbon Inorganic materials 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of bamboo charcoal capable of being produced in a large scale and application of the bamboo charcoal serving as an electrode material in a sodium ion battery. The preparation method comprises the following steps: taking different kinds of bamboos including green bamboos, thin bamboos and thick bamboos as raw materials, and washing, drying and crushing the raw materials to obtain yellow powder with small particle size; and then sintering under the protection of inert atmosphere to obtain the bamboo charcoal black powder. The bamboo charcoal material with proper carbon layer spacing and pore structure can be obtained by preprocessing bamboo in the early stage and optimizing carbonization temperature, heating rate and sintering time, and the bamboo charcoal material shows excellent electrochemical performance when being used as a negative electrode material of a sodium ion battery. The method has the advantages of abundant raw materials, low cost and simple preparation method, and the obtained bamboo charcoal powder can be applied to sodium ion battery industrialization in a large scale. Has good prospect.
Description
Technical Field
The invention relates to the field of preparation of sodium ion battery electrode materials, in particular to a preparation method of a negative electrode material capable of promoting industrialization of a low-cost high-performance sodium ion battery.
Background
The transitional use of fossil fuels is a major cause of the increase in the greenhouse effect, and therefore, the development of renewable energy has been receiving more and more attention in recent years. However, most renewable energy sources have the characteristics of intermittency, instability and the like, and if a large amount of renewable energy sources are put into a power grid, the power grid is greatly influenced. Under the background, higher requirements are put on energy storage devices, and electrochemical energy storage systems are widely concerned with the advantages of short construction period, adjustable capacity, strong flexibility and the like. Lithium ion batteries dominate the global electrochemical power market due to their high energy density, long cycle life, and good rate capability. However, lithium ion batteries cannot fully meet the requirements of large-scale electrochemical energy storage systems due to the high cost caused by insufficient lithium resources. In this regard, sodium ion batteries are considered to be the most promising candidate for electrochemical energy storage systems, with the advantages of low cost, abundant sodium reserves, and widespread distribution. Furthermore, since sodium and lithium belong to the same main group on the periodic table of the elements, they have similar chemical properties and parallel operating principles, which means that rechargeable sodium-ion batteries will be a suitable alternative to lithium-ion batteries.
The hard carbon material is considered to be the most practical sodium ion battery cathode material due to the abundant carbon source, low cost, no toxicity, environmental protection and low sodium storage potential. However, the hard carbon negative electrode also has problems of low first-cycle coulombic efficiency, poor long-cycle stability, high preparation cost and the like in practical application. For example, the use of biomass (bagasse, straw, peanut shell, cherry petal, orange peel, etc.) derived hard carbon materials for sodium ion batteries presents problems of lower first week coulombic efficiency and lower reversible capacity, as well as cumbersome preparation process, etc., making it difficult to meet the requirements of hard carbon as a negative electrode material for commercial sodium ion batteries.
Therefore, based on the challenges faced by the above hard carbon negative electrode materials, it is urgently needed to develop a sodium ion battery hard carbon negative electrode material with simple process, low cost, high first efficiency and high sodium storage capacity.
Disclosure of Invention
The invention aims to solve the problems that: the existing biomass hard carbon material has the disadvantages of complex preparation process, high energy consumption, low coulombic efficiency and low capacity when used as an electrode material for the first time.
In order to solve the problems, the technical scheme of the invention is as follows: the preparation method of bamboo charcoal capable of being produced in large scale and the application thereof in sodium ion batteries comprise the following steps:
washing bamboo with deionized water for multiple times, and drying in a forced air drying oven;
step (2) mechanically crushing the dried bamboo obtained in the step (1) into bamboo powder by using a crusher;
step (3) placing the powder material obtained in the step (2) in a tubular furnace at a high temperature, and sintering under the protection of inert gas to obtain bamboo charcoal black powder;
and (4) further grinding the black material obtained in the step (3) into powder, and sieving the powder by using a screen to obtain bamboo charcoal powder with uniform particle size distribution, so as to obtain the bamboo charcoal material used as the negative electrode material of the sodium-ion battery.
Preferably, the drying temperature in the step (1) is 60-180 ℃, and the drying time is 6-24 h.
