CN117117179A - Carbon negative electrode material, preparation method thereof and sodium ion battery - Google Patents
Carbon negative electrode material, preparation method thereof and sodium ion battery Download PDFInfo
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- CN117117179A CN117117179A CN202311387474.1A CN202311387474A CN117117179A CN 117117179 A CN117117179 A CN 117117179A CN 202311387474 A CN202311387474 A CN 202311387474A CN 117117179 A CN117117179 A CN 117117179A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 89
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 39
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 29
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 27
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 27
- 239000002077 nanosphere Substances 0.000 claims abstract description 24
- 239000010405 anode material Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 33
- 229920002472 Starch Polymers 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 26
- 235000019698 starch Nutrition 0.000 claims description 26
- 239000008107 starch Substances 0.000 claims description 26
- 239000005539 carbonized material Substances 0.000 claims description 25
- 239000002028 Biomass Substances 0.000 claims description 22
- 235000011837 pasties Nutrition 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- 238000003763 carbonization Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000009656 pre-carbonization Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 229920000297 Rayon Polymers 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000002964 rayon Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229920002994 synthetic fiber Polymers 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000011807 nanoball Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000002121 nanofiber Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 229920000742 Cotton Polymers 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 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 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000002134 carbon nanofiber Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229940100445 wheat starch Drugs 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
- H01M4/36—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
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a carbon negative electrode material, which comprises carbon nanotubes and carbon nanospheres, wherein the carbon nanospheres grow on the carbon nanotubes in situ. Compared with a composite material formed by mechanically mixing carbon nanotubes and carbon nanospheres, the carbon anode material has better structural stability, can effectively resist volume change in the charge and discharge process, further effectively improve the cycle performance and the service life of the anode material, and can also play a synergistic effect of nanofibers and carbon nanospheres; the carbon nano tube has better conductivity, is beneficial to accelerating the electron transmission rate, so that a material with high conductivity is easier to obtain, and the carbon nano ball is beneficial to the infiltration of electrolyte, and the combination of the carbon nano ball and the electrolyte is beneficial to the deintercalation of sodium ions.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a carbon negative electrode material and a preparation method thereof, a sodium ion battery, and particularly relates to a carbon negative electrode material with a carbon nano tube and carbon nano sphere composite structure and a preparation method thereof.
Background
With the development of technology and the increasing number of portable wearable devices and new energy automobiles, the need for high-performance energy storage devices is becoming urgent. The price of lithium resources is continuously increased, the storage of sodium batteries is rich, the safety is better, the rate performance and the low-temperature performance are excellent, and compared with lithium batteries, the lithium batteries have a little shortage in energy density and cycle life. But sodium ion batteries offer significant cost advantages over lithium batteries.
The current selection of the negative electrode material of the sodium battery mainly comprises carbon-based materials, organic materials and metal oxides, and the carbon-based materials have wide sources and strong sodium storage capacity, so that the negative electrode material of the sodium battery becomes the current mainstream selection. The biomass charcoal belongs to one of soft carbon, has high conductivity, high crystallinity, low cost and good reversibility and circulation stability of sodium storage. The carbon cathode material with a certain shape is designed, so that the structural advantage can be fully exerted, and the electrochemical performance is improved.
The existing carbon negative electrode materials comprise silicon carbon materials, artificial graphite, natural graphite and the like, are mostly spherical or amorphous, are generally low in sphericity and single in structural morphology, and when the carbon negative electrode materials are applied to sodium ion batteries or lithium ion batteries, repeated deintercalation of sodium ions or lithium ions in the carbon negative electrode materials in the charging and discharging processes can lead to material expansion, stress distribution is caused, and finally, the material is split and peeled off. Therefore, the volume expansion of the carbon anode material becomes a great disadvantage thereof. In addition, the reactivity of the external surface of the particles of the natural graphite powder is uneven, so that the SEI film coverage of the surface of the particles is uneven, and the initial coulomb efficiency is low and the capacity attenuation is fast when the particles are applied to a battery.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a carbon anode material, a preparation method thereof and a sodium ion battery.
The invention provides the following solutions:
the first object of the present invention is to provide a carbon negative electrode material, which comprises carbon nanotubes and carbon nanospheres, wherein the carbon nanospheres are grown on the carbon nanotubes in situ.
