CN116553514A - Preparation method of coconut shell-based hard carbon material and sodium ion battery - Google Patents
Preparation method of coconut shell-based hard carbon material and sodium ion battery Download PDFInfo
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- CN116553514A CN116553514A CN202310493118.1A CN202310493118A CN116553514A CN 116553514 A CN116553514 A CN 116553514A CN 202310493118 A CN202310493118 A CN 202310493118A CN 116553514 A CN116553514 A CN 116553514A
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- 235000013162 Cocos nucifera Nutrition 0.000 title claims abstract description 167
- 244000060011 Cocos nucifera Species 0.000 title claims abstract description 167
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 67
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 239000011257 shell material Substances 0.000 claims description 103
- 238000003763 carbonization Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 230000001681 protective effect Effects 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001351 cycling effect Effects 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 abstract description 9
- 238000002203 pretreatment Methods 0.000 abstract description 7
- 239000007833 carbon precursor Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 229910052593 corundum Inorganic materials 0.000 description 22
- 239000010431 corundum Substances 0.000 description 22
- 229910052573 porcelain Inorganic materials 0.000 description 22
- 239000002699 waste material Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000009656 pre-carbonization Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910019398 NaPF6 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 235000001759 Citrus maxima Nutrition 0.000 description 1
- 244000276331 Citrus maxima Species 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 244000082946 Tarchonanthus camphoratus Species 0.000 description 1
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a coconut shell-based hard carbon material and a sodium ion battery, and provides application of regulating and controlling oxygen content in the material in the coconut shell treatment process in improving electrochemical performance of the coconut shell-based hard carbon material. The invention also provides a method for preparing the hard carbon material by pretreating biomass coconut shells. The invention provides a plurality of pretreatment methods for treating biomass hard carbon precursor coconut shells so as to solve the problems of low specific capacity, poor circulation stability and the like of biomass hard carbon. The pretreatment method provided by the invention can effectively remove impurities in biomass, or can effectively improve the crosslinking structure of the coconut shell precursor and provide certain conditions for the subsequent formation of more closed cells. The coconut shell precursor used in the invention has the advantages of low cost, energy conservation, environmental protection, simple operation of the treatment process, no need of complex process and expensive equipment, no pollution, large-scale mass production, contribution to large-scale industrialization and suitability for industrial requirements.
Description
Technical Field
The invention belongs to the technical field of coconut shell-based hard carbon materials, relates to application of regulating and controlling oxygen content in a material in the coconut shell treatment process in improving electrochemical performance of the coconut shell-based hard carbon material, a method for preparing the hard carbon material by pretreating biomass coconut shells and a sodium ion battery, and particularly relates to a preparation method of the coconut shell-based hard carbon material and the sodium ion battery.
Background
Lithium ion batteries continue to receive attention and research in the industry because they have been successfully used in various portable devices and electric vehicles, but due to the limitation of lithium resources, the cost of lithium ion batteries increases year by year, and other rechargeable batteries must be developed instead of lithium ion batteries. Because of the similar characteristics, the sodium ions of the same main group as lithium have abundant crust reserves and low price, the lithium ion battery has attracted wide attention, and the development of a high-capacity, high-stability and high-first-efficiency negative electrode material is an unavoidable problem, and the hard carbon negative electrode becomes the most competitive material for commercialization of the negative electrode of the sodium ion battery because of the high-capacity, high-first-efficiency and high-stability. Biomass hard carbon precursors are low in cost, wide in source and free of pollution, and are attracting attention of researchers, and various precursors including corncobs, shrimp shells, camphorwood, nut shells, shaddock peels and the like are proposed by the researchers, but the development of hard carbon is always limited by lower specific capacity and low first effect.
Therefore, how to obtain a proper mode solves the problems of the biomass hard carbon precursor, further expands the application depth and breadth of the biomass hard carbon, has great significance for the practical application of the biomass hard carbon, and is one of the focuses of prospective researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide an application of regulating and controlling the oxygen content in the material in the coconut shell treatment process in the aspect of improving the electrochemical performance of the coconut shell-based hard carbon material, a method for preparing the hard carbon material by pretreating biomass coconut shells and a sodium ion battery.