Preferably, the mechanical crushing time in the step (2) is 10 min to 60 min.
Preferably, the inert gas in the step (3) is argon or nitrogen, the sintering temperature is 1200-1600 ℃, the heating rate is 1-5 ℃/min, and the sintering time is 1-6 h.
Preferably, the size of the screen mesh in the step (4) is 200-500 meshes.
According to the invention, a series of bamboo charcoal powder with different particle sizes and microstructures is obtained by controlling the size of the precursor and adjusting the reaction temperature, the heating rate and the reaction time, and the prepared bamboo charcoal powder has high coulombic efficiency and circulation stability when being used for a sodium ion battery. The method has the advantages of wide raw material source, simple operation and environmental protection, and is suitable for the production of large-scale sodium ion battery cathode materials.
Drawings
Fig. 1 is an XRD pattern of the bamboo charcoal material prepared in example 1 of the present invention;
FIG. 2 is a preferred, Raman plot prepared in example 1 of the present invention;
FIG. 3 is a first-turn charge-discharge curve diagram of a sodium-ion battery prepared in example 1 of the present invention, wherein the current density of the prepared sodium-ion battery is 20 mA/g;
FIG. 4 is a graph of the long cycle performance of the sodium ion battery prepared in example 1 of the present invention at a current density of 20 mA/g.
Detailed Description
In order that the invention may be better understood, the invention will now be further described by way of specific examples.
The present invention will be further illustrated by the following specific examples.
Example 1: the preparation method of bamboo charcoal capable of being produced in large scale and the application thereof in sodium ion batteries comprise the following steps:
washing bamboo with deionized water for multiple times, and drying in a forced air drying oven at 80 ℃ for 12 h;
step (2), mechanically crushing the material in the step (1) for 30 min by using a crusher;
in an argon atmosphere, heating the material in the step (3) to 1400 ℃ in a tubular furnace at a heating rate of 5 ℃/min, preserving the heat for 2 h, and then cooling to room temperature to obtain bamboo charcoal powder;
and (4) taking out the obtained bamboo charcoal powder, grinding the bamboo charcoal powder into powder, and sieving the powder by using a 300-mesh sieve to obtain the hard carbon cathode material of the sodium ion battery.
Fig. 1 is an XRD chart of the bamboo charcoal powder, from which it can be seen that all diffraction peaks are typical characteristic peaks of hard carbon materials, and no obvious impurity peak appears.
Fig. 2 is a Raman chart of the bamboo charcoal powder, and it can be seen from the chart that the material has a disordered structure.
FIG. 3 is a first-cycle charge-discharge curve diagram of the sodium ion battery prepared from the bamboo charcoal powder with a current density of 20 mA/g, and it can be seen from the first-cycle charge-discharge capacity of 280/310 mAh/g, respectively, and the corresponding first-cycle coulombic efficiency is 90%.
FIG. 4 is a long cycle performance diagram of the sodium ion battery prepared from the bamboo charcoal powder with a current density of 20 mA/g, and it can be seen that the capacity is still close to 300 mAh/g after 60 circles.
Example 2: a preparation method of bamboo charcoal capable of being produced in large scale and application thereof in a sodium ion battery comprise the following steps:
washing bamboo with deionized water for multiple times, and drying in a forced air drying oven at 80 ℃ for 12 h;
mechanically crushing the material in the step (1) for 30 min by using a crusher;
in an argon atmosphere, heating the material in the step (3) to 1400 ℃ in a tubular furnace at a heating rate of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature to obtain bamboo charcoal powder;
and (4) taking out the obtained bamboo charcoal powder, grinding the bamboo charcoal powder into powder, and sieving the powder by using a 300-mesh sieve to obtain the hard carbon cathode material of the sodium ion battery.
Example 3: a preparation method of bamboo charcoal capable of being produced in large scale and application thereof in a sodium ion battery comprise the following steps:
washing bamboos with deionized water for multiple times, and then placing the bamboos in a forced air drying box at the temperature of 80 ℃ for drying for 12 hours;
mechanically crushing the material in the step (1) for 10 min by using a crusher;
in an argon atmosphere, heating the material in the step (3) to 1400 ℃ in a tubular furnace at a heating rate of 1 ℃/min, preserving the heat for 2 h, and then cooling to room temperature to obtain bamboo charcoal powder;
and (4) taking out the obtained bamboo charcoal powder, grinding the bamboo charcoal powder into powder, and sieving the powder by using a 300-mesh sieve to obtain the hard carbon cathode material of the sodium ion battery.
