CN115557486B - Hard carbon negative electrode material, preparation method thereof, negative electrode plate and sodium ion battery - Google Patents
Hard carbon negative electrode material, preparation method thereof, negative electrode plate and sodium ion battery Download PDFInfo
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- CN115557486B CN115557486B CN202211402388.9A CN202211402388A CN115557486B CN 115557486 B CN115557486 B CN 115557486B CN 202211402388 A CN202211402388 A CN 202211402388A CN 115557486 B CN115557486 B CN 115557486B
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 101
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 43
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 91
- 239000010405 anode material Substances 0.000 claims abstract description 52
- 238000003763 carbonization Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
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- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
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- 229920002678 cellulose Polymers 0.000 claims description 3
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- 230000000977 initiatory effect Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 20
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001295 No alloy Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon negative electrode material and a preparation method thereof, a negative electrode plate and a sodium ion battery. The preparation method of the hard carbon anode material comprises the following steps: mixing and/or reacting the nano porous carbon and the carbon-containing material, and then performing high-temperature carbonization treatment to obtain the hard carbon anode material; the carbon-containing material comprises a thermoplastic organic carbon source; the mass ratio of the nano porous carbon to the thermoplastic organic carbon source is 0.1-2: 10 to 150. The preparation method can improve the capacity and initial effect of the hard carbon anode material and reduce the specific surface area of the hard carbon anode material.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon negative electrode material and a preparation method thereof, a negative electrode plate and a sodium ion battery.
Background
The advantages of the sodium ion battery are increasingly prominent because the sodium element has the advantages of rich resources, wide sources, low cost and the like. In addition, compared with a lithium ion battery, the sodium ion battery has the advantages of good safety performance, no alloy with aluminum, further cost reduction by adopting aluminum foil as a current collector for the negative electrode, capability of being released or maintained under the voltage of 0V without changing the subsequent performance and the like. However, the radius of sodium ions is larger than that of lithium ions, and the traditional graphite cathode is not matched with sodium ions, so that the sodium ions are not electrochemically active after intercalation.
The research shows that the interlayer space of the hard carbon material is relatively large, holes in which sodium ions can be embedded are relatively large, and a channel and a negative electrode which can enable the sodium ions to be unobstructed can be obtained after the hard carbon material is treated by a certain means.
However, existing hard carbon materials are limited by adsorption-intercalation-pore-filling mechanisms, often with capacities below 300mAh/g.
In view of this, the present invention has been made.
Disclosure of Invention
A first object of the present invention is to provide a method for producing a hard carbon anode material, which can improve the capacity of the hard carbon anode material. The method solves the problem that the hard carbon material in the prior art is limited by an adsorption-embedding-pore filling mechanism, and the capacity is often lower than 300mAh/g.
The second object of the present invention is to provide a hard carbon anode material.
A third object of the present invention is to provide a negative electrode tab.
A fourth object of the present invention is to provide a sodium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a preparation method of a hard carbon anode material, which comprises the following steps:
mixing and/or reacting the nano porous carbon and the carbon-containing material, and then performing high-temperature carbonization treatment to obtain the hard carbon anode material;
wherein the carbon-containing material comprises a thermoplastic organic carbon source;
the mass ratio of the nano porous carbon to the thermoplastic organic carbon source is 0.1-2: 10 to 150.
Preferably, the D50 particle size of the nanoporous carbon is less than 500nm, preferably less than 100nm;
preferably, the pore diameter of the nano porous carbon is 1-10 nm;
preferably, the specific surface area of the nano porous carbon is more than or equal to 400m 2 /g。
Preferably, the thermoplastic organic carbon source comprises at least one of cellulose, lignin, glucose, sucrose, starch, pitch, phenolic resin, coumarone resin, epoxy resin, polyester resin, polyamide resin, citric acid, and dopamine.
Preferably, the carbonaceous material further comprises a solvent;
preferably, the solvent comprises water and/or an organic solvent;
preferably, the organic solvent includes at least one of ethanol, methanol, acetone, and isopropanol.
Preferably, the method of mixing includes at least one of stirring mixing, ball milling mixing, and melt mixing;
preferably, the temperature of the melt mixing is 250-400 ℃;
preferably, the reaction comprises a hydrothermal reaction;
preferably, the temperature of the hydrothermal reaction is 150-200 ℃, and the time of the hydrothermal reaction is 10-15 h.