The invention provides an application of regulating and controlling oxygen content in a material in a coconut shell treatment process in improving electrochemical performance of a coconut shell-based hard carbon material.
Preferably, the regulating method comprises one or more of hydrothermal pretreatment of coconut shells, low-temperature pretreatment of the coconut shells under an air atmosphere, low-temperature pretreatment of the coconut shells under a protective atmosphere and low-temperature pretreatment of the coconut shells under a mixed atmosphere of hydrogen and protective gas;
the oxygen content includes the oxygen content of the pre-treated precursor material and/or the oxygen content of the coconut shell based hard carbon material.
Preferably, the temperature of the hydrothermal pretreatment is 100-200 ℃;
the hydrothermal pretreatment time is 2-24 hours;
the temperature of the low-temperature pretreatment under the air atmosphere is 100-300 ℃;
the time for the low-temperature pretreatment under the air atmosphere is 1-12 h.
Preferably, the temperature of the low-temperature pretreatment under the protective atmosphere is 100-300 ℃;
the time for low-temperature pretreatment under protective atmosphere is 1-12 h;
the temperature of the low-temperature pretreatment under the mixed atmosphere of hydrogen and protective gas is 100-300 ℃;
the time for the low-temperature pretreatment under the mixed atmosphere of hydrogen and shielding gas is 1-12 h.
Preferably, the shielding gas comprises nitrogen and/or inert gas;
the volume ratio of the hydrogen to the shielding gas in the mixed atmosphere is (5-10): 100;
the electrochemical properties include one or more of initial charge-discharge coulombic efficiency, specific capacity, and cycling performance.
Preferably, the pretreatment is a pretreatment process for improving the crosslinking structure of the coconut shell precursor;
the treatment process also comprises a carbonization step after pretreatment;
the hard carbon material is a hard carbon negative electrode material;
the negative electrode material comprises a sodium ion battery negative electrode material.
Preferably, the coconut shell comprises coconut shell powder;
the granularity of the coconut shell powder is 0.5-50 mu m;
the oxygen content is specifically that the atomic content of oxygen in the material is 1% -10%;
the coconut shell comprises one or more steps of coconut shell materials after cleaning, drying and crushing.
The invention provides a method for preparing a hard carbon material by pretreating biomass coconut shells, which comprises the following steps:
1) Pretreating cleaned coconut shell powder to obtain a coconut shell precursor;
2) Carbonizing the coconut shell precursor obtained in the step 1) to obtain the coconut shell-based hard carbon material.
Preferably, the cleaning comprises one or more of washing, drying and pulverizing;
the pretreatment comprises one or more of hydrothermal pretreatment, low-temperature pretreatment under air atmosphere, low-temperature pretreatment under protective atmosphere and low-temperature pretreatment under mixed atmosphere of hydrogen and protective gas;
the carbonization temperature is 1000-1600 ℃;
the carbonization time is 1-12 h.
The invention also provides a sodium ion battery, which comprises a negative electrode material;
the anode material comprises the coconut shell-based hard carbon material applied in any one of the technical schemes or the coconut shell-based hard carbon material prepared by the preparation method in any one of the technical schemes.
The invention provides an application of regulating and controlling oxygen content in a material in a coconut shell treatment process in improving electrochemical performance of a coconut shell-based hard carbon material. Compared with the prior art, the invention provides a plurality of pretreatment methods for treating biomass hard carbon precursor coconut shells so as to solve the problems of low specific capacity of biomass hard carbon, poor circulation stability and the like. The pretreatment method provided by the invention can effectively remove impurities in biomass, or can effectively improve the crosslinking structure of the coconut shell precursor and provide certain conditions for the subsequent formation of more closed cells. The coconut shell precursor used in the invention has the advantages of low cost, energy conservation, environmental protection, simple operation of the treatment process, no need of complex process and expensive equipment, no pollution, large-scale mass production, contribution to large-scale industrialization and suitability for industrial requirements.
Experimental results show that the biomass hard carbon anode provided by the invention has the coulomb efficiency of 83% and the specific capacity of 314mAh/g for the first time, has stable cycle performance, and can meet the requirements of industrial application.