Preferably, the carbon anode material is obtained by carbonizing a carbon sphere precursor grown in situ on the surface of a biomass fiber and/or a rayon fiber.
The second object of the present invention is to provide a method for preparing a carbon anode material, comprising:
(1) Preparing starch into starch paste;
(2) Adding biomass fibers and/or artificial fibers into starch pasty liquid, performing hydrothermal reaction, performing solid-liquid separation, washing and drying on the obtained product to obtain a mixed material;
(3) Pre-carbonizing the obtained mixed material in a non-oxidizing atmosphere to obtain a pre-carbonized material;
(4) Carbonizing the pre-carbonized material to obtain the anode material of the carbon nanospheres grown in situ by the porous biomass carbon nanotube fiber.
Preferably, in the step (3), the temperature of the pre-carbonization is 400-600 ℃; the pre-carbonization time is 4-6 hours; the non-oxidizing atmosphere is an inert atmosphere or a nitrogen atmosphere.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 170-220 ℃; the reaction time is 6-15 h.
Preferably, in the step (4), the carbonization temperature is 800-1000 ℃; the carbonization time is 1-5 h; the carbonization atmosphere is an inert atmosphere or a nitrogen atmosphere.
Preferably, between the step (3) and the step (4), a step of treating and drying the obtained pre-carbonized material by adopting KOH solution is further included.
Preferably, the mass ratio of the pre-carbonized material to KOH is 1:1 to 1:4.
preferably, step (1) includes: adding a proper amount of starch into a solvent, uniformly stirring, and then carrying out heat preservation and stirring at 60-95 ℃ to form pasty liquid;
in the step (2), the biomass fiber and/or the artificial fiber are cleaned and dried.
The third object of the present invention is to provide a sodium ion battery, which comprises the carbon negative electrode material or the carbon negative electrode material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the carbon ball precursor grows on the fiber surface in situ, and then the carbon negative electrode material comprising the carbon nano tube and the carbon nano ball growing on the carbon nano tube in situ is obtained through carbonization, compared with a composite material formed by mechanically mixing the carbon nano tube and the carbon nano ball, the carbon negative electrode material has better structural stability, can effectively resist volume change in the charge and discharge process, further effectively improve the cycle performance and service life of the negative electrode material, and simultaneously can exert the synergistic effect of the carbon nano tube and the carbon nano ball, the carbon nano tube has better conductivity, is beneficial to accelerating the electron transmission rate, so that a material with high conductivity is easier to obtain, the carbon nano ball is beneficial to wetting of electrolyte, and the combination of the carbon nano tube and the carbon nano ball is beneficial to the deintercalation of sodium ions.
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 required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the carbon negative electrode material obtained in example 1 of the present invention.
Fig. 2 is a graph showing cycle performance of button cells assembled from the carbon negative electrode materials obtained in examples 1 to 3 and comparative example 1 according to the present invention.
Detailed Description
The invention provides a carbon negative electrode material, which comprises a carbon nano tube and carbon nano spheres, wherein the carbon nano spheres are grown on the carbon nano tube in situ.
In some embodiments, the length of the carbon nanotubes is between 10 and 100 μm, the diameter of the carbon nanotubes is within the nanometer size range, no special requirement is required, and the diameter of the carbon nanospheres is between 500nm and 5 μm.
In some embodiments, the carbon negative electrode material is obtained by carbonizing a carbon sphere precursor grown in situ on the surface of a biomass fiber and/or a rayon fiber. In some preferred embodiments, the carbon negative electrode material is obtained by pre-carbonization and carbonization after in-situ growth of carbon sphere precursors on the surface of biomass fibers and/or rayon fibers.
The invention also provides a preparation method of the carbon anode material, which comprises the following steps:
(1) Preparing starch into starch paste;
(2) Adding biomass fibers and/or artificial fibers into starch pasty liquid, performing hydrothermal reaction, growing carbon sphere precursors on the surfaces of the fibers in situ, performing solid-liquid separation, washing and drying on the obtained products to obtain a mixed material;
(3) Pre-carbonizing the obtained mixed material in a non-oxidizing atmosphere to obtain a pre-carbonized material;
(4) Carbonizing the pre-carbonized material to obtain the anode material of the carbon nanospheres grown in situ by the porous biomass carbon nanotube fiber.