Preferably, the temperature of the high-temperature carbonization treatment is 1200-1600 ℃, and the heat preservation time of the high-temperature carbonization treatment is 2-6 h.
Further, the invention also provides the hard carbon anode material prepared by the preparation method of the hard carbon anode material.
Preferably, the specific surface area of the hard carbon anode material is less than 10m 2 /g；
Preferably, the first discharge specific capacity of the hard carbon anode material at the current density of 30mA/g is more than 330mA/g, and the first coulomb efficiency is more than 90%.
The invention further provides a negative electrode plate which is mainly prepared from the hard carbon negative electrode material.
Further, the invention also provides a sodium ion battery, which comprises the negative electrode plate.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the hard carbon anode material, the thermoplastic organic carbon source is used as a carbon source, the nano porous carbon is used as a self-template, the thermoplastic organic carbon source and the nano porous carbon are compounded by means of mixing and/or reaction, and then the first effect and the capacity of the hard carbon anode material can be improved through high-temperature carbonization treatment.
(2) The preparation method of the hard carbon negative electrode material can reduce the specific surface area of the hard carbon negative electrode material, thereby improving the first effect of the hard carbon negative electrode material.
(3) The specific surface area of the hard carbon anode material provided by the invention is less than 10m 2 And its first discharge specific capacity is greater than 330mA/g at a current density of 30mA/g and its first coulomb efficiency is greater than 90%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the results of electrochemical performance test of the hard carbon negative electrode material prepared in example 1 provided by the present invention;
fig. 2 is a graph showing the results of electrochemical performance test of the hard carbon anode material prepared in comparative example 1 provided by the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. 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.
In a first aspect, the invention provides a method for preparing a hard carbon anode material, comprising the following steps:
and mixing and/or reacting the nano porous carbon and the carbon-containing material, and then performing high-temperature carbonization treatment to obtain the hard carbon anode material.
In some specific embodiments of the present invention, the nano-porous carbon and the carbon-containing material may be mixed uniformly and then subjected to high temperature carbonization treatment directly, or the nano-porous carbon and the carbon-containing material may be mixed uniformly and reacted and then subjected to high temperature carbonization treatment.
I.e., the nanoporous carbon and the carbonaceous material may be physically and/or chemically composited.
In some embodiments of the present invention, the mixing may be by any of the conventional mixing methods, such as stirring, heating, milling, spray drying granulation, etc., but is not limited thereto.
The reaction includes any, conventional chemical reaction, such as a hydrothermal reaction.
Wherein the carbon-containing material comprises a thermoplastic organic carbon source; wherein, thermoplastic refers to the property that a substance can flow and deform when heated, and can keep a certain shape after cooling.
The mass ratio of the nano porous carbon to the thermoplastic organic carbon source is 0.1-2: 10 to 150. Wherein in the mass ratio described above, the mass of the nanoporous carbon includes, but is not limited to, a dot value of any one of 0.3, 0.5, 0.8, 1, 1.2, 1.4, 1.5, 1.7, 1.9 or a range value therebetween; the mass of the thermoplastic organic carbon source includes, but is not limited to, a point value of any one of 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or a range value therebetween.
Preferably, the mass ratio of the nano porous carbon to the thermoplastic organic carbon source is 0.5 to 1:20 to 100.
According to the invention, a thermoplastic organic carbon source is used as a carbon source precursor, nano porous carbon is used as a self-template, the thermoplastic organic carbon source and the nano porous carbon are compounded by means of mixing and/or reaction, and then high-temperature carbonization treatment is carried out, so that the high-capacity hard carbon anode material is prepared. The material can be used as a negative electrode material of a sodium ion battery, and can show high initial effect and high capacity.
The nano porous carbon is a three-dimensional material, a large number of nano holes exist on the surface of the nano porous carbon, and the specific surface area is large. The thermoplastic organic carbon source high-temperature melting can coat the nano porous carbon inside, the carbonized nano porous carbon exists inside, a large number of closed pores in the inside of the nano porous carbon obviously improve the sodium storage capacity, and the porous carbon forms the closed pores inside, so that the specific surface area is smaller, and the initial effect is higher.
The preparation method of the hard carbon negative electrode material provided by the invention has the advantages of simple method, low cost, short process flow, suitability for mass production, low specific surface area of the prepared hard carbon negative electrode material, good electrochemical performance and the like.