Drawings
FIG. 1 is an SEM image of the coconut shell of example 1 after hydrothermal pretreatment and high temperature carbonization of the coconut shell;
FIG. 2 is an XRD pattern of the coconut shell of example 1 of the present invention after hydrothermal pretreatment and high temperature carbonization;
FIG. 3 is a graph showing the charge and discharge of an assembled battery after hydrothermal pretreatment and high temperature carbonization of coconut shells in example 1 of the present invention;
FIG. 4 is a graph showing the cycle power of the assembled battery after hydrothermal pretreatment and high temperature carbonization of coconut shells in example 1 of the present invention;
FIG. 5 is an SEM image of the coconut shell air pre-treated and high temperature carbonized of example 2 of the present invention;
FIG. 6 is an XRD pattern of coconut shell air pre-treated and high temperature carbonized in example 2 of the present invention;
FIG. 7 is a graph showing charge and discharge of an assembled battery after pretreatment of coconut shell air and high temperature carbonization in example 2 of the present invention;
FIG. 8 is a graph showing the cycle power of an assembled battery after pretreatment of coconut shell air and high temperature carbonization in example 2 of the present invention;
FIG. 9 is a graph showing the charge and discharge of the assembled battery after pretreatment and high temperature carbonization of coconut shell argon gas in example 3 of the present invention;
FIG. 10 is a diagram of a coconut shell 5%H in example 4 of the present invention 2 And (3) carrying out Ar pretreatment and high-temperature carbonization, and then assembling a charge-discharge curve diagram of the battery.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs conventional purities used in the field of the preparation of analytically pure or bio-based hard carbon materials.
The invention provides an application of regulating and controlling oxygen content in a material in a coconut shell treatment process in improving electrochemical performance of a coconut shell-based hard carbon material.
In the present invention, the above application may be a method for controlling oxygen content in a material during coconut shell treatment or a method for improving electrochemical properties of a coconut shell based hard carbon material.
In the present invention, the method of controlling preferably includes one or more of hydrothermal pretreatment of coconut shells, low-temperature pretreatment of coconut shells under an air atmosphere, low-temperature pretreatment of coconut shells under a protective atmosphere, and low-temperature pretreatment of coconut shells under a mixed atmosphere of hydrogen and a protective gas, more preferably, hydrothermal pretreatment of coconut shells, low-temperature pretreatment of coconut shells under an air atmosphere, low-temperature pretreatment of coconut shells under a protective atmosphere, and low-temperature pretreatment of coconut shells under a mixed atmosphere of hydrogen and a protective gas.
In the present invention, the oxygen content preferably includes the oxygen content of the pretreated precursor material and/or the oxygen content in the coconut shell based hard carbon material, more preferably the oxygen content of the pretreated precursor material or the oxygen content in the coconut shell based hard carbon material.
In the present invention, the temperature of the hydrothermal pretreatment is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, and still more preferably 140 to 160 ℃.
In the present invention, the time of the hydrothermal pretreatment is preferably 2 to 24 hours, more preferably 7 to 19 hours, and still more preferably 12 to 14 hours.
In the present invention, the temperature at which the low-temperature pretreatment is performed under an air atmosphere is preferably 100 to 300 ℃, more preferably 140 to 260 ℃, and still more preferably 180 to 220 ℃.
In the present invention, the time for the low-temperature pretreatment under an air atmosphere is preferably 1 to 12 hours, more preferably 3 to 10 hours, and still more preferably 5 to 7 hours.
In the present invention, the temperature at which the low-temperature pretreatment is performed under a protective atmosphere is preferably 100 to 300 ℃, more preferably 140 to 260 ℃, and still more preferably 180 to 220 ℃.
In the present invention, the time for the low-temperature pretreatment under a protective atmosphere is preferably 1 to 12 hours, more preferably 3 to 10 hours, and still more preferably 5 to 7 hours.
In the present invention, the temperature at which the low-temperature pretreatment is performed under a mixed atmosphere of hydrogen and a shielding gas is preferably 100 to 300 ℃, more preferably 140 to 260 ℃, and still more preferably 180 to 220 ℃.
In the present invention, the time for the low-temperature pretreatment in the mixed atmosphere of hydrogen and a shielding gas is preferably 1 to 12 hours, more preferably 3 to 10 hours, and still more preferably 5 to 7 hours.