Example 4: a preparation method of bamboo charcoal capable of being produced in large scale and application of the bamboo charcoal in a sodium ion battery comprise the following steps:
washing bamboo with deionized water for multiple times, and drying in a forced air drying oven at 80 ℃ for 12 h;
mechanically crushing the material in the step (1) for 10 min by using a crusher;
in an argon atmosphere, heating the material in the step (3) to 1200 ℃ in a tubular furnace at a heating rate of 1 ℃/min, preserving the heat for 4 h, and then cooling to room temperature to obtain bamboo charcoal powder;
and (4) taking out the obtained bamboo charcoal powder, grinding the bamboo charcoal powder into powder, and sieving the powder by using a 300-mesh sieve to obtain the hard carbon cathode material of the sodium ion battery.
Example 5: a preparation method of bamboo charcoal capable of being produced in large scale and application thereof in a sodium ion battery comprise the following steps:
washing bamboo with deionized water for multiple times, and drying in a forced air drying oven at 80 ℃ for 12 h;
mechanically crushing the material in the step (1) for 10 min by using a crusher;
in an argon atmosphere, heating the material in the step (3) to 1200 ℃ in a tubular furnace at a heating rate of 1 ℃/min, preserving the heat for 6 hours, and then cooling to room temperature to obtain bamboo charcoal powder;
and (4) taking out the obtained bamboo charcoal powder, grinding the bamboo charcoal powder into powder, and sieving the powder by using a 500-mesh sieve to obtain the hard carbon cathode material of the sodium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of bamboo charcoal capable of being produced in large scale and application of the bamboo charcoal in a sodium ion battery are characterized by comprising the following steps:
washing bamboos with deionized water for multiple times, and placing the bamboos in a forced air drying oven for drying;
step (2) mechanically crushing the material obtained in the step (1) by using a crusher to obtain bamboo powder;
step (3) placing the powder material obtained in the step (2) in a tube furnace, and sintering under the protection of inert gas to obtain bamboo charcoal black powder;
and (4) further grinding the black powder material obtained in the step (3), and sieving the ground black powder material by using a mesh sieve to obtain bamboo charcoal powder with uniform particle size distribution, so as to obtain the bamboo charcoal material serving as the negative electrode material of the sodium-ion battery.
2. The method for preparing bamboo charcoal capable of being produced in large scale and the application of the bamboo charcoal in sodium ion batteries according to claim 1, wherein the bamboo in the step (1) is green bamboo, fine bamboo or coarse bamboo.
3. The preparation method of bamboo charcoal capable of being produced in large scale and the application of bamboo charcoal in sodium ion batteries according to claim 1 are characterized in that the forced air drying temperature in the step (1) is 60-180 ℃, and the drying time is 6-24 h.
4. The method for preparing bamboo charcoal capable of being produced in large scale and the application of the bamboo charcoal in sodium ion batteries according to claim 1, wherein the mechanical crushing time in the step (2) is 10-60 min.
5. The preparation method of bamboo charcoal capable of being produced in large scale and the application of bamboo charcoal in sodium ion batteries according to claim 1 are characterized in that the inert gas in the step (3) is argon or nitrogen, the sintering temperature is 1200-1600 ℃, the heating rate is 1-5 ℃/min, and the sintering time is 1-6 h.
6. The method for preparing bamboo charcoal capable of being produced in large scale according to claim 1, wherein the size of the screen mesh in step (4) is 200-500 meshes.
7. A sodium ion battery, characterized by: comprising the bamboo charcoal prepared by the method for preparing bamboo charcoal which can be produced on a large scale according to any one of claims 1-6.
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|---|---|---|---|
| CN202210603395.9A CN114890404A (en) | 2022-05-31 | 2022-05-31 | Preparation method of bamboo charcoal capable of being produced in large scale and application of bamboo charcoal in sodium ion battery |
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2022
- 2022-05-31 CN CN202210603395.9A patent/CN114890404A/en active Pending
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