In the carbon negative electrode material, the mass ratio of the carbon nano tube to the carbon nano sphere is not particularly required, and the carbon negative electrode material can be prepared by in-situ growth and comprises the materials with the two structures, so that the mass ratio of raw material starch to biomass fiber to artificial fiber is not particularly required.
In some embodiments, the biomass fiber may be a material with a microstructure of fibers, such as catkin, cotton, common commercially available nanofibers, and the like; the rayon may be any rayon that can be carbonized to form carbon materials.
In some embodiments, the starch may be a starch-containing material such as corn starch, potato starch, wheat starch, and the like.
In a partially preferred embodiment, in step (3), the pre-carbonization temperature is 400 to 600 ℃; the pre-carbonization time is 4-6 hours; the non-oxidizing atmosphere is an inert atmosphere or a nitrogen atmosphere.
In a part of preferred embodiments, in the step (2), the temperature of the hydrothermal reaction is 170 to 220 ℃; the reaction time is 6-15 h.
In a part of preferred embodiments, between the step (3) and the step (4), the method further comprises the steps of treating and drying the obtained pre-carbonized material by adopting KOH solution. The step is not necessary, and whether pore formation is carried out or not can be selected according to the requirement, and the arrangement of the step is favorable for improving the porosity in the anode material, so that the wettability of the anode material in electrolyte is favorable for improving the electron and/or ion conduction.
In a part of preferred embodiments, in the step (4), the carbonization temperature is 800 to 1000 ℃; the carbonization time is 1-5 h; the carbonization atmosphere is an inert atmosphere or a nitrogen atmosphere. When a KOH solution treatment step is arranged between the step (3) and the step (4), the step can realize carbonization and pore-forming.
In some preferred embodiments, when a KOH solution treatment step is provided between step (3) and step (4), step (4) further comprises the step of washing and drying the carbonized material.
In a partially preferred embodiment, the mass ratio of the pre-carbonized material to KOH in KOH solution is 1:1 to 1:4, a step of; there is no special requirement on the concentration of KOH solution, and the solution can dissolve KOH.
In some embodiments, the drying is freeze-drying or oven-drying, provided that drying is achieved.
In a partially preferred embodiment, treating the resulting pre-carbonized material with a KOH solution comprises: dispersing the obtained pre-carbonized material in KOH solution for ultrasonic treatment.
In a partially preferred embodiment, step (1) comprises: adding a proper amount of starch into a solvent, uniformly stirring, and then carrying out heat preservation and stirring at 60-95 ℃ to gelatinize to form pasty liquid. In some embodiments, the solvent may be water or other solvent capable of achieving gelatinization of starch. The gelatinization temperature may be reasonably adjusted according to the nature of the starch selected and may not be limited to 60-95 ℃.
In a part of preferred embodiments, in the step (2), the biomass fiber and/or the rayon are washed and dried biomass fiber and/or rayon.
The invention also provides a sodium ion battery, which comprises the carbon anode material or the carbon anode material prepared by the preparation method.
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a preparation method of a negative electrode material of a porous biomass carbon nanofiber in-situ grown carbon nanosphere comprises the following steps:
step (1): taking 2.5g of commercial absorbent cotton, ultrasonically cleaning the commercial absorbent cotton with a mixed solution of alcohol and ultrapure water for 30min, and then drying the commercial absorbent cotton for later use;
step (2): adding 4g of starch into a beaker containing a certain amount of deionized water, stirring for 20min, placing the beaker into an oil bath pot at 90 ℃, and stirring for 30min to gelatinize the starch to form a pasty solution;
and (3) growing carbon spheres in situ: adding the pretreated absorbent cotton into the pasty solution, transferring to a reaction kettle for hydrothermal reaction at 190 ℃ for 12 hours, growing carbon sphere precursors on the surfaces of fibers in situ, and cooling to room temperature;
step (4): the solution with absorbent cotton is obtained, and is dried for 12 hours in a drying oven at 60 ℃ after being subjected to suction filtration and washing for 5 times and centrifugal washing for 10 times by using deionized water and ethanol;
step (5) pre-carbonization: placing the obtained substance in a tube furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 5 hours to obtain a pre-carbonized material;
step (6): dispersing the obtained pre-carbonized material in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:3, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
step (7) pore-forming treatment and carbonization: the freeze-dried product is kept at 800 ℃ for 2 hours in a tubular furnace under the argon atmosphere and then cooled to room temperature, and the product is filtered and washed for a plurality of times until the pH value is 7, and is dried at 60 ℃ to obtain the porous material C2.