Preferably, the D50 particle size of the nanoporous carbon is less than 500nm, including but not limited to a point value of any one of 400nm, 300nm, 200nm, 100nm, 80nm, 60nm, 50nm, 30nm, 20nm, 10nm, 5nm or a range value between any two; preferably less than 100nm.
Preferably, the pore diameter of the nano porous carbon is 1-10 nm; including but not limited to a point value of any one of 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or a range value between any two.
Preferably, the specific surface area of the nano porous carbon is more than or equal to 400m 2 /g, including but not limited to 500m 2 /g、600m 2 /g、700m 2 /g、800m 2 /g、900m 2 /g、1000m 2 /g、1200m 2 /g、1500m 2 A point value of any one of/g or a range value between any two.
The nano porous carbon with the parameters is beneficial to improving the first effect and the capacity of the hard carbon anode material. Specifically, the sodium storage mechanism is adsorption-embedding-pore filling, the hard carbon capacity of the adsorption-embedding mechanism is about 300, and the hard carbon capacity can be obviously improved after the pore filling is introduced. Thus, the larger the specific surface area of the porous carbon, the more closed pores are formed, which contributes to the improvement of the hard carbon capacity.
Preferably, the thermoplastic organic carbon source comprises at least one of cellulose, lignin, glucose, sucrose, starch, pitch, phenolic resin, coumarone resin, epoxy resin, polyester resin, polyamide resin, citric acid, and dopamine.
In some specific embodiments of the present invention, the phenolic resin includes, but is not limited to, at least one of a nitrogen-containing phenolic resin and a phosphorus-containing phenolic resin.
In some specific embodiments of the invention, the conductive polymer includes, but is not limited to, at least one of polypyrrole, polyaniline, and polythiophene.
Preferably, the carbonaceous material further comprises a solvent.
Preferably, the solvent comprises water and/or an organic solvent.
In some embodiments of the invention, the ratio of the volume of solvent (mL) to the mass sum (g) of nanoporous carbon and thermoplastic organic is from 20 to 100mL: 20-150 g.
Preferably, the organic solvent includes at least one of ethanol, methanol, acetone, and isopropanol.
Preferably, the method of mixing includes at least one of stirring mixing, ball milling mixing, and melt mixing; two or three of them may also be selected simultaneously.
In some specific embodiments of the invention, the ball milling includes dry ball milling and wet ball milling; preferably dry ball milling.
In some specific embodiments of the invention, the mixing time is 3 to 15 hours; including but not limited to a point value of any one of 4h, 5h, 7h, 9h, 10h, 12h, 14h or a range value therebetween.
Preferably, the temperature of the melt mixing is 250-400 ℃; including but not limited to any one of the point values or range values between any two of 280 ℃, 300 ℃, 320 ℃, 340 ℃, 350 ℃, 380 ℃.
In some specific embodiments of the invention, agitation is accompanied during the melt mixing.
In some embodiments of the invention, the ball milling temperature may be any conventional ball milling temperature, preferably 5-40 ℃, including, but not limited to, any one point value or any range value between 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, or both; more preferably at room temperature.
Preferably, the reaction comprises a hydrothermal reaction.
In some embodiments of the invention, the carbonaceous material comprises solvent-water during the hydrothermal reaction.
Preferably, the temperature of the hydrothermal reaction is 150-200 ℃, including but not limited to a point value of any one of 160 ℃, 170 ℃, 180 ℃, 190 ℃ or a range value between any two; the hydrothermal reaction time is 10-15 h, including but not limited to a point value of any one of 11h, 12h, 13h, 14h or a range value between any two.
In some specific embodiments of the present invention, after the hydrothermal reaction, the method further comprises a step of solid-liquid separation of the mixed material.
In some preferred embodiments of the invention, the nanoporous carbon and the carbonaceous material are composited using at least one of the following methods. Firstly, mixing nano porous carbon, a thermoplastic organic carbon source and water, and then carrying out hydrothermal reaction; secondly, mixing the nano porous carbon and a thermoplastic organic carbon source, and performing dry ball milling; thirdly, mixing and uniformly stirring the nano porous carbon, the thermoplastic organic carbon source and the organic solvent; fourthly, heating, melting and stirring the nano porous carbon and the thermoplastic organic carbon source; fifth, the nanoporous carbon, the thermoplastic organic carbon source and the water are mixed and stirred uniformly. And after the compounding is completed, carrying out high-temperature carbonization treatment.
