CN117049505A - Preparation method of hard carbon negative electrode material, hard carbon negative electrode material and sodium ion battery - Google Patents
Preparation method of hard carbon negative electrode material, hard carbon negative electrode material and sodium ion battery Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 106
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 95
- 239000008367 deionised water Substances 0.000 claims abstract description 86
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000005406 washing Methods 0.000 claims abstract description 73
- 238000001035 drying Methods 0.000 claims abstract description 51
- 239000010405 anode material Substances 0.000 claims abstract description 42
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 38
- 238000003763 carbonization Methods 0.000 claims abstract description 30
- 239000002028 Biomass Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 238000009656 pre-carbonization Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000011734 sodium Substances 0.000 abstract 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 abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 99
- 235000004936 Bromus mango Nutrition 0.000 description 51
- 241001093152 Mangifera Species 0.000 description 51
- 235000014826 Mangifera indica Nutrition 0.000 description 51
- 235000009184 Spondias indica Nutrition 0.000 description 51
- 238000000227 grinding Methods 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 31
- 239000012300 argon atmosphere Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 238000010298 pulverizing process Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000004570 mortar (masonry) Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 230000007935 neutral effect Effects 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 244000288157 Passiflora edulis Species 0.000 description 1
- 235000000370 Passiflora edulis Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application is suitable for the technical field of materials, and provides a preparation method of a hard carbon negative electrode material, the hard carbon negative electrode material and a sodium ion battery, and the preparation method comprises the following steps: placing the biomass material and deionized water into a hydrothermal reaction at 180-200 ℃ for 12-24 hours, and performing washing and drying treatment to obtain a pre-carbonized intermediate; and (3) performing alkali treatment on the pre-carbonized intermediate after sintering carbonization treatment for 12-36 hours, and performing washing and drying treatment to obtain the hard carbon anode material. According to the application, after the biomass material is subjected to the action of specific hydrothermal treatment conditions, the porous spherical hard carbon anode material with uniformly dispersed holes is formed after high-temperature carbonization and alkali treatment, the hard carbon anode material is favorable for increasing electrochemical active sites and improving the specific capacity of sodium storage, and is an ideal sodium ion battery anode material.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a preparation method of a hard carbon negative electrode material, the hard carbon negative electrode material and a sodium ion battery.
Background
Sodium ion batteries are one of the electrochemically high-activity and high-yield element-based electrical energy storage devices, and the resource cost is lower compared with lithium ion batteries. Commercial lithium ion batteries use graphitic carbon as the negative electrode with low cost, high coulombic efficiency and excellent cycling performance. However, na + The ionic radius (0.102 nm) is larger than the ionic diameter (0.076 nm) of lithium ions. It is difficult to embed into the conventional graphite negative electrode, so that the graphite negative electrode is not suitable for sodium ion batteries.
Therefore, developing a suitable negative electrode material for sodium-ion batteries is a problem to be solved. Biomass waste exists in a large amount in the market, and considering that biomass is organic matter, if the biomass waste is carbonized to prepare hard carbon anode materials, high value-added utilization of waste biomass resources is realized. The hard carbon material has a larger interlayer spacing and a long-range disordered structure than graphite, which is beneficial to Na + Is stored in the memory. Although Na is + The intercalation mechanism is still controversial, but the intercalation, adsorption and packing mechanisms and the combination of the three have gained acceptance by most people, so that the current adjustment of hard carbon structure, porosity, surface chemistry and defects are important for improving the anode performance of sodium ion batteries. Studies have shown that at a given sintering temperature, the properties of the carbon material obtained depend on the composition and molecular structure of the precursor. Because of the diversity of biomass, hard carbon materials directly carbonized from biomass have the problems of large impurity and microstructure uncertainty, so that the electrochemical performance of the hard carbon materials cannot be ensured.
Disclosure of Invention
The embodiment of the application aims to provide a preparation method of a hard carbon negative electrode material, and aims to solve the problems of high uncertainty of impurities and microstructure and unstable electrochemical performance of the existing hard carbon material.
The embodiment of the application is realized in such a way that the preparation method of the hard carbon anode material comprises the following steps:
placing the biomass material and deionized water into a hydrothermal reaction at 180-200 ℃ for 12-24 hours, and performing washing and drying treatment to obtain a pre-carbonized intermediate;
and (3) performing alkali treatment on the pre-carbonized intermediate after sintering carbonization treatment for 12-36 hours, and performing washing and drying treatment to obtain the hard carbon anode material.
Another object of the embodiment of the present application is to provide a hard carbon negative electrode material, which is prepared by the preparation method of the hard carbon negative electrode material.