In the present invention, the shielding gas preferably includes nitrogen and/or an inert gas, more preferably nitrogen or an inert gas.
In the invention, the volume ratio of the hydrogen to the shielding gas in the mixed atmosphere is preferably (5-10): 100, more preferably (6 to 9): 100, more preferably (7 to 8): 100.
in the present invention, the electrochemical properties preferably include one or more of a first charge-discharge coulombic efficiency, a specific capacity, and a cycle property, more preferably a first charge-discharge coulombic efficiency, a specific capacity, or a cycle property.
In the present invention, the pretreatment is preferably a pretreatment process for improving the crosslinked structure of the coconut shell precursor.
In the present invention, the treatment process preferably further includes a carbonization step after the pretreatment.
In the present invention, the hard carbon material is preferably a hard carbon negative electrode material.
In the present invention, the negative electrode material preferably includes a sodium ion battery negative electrode material.
In the present invention, the coconut shell preferably comprises coconut shell powder.
In the present invention, the particle size of the coconut shell powder is preferably 0.5 to 50. Mu.m, more preferably 5 to 40. Mu.m, still more preferably 15 to 30. Mu.m.
In the present invention, the oxygen content is specifically such that the atomic content of oxygen in the material is preferably 1% to 10%, more preferably 3% to 8%, and still more preferably 5% to 6%.
In the present invention, the coconut shell preferably comprises one or more steps of coconut shell material after washing, drying and pulverizing.
The invention provides a method for preparing a hard carbon material by pretreating biomass coconut shells, which comprises the following steps:
1) Pretreating cleaned coconut shell powder to obtain a coconut shell precursor;
2) Carbonizing the coconut shell precursor obtained in the step 1) to obtain the coconut shell-based hard carbon material.
The method comprises the steps of firstly, preprocessing cleaned coconut shell powder to obtain a coconut shell precursor.
In the present invention, the cleaning preferably includes one or more of cleaning, drying, and pulverizing, more preferably, a plurality of steps of cleaning, drying, and pulverizing.
In the present invention, the pretreatment preferably includes one or more of hydrothermal pretreatment, low-temperature pretreatment under an air atmosphere, low-temperature pretreatment under a protective atmosphere, and low-temperature pretreatment under a mixed atmosphere of hydrogen and a protective gas, more preferably a plurality of hydrothermal pretreatment, low-temperature pretreatment under an air atmosphere, low-temperature pretreatment under a protective atmosphere, and low-temperature pretreatment under a mixed atmosphere of hydrogen and a protective gas.
Finally, carbonizing the coconut shell precursor obtained in the steps to obtain the coconut shell-based hard carbon material.
In the present invention, the carbonization temperature is preferably 1000 to 1600 ℃, more preferably 1100 to 1500 ℃, and even more preferably 1200 to 1400 ℃.
In the present invention, the carbonization time is preferably 1 to 12 hours, more preferably 3 to 10 hours, and still more preferably 5 to 7 hours.
The invention relates to a complete and refined integral technical scheme, which better improves the electrochemical performance of biomass hard carbon, and the method for preparing hard carbon materials by pretreating biomass coconut shells specifically comprises the following steps:
the preparation method of the hard carbon anode material by pretreating the coconut shells comprises the following steps of hydrothermal treatment, pre-oxidation, pre-carbonization and acid-base cleaning:
(1) Firstly flushing waste biomass coconut shells with a large amount of clear water, drying, crushing, and then adding the biomass coconut shells into a reaction kettle for low-temperature pretreatment;
(2) Washing waste biomass coconut shells with a large amount of clear water, drying, crushing, and then pretreating in air at low temperature;
(3) Washing waste biomass coconut shells with a large amount of clear water, drying, crushing, and then pretreating in argon at low temperature;
(4) Washing waste biomass coconut shells with a large amount of clear water, drying, crushing, and then pretreating in argon-hydrogen mixed gas at low temperature;
(5) Carbonizing the precursor obtained by pretreatment in the step (1), the step (2), the step (3) or the step (4) in a high-temperature tube furnace to obtain different pretreated hard carbon cathodes.
Specifically, different pretreatment modes control the oxygen content in the carbon material, the oxygen content is controlled to be 1-10% (atomic ratio) in a specific range, and the initial charge-discharge coulomb efficiency and specific capacity are improved.