Preferably, the high temperature carbonization treatment temperature is 1200-1600 ℃, including but not limited to any one of 1300 ℃, 1400 ℃, 1500 ℃ or a range between any two; the heat preservation time of the high-temperature carbonization treatment is 2-6 h, including but not limited to any one point value or range value between any two of 3h, 4h and 5h.
In some specific embodiments of the invention, the elevated temperature carbonization process has a heating rate of 1-20 ℃/min, including but not limited to a point value of any one of, or a range of values between any two of, 2 ℃/min, 4 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 13 ℃/min, 15 ℃/min, 18 ℃/min.
In some specific embodiments of the invention, the high temperature carbonization treatment is performed in a non-oxidizing atmosphere; wherein the non-oxidizing atmosphere includes, but is not limited to, at least one of nitrogen, argon, helium, ammonia, and hydrogen.
In a second aspect, the present invention provides a hard carbon anode material prepared by the method for preparing a hard carbon anode material as described above.
The hard carbon anode material provided by the invention has a relatively low specific surface area, and has relatively high initial effect and charge-discharge capacity.
Preferably, the specific surface area of the hard carbon anode material is less than 10m 2 /g; including but not limited to 9m 2 /g、8m 2 /g、7m 2 /g、6m 2 /g、5m 2 /g、4m 2 /g、3m 2 /g、2m 2 /g、1m 2 A point value of any one of/g or a range value between any two.
Preferably, the hard carbon negative electrode material has a specific first discharge capacity at a current density of 30mA/g of greater than 330mA/g, including but not limited to a point value of any one of 331mA/g, 332mA/g, 333mA/g, 334mA/g, 335mA/g, 336mA/g, 337mA/g, 338mA/g, 339mA/g, 340mA/g, 345mA/g, 350mA/g, or a range value between any two thereof; the hard carbon negative electrode material has a first coulombic efficiency greater than 90% at a current density of 30mA/g, including but not limited to a point value of any one of 90.3%, 90.5%, 90.8%, 91%, 91.5%, 92%, 92.5%, 93%, 94%, 95%, or a range of values between any two.
In a third aspect, the present invention provides a negative electrode sheet, made mainly of a hard carbon negative electrode material as described above.
In a fourth aspect, the invention provides a sodium ion battery comprising a negative electrode sheet as described above.
The sodium ion battery has the advantages of high first efficiency, high specific capacity, low cost and high safety.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. 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.
The manufacturer of the nanoporous carbon used in the following examples and comparative examples of the present invention was GB/T24533-2009. Among them, the method of assembling the hard carbon negative electrode materials prepared in each example and each comparative example into a battery is as follows: assembling the battery in a glove box with high-purity argon atmosphere, wherein a CR2032 button battery shell is adopted, and the electrolyte is as follows: 1.0M NaPF 6 in ec:dmc=1:1vol), membrane is: a glass fiber separator.
Example 1
0.5g of nano porous carbon (D50 particle diameter of 50nm, pore diameter of 3-5 nm, specific surface area of 400 m) 2 Per g), 100g sucrose and 60mL water were mixed and then hydrothermally heated at 180℃for 12 hours, followed by filtration to give a solid material. And (3) placing the solid material into a tubular furnace in Ar atmosphere, heating to 1400 ℃ at a heating rate of 2 ℃/min, preserving heat for 6 hours, and performing high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 5.2m 2 /g。
The electrochemical performance test results of the hard carbon anode material prepared in this example are shown in fig. 1. The hard carbon negative electrode material has a first discharge specific capacity of 334.7mAh/g and a first effect of 90.3% under the current density of 30 mA/g.
Example 2
0.5g of nano porous carbon (D50 particle diameter 100nm, pore diameter 2-4 nm, specific surface area 600 m) 2 /g) and 100g glucose were dry ball milled and mixed for 12h (normal temperature). Then put the ball-milled material into N 2 And (3) heating to 1500 ℃ at a heating rate of 2 ℃/min in a tube furnace in the atmosphere, and preserving heat for 3 hours, so as to carry out high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 6.3m 2 /g。
The hard carbon negative electrode material has a first discharge specific capacity of 336.2mAh/g under the current density of 30mA/g and a first effect of 90.2%.