Another object of the embodiment of the present application is a sodium ion battery including the hard carbon anode material described above
According to the preparation method of the hard carbon negative electrode material, the biomass material is subjected to the action of specific hydrothermal treatment conditions and then subjected to high-temperature carbonization and alkali treatment to form the porous spherical hard carbon negative electrode material with uniformly dispersed holes, the hard carbon negative electrode material is favorable for increasing electrochemical active sites and improving the specific capacity of sodium storage, and the hard carbon negative electrode material is an ideal negative electrode material of a sodium ion battery.
Drawings
FIG. 1 is an SEM image of a hard carbon anode material provided in example 1 of the present application;
FIG. 2 is an SEM image of a hard carbon negative electrode material provided by comparative example 1;
FIG. 3 is an SEM image of a hard carbon negative electrode material provided in comparative example 3 of the application;
FIG. 4 is an SEM image of a hard carbon negative electrode material provided by comparative example 4;
FIG. 5 is an SEM image of a hard carbon negative electrode material provided by comparative example 8;
FIG. 6 shows that the hard carbon anode material of example 1 and comparative examples 1-2 of the present application was prepared at a temperature of 50mA.g -1 And a graph of first charge and discharge at current density.
FIG. 7 shows that the hard carbon anode material of example 1 and comparative examples 1-2 of the present application was prepared at 100 mA.g -1 Cycling performance plot at current density.
Fig. 8 is a graph showing the rate performance of the hard carbon negative electrode materials provided in example 1 and comparative examples 1-2 of the present application at 0.01-3V voltage.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The embodiment of the application provides a preparation method of a hard carbon negative electrode material based on the problem that hard carbon materials directly carbonized from various biomasses have impurities and microstructures (such as porosity, interlayer spacing, surface groups, defect conditions and the like) with large uncertainty.
The embodiment of the application provides a preparation method of a hard carbon anode material, which comprises the following steps:
placing the biomass material and deionized water into a hydrothermal reaction at 180-200 ℃ for 12-24 hours, and performing washing and drying treatment to obtain a pre-carbonized intermediate;
and (3) performing alkali treatment on the pre-carbonized intermediate after sintering carbonization treatment for 12-36 hours, and performing washing and drying treatment to obtain the hard carbon anode material.
In the embodiment of the application, the control of the hydrothermal reaction temperature and the hydrothermal reaction time directly influences the formation of the porous spherical morphology of the obtained hard carbon anode material, thereby influencing the electrochemical performance. When the hydrothermal reaction temperature is lower than 180 ℃, spherical and porous morphology cannot be obtained, and when the hydrothermal reaction temperature is higher than 200 ℃, the phenomenon of spherical hard carbon agglomeration occurs, and the reversible specific capacity of the material is reduced. In addition, when the hydrothermal reaction time is less than 12 hours, the reaction time is insufficient, only a small amount of porous spherical hard carbon morphology can be obtained, and when the hydrothermal reaction time exceeds 24 hours, spherical morphology with burrs on the surface is formed, and the reversible specific capacity of the material is reduced. Preferably, when the hydrothermal reaction temperature is 200 ℃ and the hydrothermal reaction time is 24 hours, the porous spherical morphology of the obtained hard carbon anode material is optimal, and the reversible specific capacity of the material is highest.
In the embodiment of the application, the alkali treatment time also directly influences the formation of the porous spherical morphology of the obtained hard carbon anode material, when the alkali treatment time is less than 12 hours, the reaction time is insufficient, only a small amount of porous spherical hard carbon morphology can be obtained, and when the alkali treatment time exceeds 36 hours, the spherical morphology with burrs on the surface is formed, and the reversible specific capacity of the material is greatly reduced. Preferably, the alkaline treatment is carried out for 12 hours.
Optionally, the biomass material and deionized water are subjected to hydrothermal reaction at 180-200 ℃ for 12-36 hours, and are subjected to washing and drying treatment to obtain a pre-carbonized intermediate, which comprises the following steps:
fully stirring the biomass material and deionized water, placing the mixture into a hydrothermal reaction at 180-200 ℃ for 12-36 hours, washing the mixture, and placing the washed mixture into a vacuum drying condition at 50-110 ℃ for 12-36 hours to obtain a pre-carbonized intermediate.
The biomass material and a proper amount of deionized water are fully stirred and mixed, and the specific dosage can be determined according to actual requirements, for example, 2-3g of mango peel biomass material and 50mL of deionized water are mixed and stirred.
Optionally, the pre-carbonized intermediate is subjected to alkali treatment for 12-36 hours after sintering carbonization treatment, and is subjected to washing and drying treatment to obtain the hard carbon anode material, which comprises the following steps:
after the pre-carbonization intermediate is crushed, sintering and carbonizing the pre-carbonization intermediate for 1 to 5 hours at the carbonization temperature of 600 to 1800 ℃ to obtain a carbonized product;
and mixing and stirring the carbonized product and the alkali solution for 12-36 hours, and washing and drying to obtain the hard carbon anode material.