Specifically, the temperature of the hydrothermal reaction in the step (1) is 150-200 ℃, specifically, coconut shell powder is placed in a Teflon reaction kettle, a proper amount of deionized water is added, the temperature is raised to 150-200 ℃ from room temperature, and the temperature is kept for 2-24 hours.
Specifically, the pre-carbonization temperature in the air in the step (2) is 100-300 ℃, specifically, coconut shell powder is placed in a corundum porcelain boat and placed in a muffle furnace, the temperature is raised from room temperature to 100-300 ℃, and the heat is preserved for 1-12 h.
Specifically, the pre-carbonization temperature in the step (3) is 100-300 ℃, specifically, coconut shell powder is placed in a corundum porcelain boat and is placed in a tube furnace, and the temperature is raised from room temperature to 100-300 ℃ and is kept for 1-12 h under the protection of argon.
Specifically, the argon-hydrogen mixture gas (5-10% H) in the step (4) 2 Ar) the pre-carbonization temperature is 100-300 ℃, and particularly, coconut shell powder is placed in a corundum porcelain boat and is placed in a tube furnace, and the temperature is raised from room temperature to 100-300 ℃ and is kept for 1-12 h under the atmosphere of argon-hydrogen mixed gas protection.
Further, the biomass coconut shell pretreatment method can also comprise the following steps:
(1) And (3) putting the coconut shell powder with a certain mass into a Teflon reaction kettle, adding deionized water with a certain proportion, and carrying out hydrothermal treatment in a blast oven for a certain time.
(2) The coconut shell powder with certain mass is placed in a corundum porcelain boat and placed in a muffle furnace for carbonization for a period of time at low temperature.
(3) The coconut shell powder with certain mass is placed in a corundum porcelain boat, and is placed in a tube furnace for carbonization for a period of time at low temperature, and argon is introduced as shielding gas during the carbonization.
(4) The coconut shell powder with certain mass is placed in a corundum porcelain boat, and is placed in a tube furnace for carbonization for a period of time at low temperature, and argon-hydrogen mixed gas is introduced as shielding gas during the carbonization.
(5) And (3) placing the pretreated coconut shell powder obtained in the step (1) or (2) or (3) or (4) in a tube furnace, and carbonizing at high temperature for a period of time.
Specifically, the hydrothermal temperature in the step (1) is 100-200 ℃.
Specifically, the pre-carbonization temperature in the step (2) is 100-300 ℃, and the pre-carbonization time is 1-12 h.
Specifically, the pre-carbonization temperature in the step (3) is 100-300 ℃, and the pre-carbonization time is 1-12 h.
Specifically, the pre-carbonization temperature in the step (4) is 100-300 ℃, and the pre-carbonization time is 1-12 h.
Specifically, the carbonization temperature in the step (5) is 1000-1600 ℃, and the carbonization time is 1-12 h.
The invention also provides a sodium ion battery, which comprises a negative electrode material.
The anode material comprises the coconut shell-based hard carbon material applied in any one of the technical schemes or the coconut shell-based hard carbon material prepared by the preparation method in any one of the technical schemes.
The invention provides an application of regulating and controlling oxygen content in a material in a coconut shell treatment process in improving electrochemical performance of a coconut shell-based hard carbon material, a method for preparing the hard carbon material by pretreating biomass coconut shells and a sodium ion battery. The invention provides a plurality of pretreatment methods for treating biomass hard carbon precursor coconut shells so as to solve the problems of low specific capacity, poor circulation stability and the like of biomass hard carbon. The pretreatment method provided by the invention can effectively remove impurities in biomass, or can effectively improve the crosslinking structure of the coconut shell precursor and provide certain conditions for the subsequent formation of more closed cells. The coconut shell precursor used in the invention has the advantages of low cost, energy conservation, environmental protection, simple operation of the treatment process, no need of complex process and expensive equipment, no pollution, large-scale mass production, contribution to large-scale industrialization and suitability for industrial requirements.
Experimental results show that the biomass hard carbon anode provided by the invention has the coulomb efficiency of 83% and the specific capacity of 314mAh/g for the first time, has stable cycle performance, and can meet the requirements of industrial application.