The SEM image of the obtained porous material C2 is shown in fig. 1, and it can be seen from fig. 1 that the carbon nanoballs were grown on the carbon nanotubes in situ.
Example 2:
a preparation method of a negative electrode material of a porous biomass carbon nanofiber in-situ grown carbon nanosphere comprises the following steps:
step (1): taking 2.5g of commercial absorbent cotton, ultrasonically cleaning the commercial absorbent cotton with a mixed solution of alcohol and ultrapure water for 30min, and then drying the commercial absorbent cotton for later use;
step (2): adding 4g of starch into a beaker containing a certain amount of deionized water, stirring for 20min, placing the beaker into an oil bath pot at 90 ℃, and stirring for 30min to form a pasty solution;
and (3) growing carbon spheres in situ: adding the pretreated absorbent cotton into the pasty solution, transferring to a reaction kettle for hydrothermal reaction at 200 ℃ for 12 hours, and cooling to room temperature;
step (4): the solution with absorbent cotton is obtained, and is dried for 12 hours in a drying oven at 60 ℃ after being subjected to suction filtration and washing for 5 times and centrifugal washing for 10 times by using deionized water and ethanol;
step (5) pre-carbonization and re-balling: placing the obtained substance in a tube furnace, heating to 400 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 5 hours to obtain a pre-carbonized material;
step (6): dispersing the obtained pre-carbonized material in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:2, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
step (7): pore-forming treatment: the freeze-dried product is kept at 800 ℃ for 2 hours in a tubular furnace under the argon atmosphere and then cooled to room temperature, and the product is filtered and washed for a plurality of times until the pH value is 7, and is dried at 60 ℃ to obtain the porous material C2.
Example 3:
a preparation method of a negative electrode material of a porous biomass carbon nanofiber in-situ grown carbon nanosphere comprises the following steps:
step (1): taking 2.5g of commercial absorbent cotton, ultrasonically cleaning the commercial absorbent cotton with a mixed solution of alcohol and ultrapure water for 30min, and then drying the commercial absorbent cotton for later use;
step (2): adding 4g of starch into a beaker containing a certain amount of deionized water, stirring for 20min, placing the beaker into an oil bath pot at 90 ℃, and stirring for 30min to form a pasty solution;
and (3) growing carbon spheres in situ: adding the pretreated absorbent cotton into the pasty solution, transferring to a reaction kettle for hydrothermal reaction at 200 ℃ for 12 hours, and cooling to room temperature;
step (4): the solution with absorbent cotton is obtained, and is dried for 12 hours in a drying oven at 60 ℃ after being subjected to suction filtration and washing for 5 times and centrifugal washing for 10 times by using deionized water and ethanol;
step (5) pre-carbonization and re-balling: placing the obtained substance in a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 5 hours to obtain a pre-carbonized material;
step (6): dispersing the obtained pre-carbonized material in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:2, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
step (7): pore-forming treatment: the freeze-dried product is kept at 800 ℃ for 2 hours in a tubular furnace under the argon atmosphere and then cooled to room temperature, and the product is filtered and washed for a plurality of times until the pH value is 7, and is dried at 60 ℃ to obtain the porous material C2.