The sintering carbonization treatment is performed in an inert gas atmosphere, and can be nitrogen, argon or other inert gases.
Wherein the alkali solution can be one or two of sodium hydroxide and potassium hydroxide with the concentration of 0.5-2M.
The biomass material can be fruit peel with a certain thickness of more than 2 mm, fruit peel contains more pectin and sugar, mango peel treated by a hydrothermal method can generate spherical hard carbon, porous spherical morphology can be formed after high-temperature carbonization and alkali treatment, the electrochemical active site can be increased, and the specific sodium storage capacity can be improved, for example, mango peel, passion fruit peel, banana peel, orange peel and the like can be used. Considering that mango is a fruit widely planted in south China, mango peel is wide in source and low in cost, and is one of ideal biomass carbon sources, the following specific examples take waste mango peel as a carbon source for illustration, and the protection scope of the application is not limited by the fact.
The embodiment of the application also provides a hard carbon negative electrode material, which is prepared by the preparation method of the hard carbon negative electrode material.
The embodiment of the application also provides a sodium ion battery, which comprises the hard carbon anode material.
Specific examples of certain embodiments of the application are given below and are not intended to limit the scope of the application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M sodium hydroxide, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material.
Example 2
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 190 ℃ for 12 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M sodium hydroxide, stirring for 24 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material.
Example 3
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 12 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M sodium hydroxide, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material.
Example 4
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 12 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 36 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material.
Example 5
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 190 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 36 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material.
Example 6
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 24 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material.
Scanning Electron Microscope (SEM) observation was performed on the hard carbon anode materials prepared in examples 1-6, fig. 1 is a morphology diagram of the hard carbon anode material prepared in example 1, and the morphologies of the hard carbon anode materials prepared in other examples 2-6 are equivalent to those of fig. 1, and are not shown one by one, so that it can be seen that the prepared hard carbon anode material is spherical with uniformly dispersed holes.
The hard carbon negative electrode materials prepared in examples 1 to 6 were subjected to sodium ion battery assembly, specifically, 0.2g of the synthesized hard carbon negative electrode material, 0.025g of PVDF binder and 0.025g of ketjen conductive agent were weighed according to the weight ratio of 8:1:1, a proper amount of NMP solvent was dropped to prepare slurry, the slurry was coated on a copper foil, dried and then cut into electrode wafers, and CR2025 button cell was assembled for electrochemical performance test, and the test results are shown in Table 1.
TABLE 1
The research of the application shows that the hydrothermal treatment process parameter and the alkali treatment time parameter have remarkable influence on the morphology and the electrochemical performance of the hard carbon anode material, and the specific reference is shown in the following comparative examples 1-14:
comparative example 1
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. And (3) placing the mango peel powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under an argon atmosphere, preserving heat for 1 hour, and fully grinding the material after the mango peel powder is naturally cooled to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Scanning Electron Microscope (SEM) images of the mango peel biomass hard carbon cathode material prepared according to the method of comparative example 1 are shown in fig. 2, and it can be seen that the prepared hard carbon has a random morphology.
Comparative example 2
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; and (3) fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, preserving heat for 1 hour, and fully grinding the material after the dried pre-carbonized spherical intermediate powder is naturally cooled to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 3
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 170 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into a 1M sodium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Scanning Electron Microscope (SEM) images of the mango peel biomass spherical hard carbon cathode material prepared according to the method of comparative example 3 are shown in fig. 3, and it can be seen that the prepared hard carbon has an irregular block shape and a shape with a small amount of spherical mixture.
Comparative example 4
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, performing hydrothermal reaction at 210 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into a 1M sodium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Scanning Electron Microscope (SEM) images of the mango peel biomass spherical hard carbon cathode material prepared according to the method of comparative example 4 are shown in FIG. 4, and it can be seen that the prepared hard carbon has a partially agglomerated spherical morphology.
Comparative example 5
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 170 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 6
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, performing hydrothermal reaction at 210 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 7
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction for 8 hours at 200 ℃, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into a 1M sodium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 8
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 36 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into a 1M sodium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
As shown in fig. 5, a Scanning Electron Microscope (SEM) image of the mango peel biomass spherical hard carbon anode material prepared according to the method of comparative example 8 shows that the prepared hard carbon is spherical with burrs on the surface.
Comparative example 9
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction for 8 hours at 200 ℃, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 10
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 36 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 12 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 11
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into a 1M sodium hydroxide solution, stirring for 8 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 12
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into a 1M sodium hydroxide solution, stirring for 48 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon negative electrode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 13
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 8 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material. The sodium ion battery was assembled in the same manner as in the above examples.