For further explanation of the present invention, the application of adjusting oxygen content in materials in coconut shell processing procedure in improving electrochemical performance of coconut shell based hard carbon material, a method for preparing hard carbon material by pretreating biomass coconut shell and sodium ion battery are described in detail in the following with reference to examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation procedures are given only for further explanation of features and advantages of the present invention, not limitation of claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Crushing and cleaning waste biomass coconut shells, drying the waste biomass coconut shells in an oven, placing the dried coconut shells in a reaction kettle, adding a certain amount of deionized water, sealing, placing the sealed coconut shells in a blast oven, heating the sealed coconut shells to 200 ℃ from room temperature, preserving heat for 12 hours to obtain a pretreated coconut shell precursor, naturally cooling, centrifugally filtering, cleaning and drying; and (3) placing the dried particles in a corundum porcelain boat, transferring the corundum porcelain boat into a tubular furnace protected by argon, heating the corundum porcelain boat to 1300 ℃ from room temperature, preserving heat for 2 hours, cooling the corundum porcelain boat to the room temperature, and taking out the corundum porcelain boat to obtain a final product.
Referring to fig. 1, fig. 1 is an SEM image of the coconut shell of example 1 of the present invention after hydrothermal pretreatment and high temperature carbonization.
Referring to fig. 2, fig. 2 is an XRD pattern after hydrothermal pretreatment and high temperature carbonization of coconut shells in example 1 of the present invention.
And (2) uniformly mixing a hard carbon negative electrode with a conductive agent and a binder in water according to a mass ratio of 94:2:4, coating the mixture on a copper foil, vacuum drying, cutting to obtain an electrode plate, taking metal sodium as a counter electrode, taking 1M NaPF6 EC DMC (1:1) electrolyte and whatman glass fiber as a diaphragm, and assembling the 2032 battery. Adopting a new Wei battery test system, and testing conditions: charging and discharging current of 30ma/g and voltage range of 0.01-2.5V vs Na/Na + 。
Referring to fig. 3, fig. 3 is a charge-discharge graph of an assembled battery after hydrothermal pretreatment and high-temperature carbonization of coconut shells in example 1 of the present invention.
Referring to fig. 4, fig. 4 is a graph showing the cycle power of the assembled battery after hydrothermal pretreatment and high temperature carbonization of coconut shells in example 1 of the present invention.
The first charge-discharge curve is shown in FIG. 3, the specific capacity is 296mAh/g, and the first charge-discharge efficiency is 83%; the cycle performance is shown in fig. 4, and after 100 cycles, there is still 85% capacity retention.
Example 2
Crushing and cleaning waste biomass coconut shells, drying the waste biomass coconut shells in an oven, placing the dried coconut shells in a corundum porcelain boat, and keeping the temperature of 200 ℃ in a muffle furnace for 6 hours to obtain an air-pretreated coconut shell precursor; and (3) placing the ground particles in a corundum porcelain boat, transferring the corundum porcelain boat into a tubular furnace protected by argon, heating to 1300 ℃ from room temperature, preserving heat for 2 hours, cooling to the room temperature, and taking out to obtain a final product.
Referring to fig. 5, fig. 5 is an SEM image of the coconut shell air pre-treated and high temperature carbonized embodiment 2 of the present invention.
Referring to fig. 6, fig. 6 is an XRD pattern after air pretreatment and high temperature carbonization of coconut shell in example 2 of the present invention.
Uniformly mixing the agents in water according to the mass ratio of 94:2:4, coating the agents on a copper foil, vacuum drying, cutting to obtain an electrode slice, taking metal sodium as a counter electrode, taking 1M NaPF6 EC DMC (1:1) electrolyte and whatman glass fiber as a diaphragm, assembling the 2032 battery, adopting a New Wei battery test system, and testing the conditions: charging and discharging current of 30ma/g and voltage range of 0.01-2.5V vs Na/Na + 。
Referring to fig. 7, fig. 7 is a graph showing charge and discharge of an assembled battery after coconut shell air pretreatment and high temperature carbonization in example 2 of the present invention.
Referring to fig. 8, fig. 8 is a graph showing the cycle power of the assembled battery after coconut shell air pretreatment and high temperature carbonization in example 2 of the present invention.