Example 4:
a preparation method of porous biomass carbon nanofiber in-situ grown carbon nanospheres, comprising the following steps:
step (1): taking 2.5g of commercial absorbent cotton, ultrasonically cleaning the commercial absorbent cotton with a mixed solution of alcohol and ultrapure water for 30min, and then drying the commercial absorbent cotton for later use;
step (2): adding 4g of starch into a beaker containing a certain amount of deionized water, stirring for 20min, placing the beaker into an oil bath pot at 90 ℃, and stirring for 30min to gelatinize the starch to form a pasty solution;
and (3) growing carbon spheres in situ: adding the pretreated absorbent cotton into the pasty solution, transferring to a reaction kettle for hydrothermal reaction at 170 ℃ for 15 hours, growing carbon sphere precursors on the surfaces of fibers in situ, and cooling to room temperature;
step (4): the solution with absorbent cotton is obtained, and is dried for 12 hours in a drying oven at 60 ℃ after being subjected to suction filtration and washing for 5 times and centrifugal washing for 10 times by using deionized water and ethanol;
step (5) pre-carbonization: placing the obtained substance in a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 4 hours to obtain a pre-carbonized material;
step (6): dispersing the obtained pre-carbonized material in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:3, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
step (7) pore-forming treatment and carbonization: the freeze-dried product is kept at 900 ℃ for 2 hours in a tubular furnace under the argon atmosphere and then cooled to room temperature, and the product is filtered and washed for a plurality of times until the pH value is 7, and is dried at 60 ℃ to obtain the porous material C2.
Example 5:
a preparation method of porous biomass carbon nanofiber in-situ grown carbon nanospheres, comprising the following steps:
step (1): taking 2.5g of commercial absorbent cotton, ultrasonically cleaning the commercial absorbent cotton with a mixed solution of alcohol and ultrapure water for 30min, and then drying the commercial absorbent cotton for later use;
step (2): adding 4g of starch into a beaker containing a certain amount of deionized water, stirring for 20min, placing the beaker into an oil bath pot at 90 ℃, and stirring for 30min to gelatinize the starch to form a pasty solution;
and (3) growing carbon spheres in situ: adding the pretreated absorbent cotton into the pasty solution, transferring to a reaction kettle for hydrothermal reaction at 220 ℃ for 6 hours, growing carbon sphere precursors on the surfaces of fibers in situ, and cooling to room temperature;
step (4): the solution with absorbent cotton is obtained, and is dried for 12 hours in a drying oven at 60 ℃ after being subjected to suction filtration and washing for 5 times and centrifugal washing for 10 times by using deionized water and ethanol;
step (5) pre-carbonization: placing the obtained substance in a tube furnace, heating to 400 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 6 hours to obtain a pre-carbonized material;
step (6): dispersing the obtained pre-carbonized material in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:4, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
step (7) pore-forming treatment and carbonization: the freeze-dried product is kept at 1000 ℃ for 1 hour in a tubular furnace under the argon atmosphere and then cooled to room temperature, and the product is subjected to suction filtration and water washing for several times until the pH value is 7, and is dried at 60 ℃ to obtain the porous material C2.
Comparative example 1:
preparation of porous carbon nanospheres:
adding 4g of starch into a beaker containing a certain amount of deionized water, stirring for 20min, placing the beaker into an oil bath pot at 90 ℃, and stirring for 30min to form a pasty solution;
drying the obtained pasty solution, placing the pasty solution into a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 5 hours to perform pre-carbonization;
dispersing the pre-carbonized substance in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:2, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
and (3) preserving the heat of the freeze-dried product in a tube furnace at 800 ℃ for 2 hours under the argon atmosphere, cooling to room temperature, carrying out suction filtration and water washing on the product for several times until the pH value is 7, and drying at 60 ℃ to obtain the porous carbon nanospheres.
Preparation of carbon nanotubes:
taking 2.5g of commercial absorbent cotton, ultrasonically cleaning with a mixed solution of alcohol and ultrapure water for 30min, drying, placing in a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under argon atmosphere, and preserving heat for 5h;
dispersing the obtained product in KOH aqueous solution, wherein the mass ratio of the product to KOH is 1:1, after ultrasonic treatment for a period of time, placing the mixture in a freeze dryer for drying;
and (3) preserving the temperature of the freeze-dried product in a tube furnace at 800 ℃ for 2 hours in an argon atmosphere, cooling to room temperature, carrying out suction filtration and water washing on the product for several times until the pH value is 7, and drying at 60 ℃ to obtain the porous carbon nanotube.
Preparation of a composite carbon negative electrode material:
and adding the prepared porous carbon nanospheres and carbon nanotubes into water, stirring and uniformly mixing, and drying to obtain the composite carbon anode material.