Comparative example 14
Washing mango peel with deionized water, dehydrating to dryness, and pulverizing into powder. Taking 2.5g of mango peel powder and 50mL of deionized water, fully and uniformly stirring, transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and then placing into a vacuum oven at 80 ℃ for drying for 24 hours to obtain pre-carbonized spherical intermediate powder; fully grinding the dried pre-carbonized spherical intermediate powder by using a mortar, placing the ground pre-carbonized spherical intermediate powder into a tube furnace, heating to 1000 ℃ at 5 ℃/min under argon atmosphere, and preserving heat for 1 hour to finish final carbonization, thus obtaining carbonized products; and (3) fully grinding the material after natural cooling, immersing the material into 1M potassium hydroxide solution, stirring for 48 hours, washing the material with deionized water to be neutral, and finally placing the material in a vacuum oven for thorough drying to obtain the hard carbon anode material. The sodium ion battery was assembled in the same manner as in the above examples.
The hard carbon anode materials prepared in comparative examples 1 to 14 were subjected to electrochemical performance test, and the test results are shown in table 2.
TABLE 2
At normal temperature, a CT-4000 type Xinwei battery test system is adopted, and the voltage range is 0.01-3V, and the current density is 100 mA.g -1 The hard carbon negative electrode materials prepared in example 1 and comparative examples 1 to 2 were subjected to charge-discharge performance and cycle performance tests, and the test results are shown in fig. 6 to 8.
FIGS. 6-8 are initial charge-discharge curves of 100 mA.g for the materials prepared according to example 1 and comparative examples 1-2, respectively -1 Cycling performance at current density, rate performance. As shown in FIGS. 6-7, the hard carbon materials prepared in example 1 and comparative examples 1-2 have different electrochemical properties, and the specific capacities for initial charge are 301.6 mAh.g, respectively -1 、180.1mAh·g -1 And 215.1 mAh.g -1 . Example 1 has the highest first charge specific capacity and high initial coulombic efficiency. As can be seen from fig. 8, the most stable rate performance of example 1 is outstanding, which indicates that the sodium ion battery assembled by the porous spherical hard carbon anode material of example 1 has good stability. In summary, the electrochemical properties of the hard carbon negative electrode material prepared in example 1 were superior to those of the hard carbon negative electrode materials prepared in comparative examples 1 to 2.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The preparation method of the hard carbon anode material is characterized by comprising the following steps:
placing the biomass material and deionized water into a hydrothermal reaction at 180-200 ℃ for 12-24 hours, and performing washing and drying treatment to obtain a pre-carbonized intermediate;
and (3) performing alkali treatment on the pre-carbonized intermediate after sintering carbonization treatment for 12-36 hours, and performing washing and drying treatment to obtain the hard carbon anode material.
2. The method for producing a hard carbon negative electrode material according to claim 1, wherein the hydrothermal reaction temperature is 200 ℃.
3. The method for producing a hard carbon negative electrode material according to claim 1, wherein the hydrothermal reaction time is 24 hours.
4. The method for producing a hard carbon negative electrode material according to claim 1, wherein the alkali treatment is performed for 12 hours.
5. The method for preparing the hard carbon anode material according to claim 1, wherein the steps of placing the biomass material and deionized water in 180-200 ℃ for hydrothermal reaction for 12-36 hours, washing and drying to obtain a pre-carbonized intermediate comprise:
fully stirring the biomass material and deionized water, placing the mixture into a hydrothermal reaction at 180-200 ℃ for 12-36 hours, washing the mixture, and placing the washed mixture into a vacuum drying condition at 50-110 ℃ for 12-36 hours to obtain a pre-carbonized intermediate.
6. The method for preparing the hard carbon negative electrode material according to claim 1, wherein the pre-carbonizing intermediate is subjected to alkali treatment for 12-36 hours after sintering carbonization treatment, and the hard carbon negative electrode material is obtained after washing and drying treatment, and the method comprises the following steps:
after the pre-carbonization intermediate is crushed, sintering and carbonizing the pre-carbonization intermediate for 1 to 5 hours at the carbonization temperature of 600 to 1800 ℃ to obtain a carbonized product;
and mixing and stirring the carbonized product and the alkali solution for 12-36 hours, and washing and drying to obtain the hard carbon anode material.
7. The method for preparing a hard carbon negative electrode material according to claim 6, wherein the alkali solution is one or both of sodium hydroxide and potassium hydroxide.
8. The method for preparing a hard carbon negative electrode material according to claim 1, wherein the biomass material is a fruit peel.
9. The hard carbon anode material is characterized by being prepared by the preparation method of the hard carbon anode material in any one of claims 1-8.
10. A sodium ion battery comprising the hard carbon negative electrode material of claim 9.
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