The first charge-discharge curve is shown in FIG. 7, the specific capacity is 314mAh/g, and the first charge-discharge efficiency is 83%; the cycle performance is shown in fig. 8, and after 100 cycles, there is still 86% capacity retention.
Example 3
Crushing and cleaning waste biomass coconut shells, drying the waste biomass coconut shells in an oven, placing the dried coconut shells in a corundum porcelain boat, keeping the temperature in a tubular furnace at 200 ℃ for 6 hours, and introducing argon as a shielding gas to obtain a pretreated coconut shell precursor; and (3) placing the ground particles in a corundum porcelain boat, transferring the corundum porcelain boat into a tubular furnace protected by argon, heating to 1300 ℃ from room temperature, preserving heat for 2 hours, cooling to the room temperature, and taking out to obtain a final product.
Uniformly mixing a hard carbon negative electrode and a conductive agent in water according to a mass ratio of 94:2:4, coating the mixture on a copper foil, vacuum drying, cutting to obtain an electrode plate, taking metal sodium as a counter electrode, taking 1M NaPF6 EC DMC (1:1) electrolyte and whatman glass fiber as a diaphragm, assembling a 2032 battery, adopting a new Wei battery test system, and testing the conditions: charging and discharging current of 30ma/g and voltage range of 0.01-2.5V vs Na/Na + 。
Referring to fig. 9, fig. 9 is a graph showing charge and discharge of an assembled battery after coconut shell argon pretreatment and high temperature carbonization in example 3 of the present invention.
The first charge-discharge curve is shown in FIG. 9, the specific capacity is 305mAh/g, and the first charge-discharge efficiency is 78%.
Example 4
Crushing and cleaning waste biomass coconut shells, drying the waste biomass coconut shells in an oven, placing the dried coconut shells in a corundum porcelain boat, keeping the temperature in a tubular furnace at 200 ℃ for 6 hours, and introducing argon-hydrogen mixed gas as a shielding gas, wherein the hydrogen ratio is 5%, so as to obtain a pretreated coconut shell precursor; and (3) placing the ground particles in a corundum porcelain boat, transferring the corundum porcelain boat into a tubular furnace protected by argon, heating to 1300 ℃ from room temperature, preserving heat for 2 hours, cooling to the room temperature, and taking out to obtain a final product.
Uniformly mixing a hard carbon negative electrode and a conductive agent in water according to a mass ratio of 94:2:4, coating the mixture on a copper foil, vacuum drying, cutting to obtain an electrode plate, taking metal sodium as a counter electrode, taking 1M NaPF6 EC DMC (1:1) electrolyte and whatman glass fiber as a diaphragm, assembling a 2032 battery, adopting a new Wei battery test system, and testing the conditions: charging and discharging current of 30ma/g and voltage range of 0.01-2.5V vs Na/Na + 。
Referring to FIG. 10, FIG. 10 shows a coconut shell 5%H in example 4 of the present invention 2 And (3) carrying out Ar pretreatment and high-temperature carbonization, and then assembling a charge-discharge curve diagram of the battery.
The first charge-discharge curve is shown in FIG. 10, the specific capacity is 326mAh/g, and the first charge-discharge efficiency is 81%.
Example 5
Crushing and cleaning waste biomass coconut shells, drying the waste biomass coconut shells in an oven, placing the dried coconut shells in a beaker, soaking and stirring the dried coconut shells in a 1M NaOH solution for 12 hours, filtering and washing the coconut shells, adding 1M HCl into the mixture, soaking and stirring the mixture for 12 hours, filtering and washing the mixture, and drying the mixture to obtain a pretreated coconut shell precursor; and (3) placing the ground particles in a corundum porcelain boat, transferring the corundum porcelain boat into a tubular furnace protected by argon, heating to 1300 ℃ from room temperature, preserving heat for 2 hours, cooling to the room temperature, and taking out to obtain a final product.