The negative electrode materials obtained in examples 1-3 and comparative example 1 were mixed with acetylene black as a conductive agent and polyvinylidene fluoride (PVDF) as a binder in a mass ratio of 8:1:1, and N-methylpyrrolidone (NMP) as a solvent, and the mixture was stirred in a small beaker at a rotational speed of 800r/min for 2 hours to obtain a slurry. Coating the slurry on a current collector copper foil by using an automatic coating machine, horizontally placing the current collector copper foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 8 hours, preparing a pole piece with the diameter of 12mm by punching, then drying the pole piece at 90 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and punching the pole piece into a wafer electrode with the diameter of 12mm, thereby being used as a negative pole piece.
NaNi is processed by 1/3 Fe 1/3 Mn 1/3 O 2 (Parawa New energy Co., ltd.) as the active material of the positive electrode material. Mixing the material with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, mixing the mixture with N-methyl pyrrolidone (NMP) as a solvent, and preparing slurry by adopting the same method, wherein the difference is that the positive electrode material is coated on an aluminum foil to obtain a positive electrode plate. Finally, the obtained positive electrode plate and the obtained negative electrode plate are assembled into a CR2032 button battery in a glove box, wherein two electrodes (negative electrode/positive electrode) The weight ratio of the electrolyte solution to the NaPF is 1:8.8, and the electrolyte solution is 1M NaPF 6 EC: DEC (volume 4:6), the membrane was a glass fiber membrane with a diameter of 16 mm. The charge and discharge test was performed on blue-electric Land BT2000 battery test system of Wuhan, china at room temperature of 25 ℃ in a range of 1.6 to 3.0V.
The cycle performance of the button cell assembled by the anode materials obtained in examples 1-3 and comparative example 1 is shown in fig. 2, and it can be seen from fig. 2 that, compared with the anode material obtained by physical compounding in comparative example 1, the cycle performance of the anode material prepared in examples 1-3 is significantly improved, and the analysis may be caused by that the simple mechanical mixing forms a composite structure which is not stable enough, and the sodium is easily embedded and extracted during charging and discharging, which easily results in breakage or collapse of the structure.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The carbon negative electrode material is characterized by comprising carbon nanotubes and carbon nanospheres, wherein the carbon nanospheres are grown on the carbon nanotubes in situ.
2. The carbon negative electrode material according to claim 1, wherein the carbon negative electrode material is obtained by carbonization after in-situ growth of a carbon sphere precursor on the surface of a biomass fiber and/or a rayon fiber.
3. A method for preparing a carbon anode material, comprising:
(1) Preparing starch into starch paste;
(2) Adding biomass fibers and/or artificial fibers into starch pasty liquid, performing hydrothermal reaction, and performing solid-liquid separation, washing and drying on the obtained product to obtain a mixed material;
(3) Pre-carbonizing the obtained mixed material in a non-oxidizing atmosphere to obtain a pre-carbonized material;
(4) Carbonizing the pre-carbonized material to obtain the anode material of the carbon nanospheres grown in situ by the porous biomass carbon nanotube fiber.
4. The method for producing a carbon negative electrode material according to claim 3, wherein in the step (3), the pre-carbonization temperature is 400 to 600 ℃; the pre-carbonization time is 4-6 hours; the non-oxidizing atmosphere is an inert atmosphere or a nitrogen atmosphere.
5. The method for producing a carbon negative electrode material according to claim 3, wherein in the step (2), the temperature of the hydrothermal reaction is 170 to 220 ℃; the reaction time is 6-15 h.
6. The method for producing a carbon negative electrode material according to claim 3, wherein in the step (4), the carbonization temperature is 800 to 1000 ℃; the carbonization time is 1-5 h; the carbonization atmosphere is an inert atmosphere or a nitrogen atmosphere.
7. The method for producing a carbon negative electrode material according to claim 3, further comprising a step of treating the obtained pre-carbonized material with a KOH solution and drying the treated material between the step (3) and the step (4).
8. The method for producing a carbon negative electrode material according to claim 7, wherein the mass ratio of the pre-carbonized material to KOH is 1:1 to 1:4.
9. the method for producing a carbon negative electrode material according to claim 3, wherein the step (1) comprises: adding a proper amount of starch into a solvent, uniformly stirring, and then carrying out heat preservation and stirring at 60-95 ℃ to form pasty liquid;
in the step (2), the biomass fiber and/or the artificial fiber are cleaned and dried.