Example 3
0.5g of nano porous carbon (D50 particle diameter 40nm, pore diameter 5-7 nm, specific surface area 800 m) 2 Per g) and 100g of sucrose for 12 hours (normal temperature). Then put the ball-milled material into N 2 And (3) heating to 1550 ℃ at a heating rate of 2.5 ℃/min in a tube furnace in the atmosphere, preserving heat for 2 hours, and performing high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 4.8m 2 /g。
The hard carbon negative electrode material has a first discharge specific capacity of 332.2mAh/g and a first effect of 90.9% under the current density of 30 mA/g.
Example 4
0.5g of nano porous carbon (D50 particle diameter of 50nm, pore diameter of 2-4 nm, specific surface area of 1000 m) 2 Per g) and 100g of starch for 12 hours (normal temperature). Putting the ball-milled material into H 2 And (3) heating to 1300 ℃ at a heating rate of 3 ℃/min in a tube furnace in the atmosphere, preserving heat for 6 hours, and performing high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 4.6m 2 /g。
The hard carbon negative electrode material has a first discharge specific capacity of 332.1mAh/g and a first effect of 91.1% under the current density of 30 mA/g.
Example 5
0.5g of nano porous carbon (D50 particle diameter of 50nm, pore diameter of 1-3nm, specific surface area of 1200 m) 2 Per g) and 20g of a phenolic resin solution (Dow DEN 438-X80, USA) were dispersed in 30mL of ethanol. Then put the mixed material after stirring into N 2 And (3) heating to 1500 ℃ at a heating rate of 4 ℃/min in a tube furnace in the atmosphere, preserving heat for 2 hours, and performing high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 4.5m 2 /g。
The hard carbon negative electrode material has a first discharge specific capacity of 336.5mAh/g and a first effect of 91.2% under the current density of 30 mA/g.
Example 6
1g of nano porous carbon (D50 particle diameter of 60nm, pore diameter of 3-5 nm, specific surface area of 600 m) 2 Per g) and 25g of a nitrogen-containing phenolic resin (synthesized by stirring 2-aminophenol and formaldehyde in a molar ratio of 1:1 aqueous solution) were dispersed in 30mL of methanol. Then the mixed material after stirring and drying is put into H 2 And (3) heating to 1400 ℃ at a heating rate of 5 ℃/min in a tube furnace in the atmosphere, and preserving heat for 3 hours, so as to carry out high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 6.9m 2 /g。
The hard carbon negative electrode material has a specific capacity of 336.5mAh/g for the first time under the current density of 30mA/g and a first effect of 90.8%.
Example 7
1g of nano porous carbon (D50 particle diameter 40nm, pore diameter 1-2 nm, specific surface area 1000 m) 2 Per g) and 30g of a D992 phosphorus-containing phenolic resin solution (Sichuan technology) were dispersed in 30mL of acetone. And then placing the stirred and dried material into a tubular furnace in Ar atmosphere, heating to 1400 ℃ at a heating rate of 1 ℃/min, preserving heat for 6 hours, and carrying out high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 4.6m 2 /g。
The hard carbon negative electrode material has a first discharge specific capacity of 335.4mAh/g and a first effect of 91.4% under the current density of 30 mA/g.
Example 8
1g of nano porous carbon (D50 particle diameter 80nm, pore diameter 2-5 nm, specific surface area 600 m) 2 /g) and 25g of bitumen at 300℃for 12h. Then put it into N 2 In a tube furnace in atmosphere, the temperature is raised to 1400 ℃ at a heating rate of 2.5 ℃/min, and the heat is preserved for 3 hours, so that high-temperature carbonization treatment is carried out. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 5.1m 2 /g。
The hard carbon negative electrode material has a specific capacity of 330.8mAh/g for the first time under the current density of 30mA/g, and the initial effect of 90.1%.
Example 9
1g of nano porous carbon (D50 particle diameter of 60nm, pore diameter of 2-5 nm, specific surface area of 800 m) 2 Per g), 25g dopamine and 30mL water were mixed and stirred for 12h (ambient temperature). And then placing the uniformly mixed materials into a tubular furnace in Ar atmosphere, heating to 1400 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 hours, and performing high-temperature carbonization treatment. And cooling to room temperature after the high-temperature carbonization treatment is completed, so as to obtain the hard carbon anode material. Through detection, the specific surface area of the hard carbon anode material is 6.6m 2 /g。
The hard carbon negative electrode material has a specific capacity of 332.4mAh/g for the first time under the current density of 30mA/g and a first effect of 90.6%.