The application of the present invention in regulating oxygen content of a material in a coconut shell treatment process in improving electrochemical performance of a coconut shell-based hard carbon material, a method for preparing a hard carbon material by pretreating biomass coconut shells and a sodium ion battery are described in detail, and specific examples are used herein to illustrate the principles and embodiments of the present invention, and the above examples are only for aiding in understanding the method and core ideas of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any combined method. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The application of regulating the oxygen content in the material in the coconut shell treatment process in improving the electrochemical performance of the coconut shell-based hard carbon material.
2. The use according to claim 1, wherein the method of conditioning comprises one or more of hydrothermal pretreatment of coconut shells, low temperature pretreatment of coconut shells under an air atmosphere, low temperature pretreatment of coconut shells under a protective atmosphere, and low temperature pretreatment of coconut shells under a mixed atmosphere of hydrogen and a protective gas;
the oxygen content includes the oxygen content of the pre-treated precursor material and/or the oxygen content of the coconut shell based hard carbon material.
3. The use according to claim 2, characterized in that the temperature of the hydrothermal pretreatment is 100-200 ℃;
the hydrothermal pretreatment time is 2-24 hours;
the temperature of the low-temperature pretreatment under the air atmosphere is 100-300 ℃;
the time for the low-temperature pretreatment under the air atmosphere is 1-12 h.
4. The use according to claim 2, wherein the temperature of the low temperature pretreatment in a protective atmosphere is 100-300 ℃;
the time for low-temperature pretreatment under protective atmosphere is 1-12 h;
the temperature of the low-temperature pretreatment under the mixed atmosphere of hydrogen and protective gas is 100-300 ℃;
the time for the low-temperature pretreatment under the mixed atmosphere of hydrogen and shielding gas is 1-12 h.
5. The use according to claim 4, wherein the shielding gas comprises nitrogen and/or an inert gas;
the volume ratio of the hydrogen to the shielding gas in the mixed atmosphere is (5-10): 100;
the electrochemical properties include one or more of initial charge-discharge coulombic efficiency, specific capacity, and cycling performance.
6. The use according to claim 2, wherein the pretreatment is a pretreatment process that improves the cross-linked structure of the coconut shell precursor;
the treatment process also comprises a carbonization step after pretreatment;
the hard carbon material is a hard carbon negative electrode material;
the negative electrode material comprises a sodium ion battery negative electrode material.
7. The use according to claim 1, wherein the coconut shell comprises coconut shell powder;
the granularity of the coconut shell powder is 0.5-50 mu m;
the oxygen content is specifically that the atomic content of oxygen in the material is 1% -10%;
the coconut shell comprises one or more steps of coconut shell materials after cleaning, drying and crushing.
8. The method for preparing the hard carbon material by pretreating biomass coconut shells is characterized by comprising the following steps of:
1) Pretreating cleaned coconut shell powder to obtain a coconut shell precursor;
2) Carbonizing the coconut shell precursor obtained in the step 1) to obtain the coconut shell-based hard carbon material.
9. The method of claim 8, wherein the cleaning comprises one or more of washing, drying, and pulverizing;
the pretreatment comprises one or more of hydrothermal pretreatment, low-temperature pretreatment under air atmosphere, low-temperature pretreatment under protective atmosphere and low-temperature pretreatment under mixed atmosphere of hydrogen and protective gas;
the carbonization temperature is 1000-1600 ℃;
the carbonization time is 1-12 h.
10. A sodium ion battery, wherein the sodium ion battery comprises a negative electrode material;
the negative electrode material comprises the coconut shell-based hard carbon material in the application of any one of claims 1 to 7 or the coconut shell-based hard carbon material prepared by the preparation method of any one of claims 8 to 9.
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| CN117185279A (en) * | 2023-11-08 | 2023-12-08 | 宁德时代新能源科技股份有限公司 | Hard carbon, preparation method, secondary battery and electricity utilization device |
| CN118479460A (en) * | 2024-07-10 | 2024-08-13 | 江苏浦士达环保科技股份有限公司 | Preparation method of silicon-carbon negative electrode precursor |
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| CN117185279A (en) * | 2023-11-08 | 2023-12-08 | 宁德时代新能源科技股份有限公司 | Hard carbon, preparation method, secondary battery and electricity utilization device |
| CN118479460A (en) * | 2024-07-10 | 2024-08-13 | 江苏浦士达环保科技股份有限公司 | Preparation method of silicon-carbon negative electrode precursor |
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