10. A sodium ion battery comprising the carbon negative electrode material according to claim 1 or 2 or the carbon negative electrode material prepared by the preparation method according to any one of claims 3 to 9.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104179003A (en) * | 2014-08-11 | 2014-12-03 | 中北大学 | Preparation method of carbon nanosphere-carbon fiber multi-scale reinforcement |
| CN104828804A (en) * | 2015-03-25 | 2015-08-12 | 清华大学 | A preparing method of a porous carbon nanotube-charcoal spherical composite material |
| CN105869912A (en) * | 2016-04-12 | 2016-08-17 | 湘潭大学 | Preparation method of starch-based uniformly-dispersed activated carbon microsphere material and application thereof |
| CN106676677A (en) * | 2017-02-06 | 2017-05-17 | 信阳师范学院 | Method for preparing hollow carbon fiber from biomass material |
| CN107673348A (en) * | 2017-09-30 | 2018-02-09 | 青岛海澄知识产权事务有限公司 | A kind of biomass-based porous agraphitic carbon nanosphere sodium-ion battery |
| CN109742367A (en) * | 2019-01-09 | 2019-05-10 | 中南林业科技大学 | Wooden Carbon fibe/metal oxide composite cathode material and its preparation method and application |
| CN114634174A (en) * | 2020-12-16 | 2022-06-17 | 东北林业大学 | Method for synthesizing carbon nano tube by using starch or cellulose biomass as carbon source |
| CN114975929A (en) * | 2022-05-26 | 2022-08-30 | 顺德职业技术学院 | Hard carbon negative electrode material for sodium ion battery and preparation method thereof |
| CN115948820A (en) * | 2022-12-15 | 2023-04-11 | 蜂巢能源科技(上饶)有限公司 | Carbon material, preparation method thereof, conductive agent and lithium ion battery |
-
2023
- 2023-10-25 CN CN202311387474.1A patent/CN117117179A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104179003A (en) * | 2014-08-11 | 2014-12-03 | 中北大学 | Preparation method of carbon nanosphere-carbon fiber multi-scale reinforcement |
| CN104828804A (en) * | 2015-03-25 | 2015-08-12 | 清华大学 | A preparing method of a porous carbon nanotube-charcoal spherical composite material |
| CN105869912A (en) * | 2016-04-12 | 2016-08-17 | 湘潭大学 | Preparation method of starch-based uniformly-dispersed activated carbon microsphere material and application thereof |
| CN106676677A (en) * | 2017-02-06 | 2017-05-17 | 信阳师范学院 | Method for preparing hollow carbon fiber from biomass material |
| CN107673348A (en) * | 2017-09-30 | 2018-02-09 | 青岛海澄知识产权事务有限公司 | A kind of biomass-based porous agraphitic carbon nanosphere sodium-ion battery |
| CN109742367A (en) * | 2019-01-09 | 2019-05-10 | 中南林业科技大学 | Wooden Carbon fibe/metal oxide composite cathode material and its preparation method and application |
| CN114634174A (en) * | 2020-12-16 | 2022-06-17 | 东北林业大学 | Method for synthesizing carbon nano tube by using starch or cellulose biomass as carbon source |
| CN114975929A (en) * | 2022-05-26 | 2022-08-30 | 顺德职业技术学院 | Hard carbon negative electrode material for sodium ion battery and preparation method thereof |
| CN115948820A (en) * | 2022-12-15 | 2023-04-11 | 蜂巢能源科技(上饶)有限公司 | Carbon material, preparation method thereof, conductive agent and lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| ZHANG, YC等: "Rice husk-derived hierarchical silicon/nitrogen-doped carbon/carbon nanotube spheres as low-cost and high-capacity anodes for lithium-ion batteries", 《NANO ENERGY》, vol. 25, pages 120 - 127 * |
| 王慧: "钠离子电池蔗糖基硬炭负极材料的制备与电化学性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技I辑》, no. 4, pages 015 - 116 * |
| 王相文: "空心碳球修饰碳纳米管用于锂硫电池的硫载体", 《电源技术》, vol. 47, no. 4, pages 485 - 488 * |
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