Comparative example 1
The preparation method of the hard carbon negative electrode material provided in this comparative example is substantially the same as in example 1, except that the nanoporous carbon was replaced with an equal mass of conductive carbon black SP (D50 particle diameter of 35nm, specific surface area of 65m 2 /g)。
Fig. 2 is a graph showing the results of electrochemical performance test of the hard carbon anode material prepared in this comparative example. The specific surface area of the hard carbon anode material prepared in the comparative example is 32.5m 2 And/g, the initial discharge specific capacity of the composite material is 286.2mAh/g at the current density of 30mA/g, and the initial effect is 79.5%.
Comparative example 2
The preparation method of the hard carbon anode material provided in the comparative example and example 1Substantially the same except that the nanoporous carbon was replaced with nanosize carbon spheres (D50 particle diameter 100nm, specific surface area 85m 2 /g)。
Through detection, the hard carbon anode material prepared by the comparative example has a first discharge specific capacity of 287.5mAh/g and a first effect of 84.6% under a current density of 30 mA/g.
As can be seen from comparison of experimental data of the above examples and comparative examples, the present invention can improve the initial efficiency and capacity of the hard carbon negative electrode material and reduce the specific surface area of the hard carbon negative electrode material by compounding a thermoplastic organic carbon source with nanoporous carbon and then performing high-temperature carbonization treatment.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (16)
1. The preparation method of the hard carbon anode material is characterized by comprising the following steps:
mixing and/or reacting the nano porous carbon and the carbon-containing material, and then performing high-temperature carbonization treatment to obtain the hard carbon anode material; the specific surface area of the nano porous carbon is more than or equal to 400m 2 /g；
Wherein the carbon-containing material comprises a thermoplastic organic carbon source;
the mass ratio of the nano porous carbon to the thermoplastic organic carbon source is 0.1-2: 10 to 150;
the specific surface area of the hard carbon anode material is less than 10m 2 /g；
The first discharge specific capacity of the hard carbon anode material under the current density of 30mA/g is more than 330mAh/g, and the first coulomb efficiency is more than 90%.
2. The method for preparing a hard carbon negative electrode material according to claim 1, wherein the D50 particle size of the nanoporous carbon is less than 500nm.
3. The method for preparing a hard carbon negative electrode material according to claim 1, wherein the D50 particle size of the nanoporous carbon is less than 100nm.
4. The method for producing a hard carbon negative electrode material according to claim 1, wherein the pore diameter of the nanoporous carbon is 1 to 10nm.
5. The method for producing a hard carbon negative electrode material according to claim 1, wherein the thermoplastic organic carbon source comprises at least one of cellulose, lignin, glucose, sucrose, starch, pitch, phenolic resin, coumarone resin, epoxy resin, polyester resin, polyamide resin, citric acid, and dopamine.
6. The method for producing a hard carbon negative electrode material according to claim 1, wherein the carbonaceous material further comprises a solvent.
7. The method for producing a hard carbon negative electrode material according to claim 6, wherein the solvent comprises water and/or an organic solvent.
8. The method for producing a hard carbon negative electrode material according to claim 7, wherein the organic solvent includes at least one of ethanol, methanol, acetone, and isopropanol.
9. The method for producing a hard carbon negative electrode material according to claim 1, wherein the method for mixing includes at least one of stirring mixing, ball-milling mixing, and melt mixing.
10. The method for producing a hard carbon negative electrode material according to claim 9, wherein the temperature of the melt mixing is 250 to 400 ℃.
11. The method for producing a hard carbon negative electrode material according to claim 1, wherein the reaction comprises a hydrothermal reaction.
12. The method for producing a hard carbon negative electrode material according to claim 11, wherein the temperature of the hydrothermal reaction is 150 to 200 ℃, and the time of the hydrothermal reaction is 10 to 15 hours.
13. The method for producing a hard carbon negative electrode material according to claim 1, wherein the high-temperature carbonization treatment is carried out at a temperature of 1200 to 1600 ℃, and the heat-preservation time of the high-temperature carbonization treatment is 2 to 6 hours.
14. A hard carbon negative electrode material produced by the method for producing a hard carbon negative electrode material according to any one of claims 1 to 13.
15. A negative electrode sheet made primarily from the hard carbon negative electrode material of claim 14.
16. A sodium ion battery comprising the negative electrode tab of claim 15.
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